United States Office of Research and EPA/600/R-01/089

Environmental Protection Development September 2001

Agency Washington, DC 20460

Innovative Technology
Verification Report

Field Measurement
Technologies for Total
Petroleum Hydrocarbons in Soil

Horiba Instruments Incorporated

OCMA-350 Oil Content Analyzer
 EPA/600/R-01/089
September 2001

Innovative Technology
Verification Report

Horiba Instruments Incorporated

OCMA-350 Oil Content Analyzer

Prepared by

Tetra Tech EM Inc.

200 East Randolph Drive, Suite 4700
Chicago, Illinois 60601

Contract No. 68-C5-0037

Dr. Stephen Billets

Characterization and Monitoring Branch
Environmental Sciences Division
Las Vegas, Nevada 89193-3478

National Exposure Research Laboratory

Office of Research and Development
U.S. Environmental Protection Agency
 Notice

This document was prepared for the U.S. Environmental Protection Agency (EPA) Superfund
Innovative Technology Evaluation Program under Contract No. 68-C5-0037. The document has
been subjected to the EPA’s peer and administrative reviews and has been approved for publication.
Mention of corporation names, trade names, or commercial products does not constitute endorsement
or recommendation for use.

ii
 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460

ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM

VERIFICATION STATEMENT

TECHNOLOGY TYPE: FIELD MEASUREMENT DEVICE

APPLICATION: MEASUREMENT OF TOTAL PETROLEUM HYDROCARBONS
TECHNOLOGY NAME: OCMA-350 OIL CONTENT ANALYZER
COMPANY: HORIBA INSTRUMENTS INCORPORATED
ADDRESS: 17671 ARMSTRONG AVENUE
IRVINE, CA 92614
WEB SITE: http://www.horiba.com
TELEPHONE: (800) 4HORIBA

VERIFICATION PROGRAM DESCRIPTION

The U.S. Environmental Protection Agency (EPA) created the Superfund Innovative Technology Evaluation (SITE) and
Environmental Technology Verification (ETV) Programs to facilitate deployment of innovative technologies through
performance verification and information dissemination. The goal of these programs is to further environmental protection
by substantially accelerating the acceptance and use of improved and cost-effective technologies. These programs assist and
inform those involved in design, distribution, permitting, and purchase of environmental technologies. This document
summarizes results of a demonstration of the OCMA-350 Oil Content Analyzer (OCMA-350) developed by Horiba
Instruments Incorporated (Horiba).

PROGRAM OPERATION

Under the SITE and ETV Programs, with the full participation of the technology developers, the EPA evaluates and
documents the performance of innovative technologies by developing demonstration plans, conducting field tests, collecting
and analyzing demonstration data, and preparing reports. The technologies are evaluated under rigorous quality assurance
(QA) protocols to produce well-documented data of known quality. The EPA National Exposure Research Laboratory, which
demonstrates field sampling, monitoring, and measurement technologies, selected Tetra Tech EM Inc. as the verification
organization to assist in field testing seven field measurement devices for total petroleum hydrocarbons (TPH) in soil. This
demonstration was funded by the SITE Program.

DEMONSTRATION DESCRIPTION

In June 2000, the EPA conducted a field demonstration of the OCMA-350 and six other field measurement devices for TPH
in soil. This verification statement focuses on the OCMA-350; a similar statement has been prepared for each of the other
six devices. The performance and cost of the OCMA-350 were compared to those of an off-site laboratory reference method,
“Test Methods for Evaluating Solid Waste” (SW-846) Method 8015B (modified). To verify a wide range of performance
attributes, the demonstration had both primary and secondary objectives. The primary objectives included (1) determining
the method detection limit, (2) evaluating the accuracy and precision of TPH measurement, (3) evaluating the effect of
interferents, and (4) evaluating the effect of moisture content on TPH measurement for each device. Additional primary
objectives were to measure sample throughput and estimate TPH measurement costs. Secondary objectives included
(1) documenting the skills and training required to properly operate the device, (2) documenting the portability of the device,
(3) evaluating the device’s durability, and (4) documenting the availability of the device and associated spare parts.

The OCMA-350 was demonstrated by using it to analyze 74 soil environmental samples, 89 soil performance evaluation (PE)
samples, and 36 liquid PE samples. In addition to these 199 samples, 9 extract duplicates prepared using the environmental
samples were analyzed. The environmental samples were collected in five areas contaminated with gasoline, diesel,
lubricating oil, or other petroleum products, and the PE samples were obtained from a commercial provider.

The accompanying notice is an integral part of this verification statement. September 2001
iii
Collectively, the environmental and PE samples provided the different matrix types and the different levels and types of
petroleum hydrocarbon contamination needed to perform a comprehensive evaluation of the OCMA-350. A complete
description of the demonstration and a summary of its results are available in the “Innovative Technology Verification Report:
Field Measurement Devices for Total Petroleum Hydrocarbons in Soil—Horiba Instruments Incorporated OCMA-350 Oil
Content Analyzer” (EPA/600/R-01/089).

TECHNOLOGY DESCRIPTION

The OCMA-350 developed by Horiba is based on infrared analysis. The OCMA-350 includes a single-beam, fixed-
wavelength, nondispersive infrared filter-based spectrophotometer. Infrared radiation from a tungsten lamp is transmitted
through a cylindrical, quartz cuvette containing a sample extract. The radiation that has passed through the extract enters
a detector containing a filter that isolates analytical wavelengths in the 3,400- to 3,500-nanometer range.

During the demonstration, Horiba dried soil by adding anhydrous sodium sulfate. Extraction of petroleum hydrocarbons in
a given soil sample was typically performed by adding 20 milliliters of Horiba’s proprietary S-316 extraction solvent to
5 grams of the sample. The mixture was agitated using an ultrasonic mixer. The sample extract was decanted into a beaker
through a filter-lined funnel, and then the filtrate was poured into a quartz cuvette. The cuvette was placed in the
spectrophotometer, and the TPH concentration in milligrams per kilogram was read on the digital display. Periodically,
Horiba recycled the extraction solvent using its Model SR-300 solvent reclaimer.

VERIFICATION OF PERFORMANCE

To ensure data usability, data quality indicators for accuracy, precision, representativeness, completeness, and comparability
were assessed for the reference method based on project-specific QA objectives. Although the reference method results
generally exhibited a negative bias, based on the results for the data quality indicators, the reference method results were
considered to be of adequate quality. The bias was considered to be significant primarily for low- and medium-
concentration-range soil samples containing diesel, which made up only 13 percent of the total number of samples analyzed
during the demonstration. The reference method recoveries observed during the demonstration were typical of the recoveries
obtained by most organic analytical methods for environmental samples. In general, the user should exercise caution when
evaluating the accuracy of a field measurement device by comparing it to reference methods because the reference methods
themselves may have limitations. Key demonstration findings are summarized below for the primary objectives.

Method Detection Limit: Based on the TPH results for seven low-concentration-range diesel soil PE samples, the method
detection limits were determined to be 15.2 and 4.79 milligrams per kilogram for the OCMA-350 and reference method,
respectively.

Accuracy and Precision: Seventy-eight of 107 OCMA-350 results (73 percent) used to draw conclusions regarding whether
the TPH concentration in a given sampling area or sample type exceeded a specified action level agreed with those of the
reference method; 6 OCMA-350 conclusions were false positives, and 23 were false negatives.

Of 102 OCMA-350 results used to assess measurement bias, 36 were within 30 percent, 16 were within 30 to 50 percent, and
50 were not within 50 percent of the reference method results; 64 OCMA-350 results were biased low, and 38 were biased
high.

For soil environmental samples, the OCMA-350 results were statistically (1) the same as the reference method results for four
of the five sampling areas and (2) different from the reference method results for one sampling area. For soil PE samples,
the OCMA-350 results were statistically (1) the same as the reference method results for blank samples and (2) different from
the reference method results for medium- and high-concentration-range weathered gasoline samples and low-, medium-, and
high-concentration-range diesel samples. For liquid PE samples, the OCMA-350 results were statistically (1) the same as
the reference method results for weathered gasoline samples and (2) different from the reference method results for diesel
samples.

The OCMA-350 results correlated highly with the reference method results for three of the five sampling areas (the square
of the correlation coefficient [R2] values were greater than or equal to 0.90, and F-test probability values were less than
5 percent). The OCMA-350 results correlated moderately with the reference method results for diesel soil PE samples (the
R2 value was 0.68, and the F-test probability value was less than 5 percent). The OCMA-350 results correlated weakly with
the reference method results for two sampling areas and for weathered gasoline soil PE samples (R2 values ranged from 0.19
to 0.53, and F-test probability values ranged from 22.58 to 62.68 percent).

Comparison of the OCMA-350 and reference method median relative standard deviations (RSD) showed that the OCMA-350
and the reference method exhibited similar overall precision. Specifically, the median RSD ranges were 1.5 to 20 percent
and 5.5 to 18 percent for the OCMA-350 and reference method, respectively. The analytical precision for the OCMA-350
(a median relative percent difference of 1) was better than that for the reference method (a median relative percent difference
of 4).

The accompanying notice is an integral part of this verification statement. September 2001
iv
Effect of Interferents: The OCMA-350 showed no response to neat tetrachloroethene (PCE); neat 1,2,4-trichlorobenzene;
or soil spiked with humic acid. The device’s mean responses for neat methyl-tert-butyl ether (MTBE), Stoddard solvent,
and turpentine were 72.5, 86, and 85 percent, respectively. The reference method showed varying mean responses for MTBE
(39 percent); PCE (17.5 percent); Stoddard solvent (85 percent); turpentine (52 percent); 1,2,4-trichlorobenzene (50 percent);
and humic acid (0 percent). For the demonstration, MTBE and Stoddard solvent were included in the definition of TPH.

Effect of Moisture Content: The OCMA-350 showed a three-fold increase in TPH results when the soil moisture content
was increased from 9 to 16 percent for weathered gasoline soil PE samples. However, the device showed a three-fold
decrease in TPH results when the soil moisture content was increased from less than 1 percent to 9 percent for diesel soil PE
samples. The reference method TPH results were unaffected when the soil moisture content was increased.

Measurement Time: From the time of sample receipt, Horiba required 46 hours, 15 minutes, to prepare a draft data package
containing TPH results for 199 samples and 9 extract duplicates compared to 30 days for the reference method, which was
used to analyze 4 additional extract duplicates.

Measurement Costs: The TPH measurement cost for 199 samples and 9 extract duplicates was estimated to be $15,750,
including the capital equipment purchase cost of $6,500, for the OCMA-350 compared to $42,050 for the reference method.

Key demonstration findings are summarized below for the secondary objectives.

Skill and Training Requirements: The OCMA-350 can be operated by one person with basic wet chemistry skills. The
sample analysis procedure for the device can be learned in the field with a few practice attempts. During the demonstration,
some of the items in the OCMA-350, including the narrow-mouth vials used for weighing and extracting soil samples and
the gravity filtration setup, made the TPH measurement procedure less simple and more time-consuming.

Portability: The OCMA-350 can be easily moved between sampling areas in the field, if necessary. It can be operated using
a 110-volt alternating current power source or a direct current power source such as a 12-volt power outlet in an automobile.

Durability and Availability of the Device: During a 1-year warranty period, Horiba will repair any malfunctioning items of
the device at no cost. During the demonstration, none of the device’s reusable items malfunctioned or was damaged. Horiba
does not supply some items necessary for TPH measurement using the device, including a test tube rack, a funnel rack and
stand, a digital balance, and miscellaneous glassware and laboratory supplies; the availability of replacement or spare parts
not supplied by Horiba depends on their manufacturer or distributor.

In summary, during the demonstration, the OCMA-350 exhibited the following desirable characteristics of a field TPH
measurement device: (1) good precision, (2) sensitivity to interferents that are petroleum hydrocarbons, and (3) high sample
throughput. In addition, the OCMA-350 exhibited moderate measurement costs. In general, however, the OCMA-350 TPH
results for the PE samples did not compare well with the reference method results. The device results were significantly
impacted by soil moisture content and by turpentine, an interferent that is not a petroleum hydrocarbon. Collectively, the
demonstration findings indicated that the OCMA-350 may be considered for TPH screening purposes; however, the user
should exercise caution when considering the device for a field TPH measurement application requiring definitive results.

Original
signed by

Gary J. Foley, Ph.D.

Director
National Exposure Research Laboratory
Office of Research and Development

NOTICE: EPA verifications are based on an evaluation of technology performance under specific, predetermined criteria and
appropriate quality assurance procedures. The EPA makes no expressed or implied warranties as to the performance of the technology
and does not certify that a technology will always operate as verified. The end user is solely responsible for complying with any and
all applicable federal, state, and local requirements.

The accompanying notice is an integral part of this verification statement. September 2001
v
 Foreword

The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation’s natural resources. Under the mandate of national environmental laws, the agency strives to
formulate and implement actions leading to a compatible balance between human activities and the
ability of natural systems to support and nurture life. To meet this mandate, the EPA’s Office of
Research and Development provides data and scientific support that can be used to solve
environmental problems, build the scientific knowledge base needed to manage ecological resources
wisely, understand how pollutants affect public health, and prevent or reduce environmental risks.

The National Exposure Research Laboratory (NERL) is the agency’s center for investigation of
technical and management approaches for identifying and quantifying risks to human health and the
environment. Goals of the laboratory’s research program are to (1) develop and evaluate methods
and technologies for characterizing and monitoring air, soil, and water; (2) support regulatory and
policy decisions; and (3) provide the scientific support needed to ensure effective implementation
of environmental regulations and strategies.

The EPA’s Superfund Innovative Technology Evaluation (SITE) Program evaluates technologies
designed for characterization and remediation of contaminated Superfund and Resource Conservation
and Recovery Act sites. The SITE Program was created to provide reliable cost and performance
data in order to speed acceptance and use of innovative remediation, characterization, and monitoring
technologies by the regulatory and user community.

Effective measurement and monitoring technologies are needed to assess the degree of
contamination at a site, provide data that can be used to determine the risk to public health or the
environment, supply the necessary cost and performance data to select the most appropriate
technology, and monitor the success or failure of a remediation process. One component of the EPA
SITE Program, the Monitoring and Measurement Technology (MMT) Program, demonstrates and
evaluates innovative technologies to meet these needs.

Candidate technologies can originate within the federal government or the private sector. Through
the SITE Program, developers are given the opportunity to conduct a rigorous demonstration of their
technologies under actual field conditions. By completing the demonstration and distributing the
results, the agency establishes a baseline for acceptance and use of these technologies. The MMT
Program is administered by the Environmental Sciences Division of NERL in Las Vegas, Nevada.

Gary J. Foley, Ph.D.

Director
National Exposure Research Laboratory
Office of Research and Development

vi
 Abstract

The OCMA-350 Oil Content Analyzer (OCMA-350) developed by Horiba Instruments Incorporated
(Horiba), was demonstrated under the U.S. Environmental Protection Agency Superfund Innovative
Technology Evaluation Program in June 2000 at the Navy Base Ventura County site in Port
Hueneme, California. The purpose of the demonstration was to collect reliable performance and cost
data for the OCMA-350 and six other field measurement devices for total petroleum hydrocarbons
(TPH) in soil. In addition to assessing ease of device operation, the key objectives of the
demonstration included determining the (1) method detection limit, (2) accuracy and precision, (3)
effects of interferents and soil moisture content on TPH measurement, (4) sample throughput, and
(5) TPH measurement costs for each device. The demonstration involved analysis of both
performance evaluation samples and environmental samples collected in five areas contaminated
with gasoline, diesel, lubricating oil, or other petroleum products. The performance and cost results
for a given field measurement device were compared to those for an off-site laboratory reference
method, “Test Methods for Evaluating Solid Waste” (SW-846) Method 8015B (modified). During
the demonstration, Horiba required 46 hours, 15 minutes, for TPH measurement of 199 samples and
9 extract duplicates. The TPH measurement costs for these samples were estimated to be $15,750
for the OCMA-350 compared to $42,050 for the reference method. The method detection limits
were determined to be 15.2 and 4.79 milligrams per kilogram for the OCMA-350 and reference
method, respectively. During the demonstration, the OCMA-350 exhibited good precision and
sensitivity to interferents that are petroleum hydrocarbons (methyl-tert-butyl ether and Stoddard
solvent). However, the OCMA-350 TPH results (1) did not compare well with the reference method
results for the performance evaluation samples and (2) were significantly impacted by soil moisture
content and by turpentine, an interferent that is not a petroleum hydrocarbon. In addition, some of
the items in the OCMA-350 made the TPH measurement procedure less simple and more time-
consuming during the demonstration. Collectively, the demonstration findings indicated that the
OCMA-350 may be considered for TPH screening purposes; however, the user should exercise
caution when considering the device for a field TPH measurement application requiring definitive
results.

vii
 Contents

Chapter Page

Notice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii

Verification Statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xii

Abbreviations, Acronyms, and Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvi

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Description of SITE Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Scope of Demonstration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Components and Definition of TPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1 Composition of Petroleum and Its Products . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1.1 Gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1.2 Naphthas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1.3 Kerosene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1.4 Jet Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1.5 Fuel Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1.6 Diesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1.7 Lubricating Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 Measurement of TPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2.1 Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2.2 Current Options for TPH Measurement in Soil . . . . . . . . . . . . . 8
1.3.2.3 Definition of TPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2 Description of Infrared Analysis and the OCMA-350 . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2.1 Description of Infrared Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Description of OCMA-350 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 Device Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.2 Operating Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

viii
 Contents (Continued)

Chapter Page

2.3 Developer Contact Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

3 Demonstration Site Descriptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

3.1 Navy Base Ventura County Site . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1.1 Fuel Farm Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1.2 Naval Exchange Service Station Area . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.1.3 Phytoremediation Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2 Kelly Air Force Base Site . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3 Petroleum Company Site . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4 Demonstration Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.1 Demonstration Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2 Demonstration Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.1 Approach for Addressing Primary Objectives . . . . . . . . . . . . . . . . . . . 22
4.2.2 Approach for Addressing Secondary Objectives . . . . . . . . . . . . . . . . . 26
4.3 Sample Preparation and Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.3.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.3.2 Sample Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

5 Confirmatory Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.1 Reference Method Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.2 Reference Laboratory Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5.3 Summary of Reference Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

6 Assessment of Reference Method Data Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

6.1 Quality Control Check Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.1.1 GRO Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.1.2 EDRO Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
6.2 Selected Performance Evaluation Sample Results . . . . . . . . . . . . . . . . . . . . . . . 56
6.3 Data Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

7 Performance of the OCMA-350 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

7.1 Primary Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
7.1.1 Primary Objective P1: Method Detection Limit . . . . . . . . . . . . . . . . . . 62
7.1.2 Primary Objective P2: Accuracy and Precision . . . . . . . . . . . . . . . . . . 62
7.1.2.1 Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
7.1.2.2 Precision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.1.3 Primary Objective P3: Effect of Interferents . . . . . . . . . . . . . . . . . . . . 77
7.1.3.1 Interferent Sample Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.1.3.2 Effects of Interferents on TPH Results for Soil Samples . . . . . 77
7.1.4 Primary Objective P4: Effect of Soil Moisture Content . . . . . . . . . . . . 85
7.1.5 Primary Objective P5: Time Required for TPH Measurement . . . . . . . 87
7.2 Secondary Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7.2.1 Skill and Training Requirements for Proper Device Operation . . . . . . 89
7.2.2 Health and Safety Concerns Associated with Device Operation . . . . . 90

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 Contents (Continued)

Chapter Page

7.2.3 Portability of the Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

7.2.4 Durability of the Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.2.5 Availability of the Device and Spare Parts . . . . . . . . . . . . . . . . . . . . . . 91

8 Economic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.1 Issues and Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.1.1 Capital Equipment Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.1.2 Cost of Supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.1.3 Support Equipment Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
8.1.4 Labor Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
8.1.5 Investigation-Derived Waste Disposal Cost . . . . . . . . . . . . . . . . . . . . . 93
8.1.6 Costs Not Included . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
8.2 OCMA-350 Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.2.1 Capital Equipment Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.2.2 Cost of Supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.2.3 Support Equipment Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.2.4 Labor Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.2.5 Investigation-Derived Waste Disposal Cost . . . . . . . . . . . . . . . . . . . . . 96
8.2.6 Summary of OCMA-350 Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.3 Reference Method Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.4 Comparison of Economic Analysis Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

9 Summary of Demonstration Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

Appendix Supplemental Information Provided by the Developer . . . . . . . . . . . . . . . . . . 105

x
 Figures

Figure Page

1-1. Distribution of various petroleum hydrocarbon types throughout boiling point

range of crude oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5-1. Reference method selection process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7-1. Summary of statistical analysis of TPH results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
7-2. Measurement bias for environmental samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
7-3. Measurement bias for soil performance evaluation samples . . . . . . . . . . . . . . . . . . . . . . 66
7-4. Linear regression plots for environmental samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7-5. Linear regression plots for soil performance evaluation samples . . . . . . . . . . . . . . . . . . 72

xi
 Tables
Table Page

1-1. Summary of Calibration Information for Infrared Analytical Method . . . . . . . . . . . . . . . 8

1-2. Current Technologies for TPH Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2-1. Infrared Absorbance Values of CH, CH2, and CH3 Groups . . . . . . . . . . . . . . . . . . . . . . 12
2-2. OCMA-350 Components and Supplies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3-1. Summary of Site Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4-1. Action Levels Used to Evaluate Analytical Accuracy . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4-2. Demonstration Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4-3. Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4-4. Performance Evaluation Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4-5. Sample Container, Preservation, and Holding Time Requirements . . . . . . . . . . . . . . . . 35
5-1. Laboratory Sample Preparation and Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . 38
5-2. Summary of Project-Specific Procedures for GRO Analysis . . . . . . . . . . . . . . . . . . . . . 40
5-3. Summary of Project-Specific Procedures for EDRO Analysis . . . . . . . . . . . . . . . . . . . . 44
6-1. Summary of Quality Control Check Results for GRO Analysis . . . . . . . . . . . . . . . . . . . 51
6-2. Summary of Quality Control Check Results for EDRO Analysis . . . . . . . . . . . . . . . . . 55
6-3. Comparison of Soil and Liquid Performance Evaluation Sample Results . . . . . . . . . . . 57
6-4. Comparison of Environmental Resource Associates Historical Results to
Reference Method Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
7-1. TPH Results for Low-Concentration-Range Diesel Soil Performance Evaluation
Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
7-2. Action Level Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
7-3. Statistical Comparison of OCMA-350 and Reference Method TPH Results for
Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
7-4. Statistical Comparison of OCMA-350 and Reference Method TPH Results for
Performance Evaluation Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7-5. Summary of Linear Regression Analysis Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
7-6. Summary of OCMA-350 and Reference Method Precision for Field Triplicates
of Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

xii
 Tables (Continued)

Table Page

7-7. Summary of OCMA-350 and Reference Method Precision for Extract Duplicates . . . . 75
7-8. Comparison of OCMA-350 and Reference Method Precision for Replicate
Performance Evaluation Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7-9. Comparison of OCMA-350 and Reference Method Results for Interferent
Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7-10. Comparison of OCMA-350 and Reference Method Results for Soil Performance
Evaluation Samples Containing Interferents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7-11. Comparison of Results for Soil Performance Evaluation Samples at Different
Moisture Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7-12. Time Required to Complete TPH Measurement Activities Using the OCMA-350 . . . . 88
8-1. OCMA-350 Cost Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
8-2. Reference Method Cost Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
9-1. Summary of OCMA-350 Results for the Primary Objectives . . . . . . . . . . . . . . . . . . . . 99
9-2. Summary of OCMA-350 Results for the Secondary Objectives . . . . . . . . . . . . . . . . . 102

xiii
 Abbreviations, Acronyms, and Symbols

> Greater than

# Less than or equal to
± Plus or minus
µg Microgram
µL Microliter
µm Micrometer
AC Alternating current
AEHS Association for Environmental Health and Sciences
AFB Air Force Base
API American Petroleum Institute
ASTM American Society for Testing and Materials
bgs Below ground surface
BTEX Benzene, toluene, ethylbenzene, and xylene
BVC Base Ventura County
CCV Continuing calibration verification
CFC Chlorofluorocarbon
CFR Code of Federal Regulations
cm Centimeter
DC Direct current
DER Data evaluation report
DRO Diesel range organics
EDRO Extended diesel range organics
EPA U.S. Environmental Protection Agency
EPH Extractable petroleum hydrocarbon
ERA Environmental Resource Associates
FFA Fuel Farm Area
FID Flame ionization detector
GC Gas chromatograph
GRO Gasoline range organics
Horiba Horiba Instruments Incorporated
HPLC High-performance liquid chromatography
ICV Initial calibration verification
IDW Investigation-derived waste
ITVR Innovative technology verification report
kg Kilogram
L Liter
LCS Laboratory control sample
LCSD Laboratory control sample duplicate
MCAWW “Methods for Chemical Analysis of Water and Wastes”
MDL Method detection limit

xiv
 Abbreviations, Acronyms, and Symbols (Continued)
Means R.S. Means Company
mg Milligram
min Minute
mL Milliliter
mm Millimeter
MMT Monitoring and Measurement Technology
MS Matrix spike
MSD Matrix spike duplicate
MTBE Methyl-tert-butyl ether
n-Cx Alkane with “x” carbon atoms
NDIR Nondispersive infrared
NERL National Exposure Research Laboratory
NEX Naval Exchange
ng Nanogram
nm Nanometer
OCMA-350 OCMA-350 Oil Content Analyzer
ORD Office of Research and Development
ORO Oil range organics
OSWER Office of Solid Waste and Emergency Response
PC Petroleum company
PCB Polychlorinated biphenyl
PCE Tetrachloroethene
PE Performance evaluation
PHC Petroleum hydrocarbon
PPE Personal protective equipment
PRA Phytoremediation Area
PRO Petroleum range organics
QA Quality assurance
QC Quality control
R2 Square of the correlation coefficient
RPD Relative percent difference
RSD Relative standard deviation
SFT Slop Fill Tank
SITE Superfund Innovative Technology Evaluation
STL Tampa East Severn Trent Laboratories in Tampa, Florida
SW-846 “Test Methods for Evaluating Solid Waste”
TPH Total petroleum hydrocarbons
UST Underground storage tank
VOA Volatile organic analysis
VPH Volatile petroleum hydrocarbon

xv
 Acknowledgments

This report was prepared for the U.S. Environmental Protection Agency (EPA) Superfund Innovative
Technology Evaluation Program under the direction and coordination of Dr. Stephen Billets of the
EPA National Exposure Research Laboratory (NERL)—Environmental Sciences Division in Las
Vegas, Nevada. The EPA NERL thanks Mr. Ernest Lory of Navy Base Ventura County, Ms. Amy
Whitley of Kelly Air Force Base, and Mr. Jay Simonds of Handex of Indiana for their support in
conducting field activities for the project. Mr. Eric Koglin of the EPA NERL served as the technical
reviewer of this report. Mr. Roger Claff of the American Petroleum Institute, Mr. Dominick
De Angelis of ExxonMobil Corporation, Dr. Ileana Rhodes of Equilon Enterprises, and Dr. Al
Verstuyft of Chevron Research and Technology Company served as the peer reviewers of this report.

This report was prepared for the EPA by Dr. Kirankumar Topudurti and Ms. Suzette Tay of Tetra
Tech EM Inc. Special acknowledgment is given to Mr. Jerry Parr of Catalyst Information Resources,
L.L.C., for serving as the technical consultant for the project. Additional acknowledgment and
thanks are given to Ms. Jeanne Kowalski, Mr. Jon Mann, Mr. Stanley Labunski, and Mr. Joe
Abboreno of Tetra Tech EM Inc. for their assistance during the preparation of this report.

xvi
 Chapter 1
Introduction

The U.S. Environmental Protection Agency (EPA) Office and reference method (Chapter 8); the demonstration
of Research and Development (ORD) National Exposure results in summary form (Chapter 9); and the references
Research Laboratory (NERL) conducted a demonstration used to prepare the ITVR (Chapter 10). Supplemental
of seven innovative field measurement devices for total information provided by Horiba is presented in the
petroleum hydrocarbons (TPH) in soil. The demonstration appendix.
was conducted as part of the EPA Superfund Innovative
Technology Evaluation (SITE) Monitoring and 1.1 Description of SITE Program
Measurement Technology (MMT) Program using TPH-
contaminated soil from five areas located in three regions Performance verification of innovative environmental
of the United States. The demonstration was conducted at technologies is an integral part of the regulatory and
Port Hueneme, California, during the week of June 12, research mission of the EPA. The SITE Program was
2000. The purpose of the demonstration was to obtain established by the EPA Office of Solid Waste and
reliable performance and cost data on field measurement Emergency Response (OSWER) and ORD under the
devices in order to provide (1) potential users with a better Superfund Amendments and Reauthorization Act of 1986.
understanding of the devices’ performance and operating The overall goal of the SITE Program is to conduct
costs under well-defined field conditions and (2) the performance verification studies and to promote the
developers with documented results that will assist them in acceptance of innovative technologies that may be used to
promoting acceptance and use of their devices. The TPH achieve long-term protection of human health and the
results obtained using the seven field measurement devices environment. The program is designed to meet three
were compared to the TPH results obtained from a primary objectives: (1) identify and remove obstacles to
reference laboratory chosen for the demonstration, which the development and commercial use of innovative
used a reference method modified for the demonstration. technologies, (2) demonstrate promising innovative
technologies and gather reliable performance and cost
This innovative technology verification report (ITVR) information to support site characterization and cleanup
presents demonstration performance results and associated activities, and (3) develop procedures and policies that
costs for the OCMA-350 Oil Content Analyzer encourage the use of innovative technologies at Superfund
(OCMA-350) developed by Horiba Instruments sites as well as at other waste sites or commercial facilities.
Incorporated (Horiba). Specifically, this report describes
the SITE Program, the scope of the demonstration, and the The intent of a SITE demonstration is to obtain
components and definition of TPH (Chapter 1); the representative, high-quality performance and cost data on
innovative field measurement device and the technology one or more innovative technologies so that potential users
upon which it is based (Chapter 2); the three can assess the suitability of a given technology for a
demonstration sites (Chapter 3); the demonstration specific application. The SITE Program includes the
approach (Chapter 4); the selection of the reference following elements:
method and laboratory (Chapter 5); the assessment of
reference method data quality (Chapter 6); the • MMT Program—Evaluates innovative technologies
performance of the field measurement device (Chapter 7); that sample, detect, monitor, or measure hazardous
the economic analysis for the field measurement device

1
 and toxic substances. These technologies are expected • Test and verify the performance of innovative field
to provide better, faster, or more cost-effective sampling and analytical technologies that enhance
methods for producing real-time data during site sampling, monitoring, and site characterization
characterization and remediation studies than do capabilities
conventional technologies.
• Identify performance attributes of innovative
• Remediation Technology Program—Conducts technologies to address field sampling, monitoring,
demonstrations of innovative treatment technologies to and characterization problems in a more cost-effective
provide reliable performance, cost, and applicability and efficient manner
data for site cleanups.
• Prepare protocols, guidelines, methods, and other
• Technology Transfer Program—Provides and technical publications that enhance acceptance of these
disseminates technical information in the form of technologies for routine use
updates, brochures, and other publications that
promote the SITE Program and participating The MMT Program is administered by the Environmental
technologies. The Technology Transfer Program also Sciences Division of the NERL in Las Vegas, Nevada.
offers technical assistance, training, and workshops to The NERL is the EPA center for investigation of technical
support the technologies. A significant number of and management approaches for identifying and
these activities are performed by EPA’s Technology quantifying risks to human health and the environment.
Innovation Office. The NERL mission components include (1) developing
and evaluating methods and technologies for sampling,
The TPH field measurement device demonstration was monitoring, and characterizing water, air, soil, and
conducted as part of the MMT Program, which provides sediment; (2) supporting regulatory and policy decisions;
developers of innovative hazardous waste sampling, and (3) providing the technical support needed to ensure
detection, monitoring, and measurement devices with an effective implementation of environmental regulations
opportunity to demonstrate the performance of their and strategies. By demonstrating innovative field
devices under actual field conditions. These devices may measurement devices for TPH in soil, the MMT Program
be used to sample, detect, monitor, or measure hazardous is supporting the development and evaluation of methods
and toxic substances in water, soil gas, soil, and sediment. and technologies for field measurement of TPH
The technologies include chemical sensors for in situ (in concentrations in a variety of soil types. Information
place) measurements, soil and sediment samplers, soil gas regarding the selection of field measurement devices for
samplers, groundwater samplers, field-portable analytical TPH is available in American Petroleum Institute (API)
equipment, and other systems that support field sampling publications (API 1996, 1998).
or data acquisition and analysis.
The MMT Program’s technology verification process is
The MMT Program promotes acceptance of technologies designed to conduct demonstrations that will generate
that can be used to (1) accurately assess the degree of high-quality data so that potential users have reliable
contamination at a site, (2) provide data to evaluate information regarding device performance and cost. Four
potential effects on human health and the environment, (3) steps are inherent in the process: (1) needs identification
apply data to assist in selecting the most appropriate and technology selection, (2) demonstration planning and
cleanup action, and (4) monitor the effectiveness of a implementation, (3) report preparation, and (4) information
remediation process. The program places a high priority distribution.
on innovative technologies that provide more cost-
effective, faster, and safer methods for producing real-time The first step of the verification process begins with
or near-real-time data than do conventional, laboratory- identifying technology needs of the EPA and the regulated
based technologies. These innovative technologies are community. The EPA regional offices, the U.S.
demonstrated under field conditions, and the results are Department of Energy, the U.S. Department of Defense,
compiled, evaluated, published, and disseminated by the industry, and state environmental regulatory agencies are
ORD. The primary objectives of the MMT Program are as asked to identify technology needs for sampling,
follows:

2
monitoring, and measurement of environmental media. requirements for conducting the demonstration; and
Once a need is identified, a search is conducted to identify (4) provide the reference laboratory with an opportunity to
suitable technologies that will address the need. The identify any matrix-specific analytical problems associated
technology search and identification process consists of with the contaminated media and to propose appropriate
examining industry and trade publications, attending solutions. Information generated through the predemon-
related conferences, exploring leads from technology stration investigation is used to develop the final
developers and industry experts, and reviewing responses demonstration design and sampling and analysis
to Commerce Business Daily announcements. Selection procedures.
of technologies for field testing includes evaluation of
the candidate technologies based on several criteria. A Demonstration planning activities also include preparing
suitable technology for field testing a detailed demonstration plan that describes the procedures
to be used to verify the performance and cost of each
• Is designed for use in the field innovative technology. The demonstration plan
incorporates information generated during the
• Is applicable to a variety of environmentally predemonstration investigation as well as input from
contaminated sites technology developers, demonstration site representatives,
and technical peer reviewers. The demonstration plan also
• Has potential for solving problems that current incorporates the quality assurance (QA) and quality
methods cannot satisfactorily address control (QC) elements needed to produce data of sufficient
quality to document the performance and cost of each
• Has estimated costs that are lower than those of technology.
conventional methods
During the demonstration, each innovative technology is
• Is likely to achieve better results than current methods evaluated independently and, when possible and
in areas such as data quality and turnaround time appropriate, is compared to a reference technology. The
performance and cost of one innovative technology are not
• Uses techniques that are easier or safer than current compared to those of another technology evaluated in the
methods demonstration. Rather, demonstration data are used to
evaluate the individual performance, cost, advantages,
• Is commercially available limitations, and field applicability of each technology.

Once candidate technologies are identified, their As part of the third step of the verification process, the
developers are asked to participate in a developer EPA publishes a verification statement and a detailed
conference. This conference gives the developers an evaluation of each technology in an ITVR. To ensure its
opportunity to describe their technologies’ performance quality, the ITVR is published only after comments from
and to learn about the MMT Program. the technology developer and external peer reviewers are
satisfactorily addressed. In addition, all demonstration
The second step of the verification process is to plan and data used to evaluate each innovative technology are
implement a demonstration that will generate high-quality summarized in a data evaluation report (DER) that
data to assist potential users in selecting a technology. constitutes a complete record of the demonstration. The
Demonstration planning activities include a DER is not published as an EPA document, but an
predemonstration sampling and analysis investigation that unpublished copy may be obtained from the EPA project
assesses existing conditions at the proposed demonstration manager.
site or sites. The objectives of the predemonstration
investigation are to (1) confirm available information on The fourth step of the verification process is to distribute
applicable physical, chemical, and biological information regarding demonstration results. To benefit
characteristics of contaminated media at the sites to justify technology developers and potential technology users, the
selection of site areas for the demonstration; (2) provide EPA distributes demonstration bulletins and ITVRs
the technology developers with an opportunity to evaluate through direct mailings, at conferences, and on the
the areas, analyze representative samples, and identify Internet. The ITVRs and additional information on the
logistical requirements; (3) assess the overall logistical

3
SITE Program are available on the EPA ORD web site investigation was to assess whether the sites and sampling
(http://www.epa.gov/ORD/SITE). areas were appropriate for evaluating the seven field
measurement devices based on the demonstration
1.2 Scope of Demonstration objectives. Demonstration field activities were conducted
between June 5 and 18, 2000. The procedures used to
The purpose of the demonstration was to evaluate field verify the performance and costs of the field measurement
measurement devices for TPH in soil in order to provide devices are documented in a demonstration plan completed
(1) potential users with a better understanding of the in June 2000 (EPA 2000). The plan also incorporates the
devices’ performance and costs under well-defined field QA/QC elements that were needed to generate data of
conditions and (2) the developers with documented results sufficient quality to document field measurement device
that will assist them in promoting acceptance and use of and reference laboratory performance and costs. The plan
their devices. is available through the EPA ORD web site
(http://www.epa.gov/ORD/SITE) or from the EPA project
Chapter 2 of this ITVR describes both the technology upon manager.
which the OCMA-350 is based and the field measurement
device itself. Because TPH is a “method-defined 1.3 Components and Definition of TPH
parameter,” the performance results for the device are
compared to the results obtained using an off-site To understand the term “TPH,” it is necessary to
laboratory measurement method—that is, a reference understand the composition of petroleum and its products.
method. Details on the selection of the reference method This section briefly describes the composition of
and laboratory are provided in Chapter 5. petroleum and its products and defines TPH from a
measurement standpoint. The organic compounds
The demonstration had both primary and secondary containing only hydrogen and carbon that are present in
objectives. Primary objectives were critical to the petroleum and its derivatives are collectively referred to as
technology verification and required the use of quantitative petroleum hydrocarbons (PHC). Therefore, in this ITVR,
results to draw conclusions regarding each field the term “PHC” is used to identify sample constituents,
measurement device’s performance as well as to estimate and the term “TPH” is used to identify analyses performed
the cost of operating the device. Secondary objectives and the associated results (for example, TPH
pertained to information that was useful but did not concentrations).
necessarily require the use of quantitative results to draw
conclusions regarding the performance of each device. 1.3.1 Composition of Petroleum and Its Products
Both the primary and secondary objectives are discussed
in Chapter 4. Petroleum is essentially a mixture of gaseous, liquid, and
solid hydrocarbons that occur in sedimentary rock
To meet the demonstration objectives, samples were deposits. On the molecular level, petroleum is a complex
collected from five individual areas at three sites. The first mixture of hydrocarbons; organic compounds of sulfur,
site is referred to as the Navy Base Ventura County (BVC) nitrogen, and oxygen; and compounds containing metallic
site; is located in Port Hueneme, California; and contained constituents, particularly vanadium, nickel, iron, and
three sampling areas. The Navy BVC site lies in EPA copper. Based on the limited data available, the elemental
Region 9. The second site is referred to as the Kelly Air composition of petroleum appears to vary over a relatively
Force Base (AFB) site; is located in San Antonio, Texas; narrow range: 83 to 87 percent carbon, 10 to 14 percent
and contained one sampling area. The Kelly AFB site lies hydrogen, 0.05 to 6 percent sulfur, 0.1 to 2 percent
in EPA Region 6. The third site is referred to as the nitrogen, and 0.05 to 1.5 percent oxygen. Metals are
petroleum company (PC) site, is located in north-central present in petroleum at concentrations of up to 0.1 percent
Indiana, and contained one sampling area. The PC site lies (Speight 1991).
in EPA Region 5.
Petroleum in the crude state (crude oil) is a mineral
In preparation for the demonstration, a predemonstration resource, but when refined it provides liquid fuels,
sampling and analysis investigation was completed at the solvents, lubricants, and many other marketable products.
three sites in January 2000. The purpose of this The hydrocarbon components of crude oil include

4
paraffinic, naphthenic, and aromatic groups. Paraffins decreases with increasing molecular weight or boiling
(alkanes) are saturated, aliphatic hydrocarbons with point fraction for a given crude oil; however, this is not
straight or branched chains but without any ring structure. true for naphthenes or aromatic hydrocarbons. The
Naphthenes are saturated, aliphatic hydrocarbons proportion of monocyclonaphthenes decreases with
containing one or more rings, each of which may have one increasing molecular weight or boiling point fraction,
or more paraffinic side chains (alicyclic hydrocarbons). whereas the opposite is true for polycyclonaphthenes (for
Aromatic hydrocarbons contain one or more aromatic example, tetralin and decalin) and polynuclear aromatic
nuclei, such as benzene, naphthalene, and phenanthrene hydrocarbons; the proportion of mononuclear aromatic
ring systems, that may be linked with (substituted) hydrocarbons appears to be independent of molecular
naphthenic rings or paraffinic side chains. In crude oil, the weight or boiling point fraction.
relationship among the three primary groups of
hydrocarbon components is a result of hydrogen gain or Various petroleum products consisting of carbon and
loss between any two groups. Another class of hydrogen are formed when crude oil is subjected to
compounds that is present in petroleum products such as distillation and other processes in a refinery. Processing of
automobile gasoline but rarely in crude oil is known as crude oil results in petroleum products with trace quantities
olefins. Olefins (alkenes) are unsaturated, aliphatic of metals and organic compounds that contain nitrogen,
hydrocarbons. sulfur, and oxygen. These products include liquefied
petroleum gas, gasoline, naphthas, kerosene, fuel oils,
The distribution of paraffins, naphthenes, and aromatic lubricating oils, coke, waxes, and asphalt. Of these
hydrocarbons depends on the source of crude oil. For products, gasoline, naphthas, kerosene, fuel oils, and
example, Pennsylvania crude oil contains high levels of lubricating oils are liquids and may be present at
paraffins (about 50 percent), whereas Borneo crude oil petroleum-contaminated sites. Except for gasoline and
contains less than 1 percent paraffins. As shown in some naphthas, these products are made primarily by
Figure 1-1, the proportion of straight or branched paraffins collecting particular boiling point fractions of crude oil

Source: Speight 1991

Figure 1-1. Distribution of various petroleum hydrocarbon types throughout boiling point range of crude oil.

5
from a distillation column. Because this classification of 1.3.1.2 Naphthas
petroleum products is based on boiling point and not on
chemical composition, the composition of these products, “Naphtha” is a generic term applied to petroleum solvents.
including the ratio of aliphatic to aromatic hydrocarbons, Under standardized distillation conditions, at least
varies depending on the source of crude oil. In addition, 10 percent of naphthas should distill below 175 °C, and at
specific information (such as boiling points and carbon least 95 percent of naphthas should distill below 240 °C.
ranges) for different petroleum products, varies slightly Naphthas can be both aliphatic and aromatic and contain
depending on the source of the information. Commonly hydrocarbons with 6 to 14 carbon atoms per molecule.
encountered forms and blends of petroleum products are Depending on the intended use of a naphtha, it may be free
briefly described below. The descriptions are primarily of aromatic hydrocarbons (to make it odor-free) and sulfur
based on information in books written by Speight (1991) (to make it less toxic and less corrosive). Many forms of
and Gary and Handwerk (1993). Additional information naphthas are commercially available, including Varnish
is provided by Dryoff (1993). Makers’ and Painters’ naphthas (Types I and II), mineral
spirits (Types I through IV), and aromatic naphthas
1.3.1.1 Gasoline (Types I and II). Stoddard solvent is an example of an
aliphatic naphtha.
Gasoline is a major exception to the boiling point
classification described above because “straight-run 1.3.1.3 Kerosene
gasoline” (gasoline directly recovered from a distillation
column) is only a small fraction of the blended gasoline Kerosene is a straight-run petroleum fraction that has a
that is commercially available as fuel. Commercially boiling point range of 205 to 260 °C. Kerosene typically
available gasolines are complex mixtures of hydrocarbons contains hydrocarbons with 12 or more carbon atoms per
that boil below 180 °C or at most 225 °C and that contain molecule. Because of its use as an indoor fuel, kerosene
hydrocarbons with 4 to 12 carbon atoms per molecule. Of must be free of aromatic and unsaturated hydrocarbons as
the commercially available gasolines, aviation gasoline has well as sulfur compounds.
a narrower boiling range (38 to 170 °C) than automobile
gasoline (-1 to 200 °C). In addition, aviation gasoline may 1.3.1.4 Jet Fuels
contain high levels of paraffins (50 to 60 percent),
moderate levels of naphthenes (20 to 30 percent), a low Jet fuels, which are also known as aircraft turbine fuels,
level of aromatic hydrocarbons (10 percent), and no are manufactured by blending gasoline, naphtha, and
olefins, whereas automobile gasoline may contain up to kerosene in varying proportions. Therefore, jet fuels may
30 percent olefins and up to 40 percent aromatic contain a carbon range that covers gasoline through
hydrocarbons. kerosene. Jet fuels are used in both military and
commercial aircraft. Some examples of jet fuels include
Gasoline composition can vary widely depending on the Type A, Type A-1, Type B, JP-4, JP-5, and JP-8. The
source of crude oil. In addition, gasoline composition aromatic hydrocarbon content of these fuels ranges from
varies from region to region because of consumer needs for 20 to 25 percent. The military jet fuel JP-4 has a wide
gasoline with a high octane rating to prevent engine boiling point range (65 to 290 °C), whereas commercial jet
“knocking.” Moreover, EPA regulations regarding the fuels, including JP-5 and Types A and A-1, have a
vapor pressure of gasoline, the chemicals used to produce narrower boiling point range (175 to 290 °C) because of
a high octane rating, and cleaner-burning fuels have safety considerations. Increasing concerns over combat
affected gasoline composition. For example, when use of hazards associated with JP-4 jet fuel led to development of
tetraethyl lead to produce gasoline with a high octane JP-8 jet fuel, which has a flash point of 38 °C and a
rating was banned by the EPA, oxygenated fuels came into boiling point range of 165 to 275 °C. JP-8 jet fuel
existence. Production of these fuels included addition of contains hydrocarbons with 9 to 15 carbon atoms per
methyl-tert-butyl ether (MTBE), ethanol, and other molecule. Type B jet fuel has a boiling point range of 55
oxygenates. Use of oxygenated fuels also results in to 230 °C and a carbon range of 5 to 13 atoms per
reduction of air pollutant emissions (for example, carbon molecule. A new specification is currently being
monoxide and nitrogen oxides). developed by the American Society for Testing and
Materials (ASTM) for Type B jet fuel.

6
1.3.1.5 Fuel Oils and viscosities. Materials suitable for production of
lubricating oils are composed principally of hydrocarbons
Fuel oils are divided into two classes: distillates and containing 25 to 35 or even 40 carbon atoms per molecule,
residuals. No. 1 and 2 fuel oils are distillates and include whereas residual stocks may contain hydrocarbons with 50
kerosene, diesel, and home heating oil. No. 4, 5, and 6 fuel to 60 or more (up to 80 or so) carbon atoms per molecule.
oils are residuals or black oils, and they all contain crude Because it is difficult to isolate hydrocarbons from the
distillation tower bottoms (tar) to which cutter stocks lubricant fraction of petroleum, aliphatic to aromatic
(semirefined or refined distillates) have been added. No. 4 hydrocarbon ratios are not well documented for lubricating
fuel oil contains the most cutter stock, and No. 6 fuel oil oils. However, these ratios are expected to be comparable
contains the least. to those of the source crude oil.

Commonly available fuel oils include No. 1, 2, 4, 5, and 6. 1.3.2 Measurement of TPH
The boiling points, viscosities, and densities of these fuel
oils increase with increasing number designation. The As described in Section 1.3.1, the composition of
boiling point ranges for No. 1, 2, and 4 fuel oils are about petroleum and its products is complex and variable, which
180 to 320, 175 to 340, and 150 to 480 °C, respectively. complicates TPH measurement. The measurement of TPH
No. 1 and 2 fuel oils contain hydrocarbons with 10 to in soil is further complicated by weathering effects. When
22 carbon atoms per molecule; the carbon range for No. 4 a petroleum product is released to soil, the product’s
fuel oil is 22 to 40 atoms per molecule. No. 5 and 6 fuel composition immediately begins to change. The
oils have a boiling point range of 150 to 540 °C but differ components with lower boiling points are volatilized, the
in the amounts of residue they contain: No. 5 fuel oil more water-soluble components migrate to groundwater,
contains a small amount of residue, whereas No. 6 fuel oil and biodegradation can affect many other components.
contains a large amount. No. 5 and 6 fuel oils contain Within a short period, the contamination remaining in soil
hydrocarbons with 28 to 90 carbon atoms per molecule. may have only some characteristics in common with the
Fuel oils typically contain about 60 percent aliphatic parent product.
hydrocarbons and 40 percent aromatic hydrocarbons.
This section provides a historical perspective on TPH
1.3.1.6 Diesel measurement, reviews current options for TPH
measurement in soil, and discusses the definition of TPH
Diesel is primarily used to operate motor vehicle and that was used for the demonstration.
railroad diesel engines. Automobile diesel is available in
two grades: No. 1 and 2. No. 1 diesel, which is sold in 1.3.2.1 Historical Perspective
regions with cold climates, has a boiling point range of 180
to 320 °C and a cetane number above 50. The cetane Most environmental measurements are focused on
number is similar to the octane number of gasoline; a identifying and quantifying a particular trace element (such
higher number corresponds to less knocking. No. 2 diesel as lead) or organic compound (such as benzene).
is very similar to No. 2 fuel oil. No. 2 diesel has a boiling However, for some “method-defined” parameters, the
point range of 175 to 340 °C and a minimum cetane particular substance being measured may yield different
number of 52. No. 1 diesel is used in high-speed engines results depending on the measurement method used.
such as truck and bus engines, whereas No. 2 diesel is used Examples of such parameters include oil and grease and
in other diesel engines. Railroad diesel is similar to No. 2 surfactants. Perhaps the most problematic of the method-
diesel but has a higher boiling point (up to 370 °C) and defined parameters is TPH. TPH arose as a parameter for
lower cetane number (40 to 45). The ratio of aliphatic to wastewater analyses in the 1960s because of petroleum
aromatic hydrocarbons in diesel is about 5. The carbon industry concerns that the original “oil and grease”
range for hydrocarbons present in diesel is 10 to 28 atoms analytical method, which is gravimetric in nature, might
per molecule. inaccurately characterize petroleum industry wastewaters
that contained naturally occurring vegetable oils and
1.3.1.7 Lubricating Oils greases along with PHCs. These naturally occurring
materials are typically long-chain fatty acids (for example,
Lubricating oils can be distinguished from other crude oil oleic acid, the major component of olive oil).
fractions by their high boiling points (greater than 400 °C)

7
Originally, TPH was defined as any material extracted with regulations as a somewhat ill-defined term, and most state
a particular solvent that is not adsorbed by the silica gel programs still have cleanup criteria for TPH.
used to remove fatty acids and that is not lost when the
solvent is evaporated. Although this definition covers 1.3.2.2 Current Options for TPH Measurement
most of the components of petroleum products, it includes in Soil
many other organic compounds as well, including
chlorinated solvents, pesticides, and other synthetic Three widely used technologies measure some form of
organic chemicals. Furthermore, because of the TPH in soil to some degree. These technologies were used
evaporation step in the gravimetric analytical method, the as starting points in deciding how to define TPH for the
definition excludes most of the petroleum-derived demonstration. The three technologies and the analytes
compounds in gasoline that are volatile in nature. For measured are summarized in Table 1-2.
these reasons, an infrared analytical method was developed
to measure TPH. In this method, a calibration standard Of the three technologies, gravimetry and infrared are
consisting of three components is analyzed at a wavelength discussed in Section 1.3.2.1. The third technology, the gas
of 3.41 micrometers (µm), which corresponds to an chromatograph/flame ionization detector (GC/FID), came
aliphatic CH2 hydrocarbon stretch. As shown in Table 1-1, into use because of the documented shortcomings of the
the calibration standard is designed to mimic a petroleum other two technologies. The GC/FID had long been used
product having a relative distribution of aliphatic and in the petroleum refining industry as a product QC tool to
aromatic compounds as well as a certain percentage of determine the boiling point distribution of pure petroleum
aliphatic CH2 hydrocarbons. The infrared analytical products. In the 1980s, environmental laboratories began
method indicates that any compound that is extracted by to apply this technology along with sample preparation
the solvent, is not adsorbed by silica gel, and contains a methods developed for soil samples to measure PHCs at
CH2 bond is a PHC. Both the gravimetric and infrared environmental levels (Zilis, McDevitt, and Parr 1988).
analytical methods include an optional, silica gel GC/FID methods measure all organic compounds that are
fractionation step to remove polar, biogenic compounds extracted by the solvent and that can be chromatographed.
such as fatty acids, but this cleanup step can also remove However, because of method limitations, the very volatile
some petroleum degradation products that are polar in portion of gasoline compounds containing four or five
nature. carbon atoms per molecule is not addressed by GC/FID
methods; therefore, 100 percent recovery cannot be
In the 1980s, because of the change in focus from achieved for pure gasoline. This omission is not
wastewater analyses to characterization of hazardous waste considered significant because these low-boiling-point
sites that contained contaminated soil, many parties began aliphatic compounds (1) are not expected to be present in
to adapt the existing wastewater analytical methods for environmental samples (because of volatilization) and
application to soil. Unfortunately, the term “TPH” was in (2) pose less environmental risk than the aromatic
common use, as many states had adopted this term (and the hydrocarbons in gasoline.
wastewater analytical methods) for cleanup activities at
underground storage tank (UST) sites. Despite efforts by The primary limitation of GC/FID methods relates to the
the API and others to establish new analyte names (for extraction solvent used. The solvent should not interfere
example, gasoline range organics [GRO] and diesel range with the analysis, but to achieve environmental levels of
organics [DRO]), “TPH” is still present in many state detection (in the low milligram per kilogram [mg/kg]

Table 1-1. Summary of Calibration Information for Infrared Analytical Method

Number of Carbon Atoms

Portion of Constituent Portion of Aliphatic CH2 in
Aliphatic Aromatic
Standard in Standard Standard Constituent
Constituent Constituent Type (percent by volume) CH3 CH2 CH CH (percent by weight)
Hexadecane Straight-chain aliphatic 37.5 2 14 0 0 91
Isooctane Branched-chain aliphatic 37.5 5 1 1 0 14
Chlorobenzene Aromatic 25 0 0 0 5 0
Average 35

8
Table 1-2. Current Technologies for TPH Measurement

Technology What Is Measured What Is Not Measured

Gravimetry All analytes removed from the sample by the Volatiles; very polar organics
extraction solvent that are not volatilized
Infrared All analytes removed from the sample by the Benzene, naphthalene, and other aromatic
extraction solvent that contain an aliphatic CH2 hydrocarbons with no aliphatic group attached;
stretch very polar organics
Gas chromatograph/flame ionization detector All analytes removed from the sample by the Very polar organics; compounds with high
extraction solvent that can be chromatographed molecular weights or high boiling points
and that respond to the detector

range) for soil, some concentration of the extract is needed method was interlaboratory-validated along with the GRO
because the sensitivity of the FID is in the nanogram (ng) and DRO methods in an API study in 1994. The PHC
range. This limitation has resulted in three basic method originally defined PHC as the sum of the
approaches for GC/FID analyses for GRO, DRO, and compounds in the boiling point range of about 70 to
PHCs. 400 °C, but it now defines PHC as the sum of the
compounds in the boiling point range of 70 to 490 °C.
For GRO analysis, a GC/FID method was developed as The method provides options for instrument calibration,
part of research sponsored by API and was the subject of including use of synthetic standards, but it recommends
an interlaboratory validation study (API 1994); the method use of products similar to the contaminants present at the
was first published in 1990. In this method, GRO is site of concern. The PHC method has not been
defined as the sum of the organic compounds in the boiling specifically incorporated into SW-846; however, the
point range of 60 to 170 °C, and the method uses a method has been used as the basis for the TPH methods in
synthetic calibration standard as both a window-defining several states, including Massachusetts, Washington, and
mix and a quantitation standard. The GRO method was Texas. The PHC method uses solvent microextraction and
specifically incorporated into EPA “Test Methods for thus has a higher detection limit than the GRO and DRO
Evaluating Solid Waste” (SW-846) Method 8015B in 1996 methods. The PHC method also begins peak integration
(EPA 1996). The GRO method uses the purge-and-trap after elution of the solvent peak for n-pentane. Thus, this
technique for sample preparation, effectively limiting the method probably cannot measure some volatile
TPH components to the volatile compounds only. compounds (for example, 2-methyl pentane and MTBE)
that are measured using the GRO method.
For DRO analysis, a GC/FID method was developed under
the sponsorship of API as a companion to the GRO method 1.3.2.3 Definition of TPH
and was interlaboratory-validated in 1994. In the DRO
method, DRO is defined as the sum of the organic It is not possible to establish a definition of TPH that
compounds in the boiling point range of 170 to 430 °C. As would include crude oil and its refined products and
in the GRO method, a synthetic calibration standard is exclude other organic compounds. Ideally, the TPH
used for quantitation. The DRO method was also definition selected for the demonstration would have
incorporated into SW-846 Method 8015B in 1996. The
technology used in the DRO method can measure • Included compounds that are PHCs, such as paraffins,
hydrocarbons with boiling points up to 540 °C. However, naphthenes, and aromatic hydrocarbons
the hydrocarbons with boiling points in the range of 430 to
540 °C are specifically excluded from SW-846 • Included, to the extent possible, the major liquid
Method 8015B so as not to include the higher-boiling- petroleum products (gasoline, naphthas, kerosene, jet
point petroleum products. The DRO method uses a solvent fuels, fuel oils, diesel, and lubricating oils)
extraction and concentration step, effectively limiting the
method to nonvolatile hydrocarbons. • Had little inherent bias based on the composition of an
individual manufacturer’s product
For PHC analysis, a GC/FID method was developed by
Shell Oil Company (now Equilon Enterprises). This

9
• Had little inherent bias based on the relative • The repeatability and versatility of sample
concentrations of aliphatic and aromatic hydrocarbons fractionation and analysis procedures are not well
present documented.

• Included much of the volatile portion of gasoline, • In some states, TPH-based action levels are still used.
including all weathered gasoline
• The associated analytical costs are high.
• Included MTBE
As stated in Section 1.3.2.2, analytical methods currently
• Excluded crude oil residuals beyond the extended available for measurement of TPH each exclude some
diesel range organic (EDRO) range portion of TPH and are unable to measure TPH alone
while excluding all other organic compounds, thus making
• Excluded nonpetroleum organic compounds (for TPH a method-defined parameter. After consideration of
example, chlorinated solvents, pesticides, all the information presented above, the GRO and DRO
polychlorinated biphenyls [PCB], and naturally analytical methods were selected for TPH measurement for
occurring oils and greases) the demonstration. However, because of the general
interest in higher-boiling-point petroleum products, the
• Allowed TPH measurement using a widely accepted integration range of the DRO method was extended to
method include compounds with boiling points up to 540 °C.
Thus, for the demonstration, the TPH concentration was
• Reflected accepted TPH measurement practice in the sum of all organic compounds that have boiling points
many states between 60 and 540 °C and that can be chromatographed,
or the sum of the results obtained using the GRO and DRO
Several states, including Massachusetts, Alaska, Louisiana, methods. This approach accounts for most gasoline,
and North Carolina, have implemented or are planning to including MTBE, and virtually all other petroleum
implement a TPH contamination cleanup approach based products and excludes a portion (25 to 50 percent) of the
on the aliphatic and aromatic hydrocarbon fractions of heavy lubricating oils. Thus, TPH measurement for the
TPH. The action levels for the aromatic hydrocarbon demonstration included PHCs as well as some organic
fraction are more stringent than those for the aliphatic compounds that are not PHCs. More specifically, TPH
hydrocarbon fraction. The approach used in the above- measurement did not exclude nonpetroleum organic
mentioned states involves performing a sample compounds such as chlorinated solvents, other synthetic
fractionation procedure and two analyses to determine the organic chemicals such as pesticides and PCBs, and
aliphatic and aromatic hydrocarbon concentrations in a naturally occurring oils and greases. A silica gel
sample. However, in most applications of this approach, fractionation step used to remove polar, biogenic
only a few samples are subjected to the dual aliphatic and compounds such as fatty acids in some GC/FID methods
aromatic hydrocarbon analyses because of the costs was not included in the sample preparation step because,
associated with performing sample fractionation and two according to the State of California, this step can also
analyses. remove some petroleum degradation products that are also
polar in nature (California Environmental Protection
For the demonstration, TPH was not defined based on the Agency 1999). The step-by-step approach used to select
aliphatic and aromatic hydrocarbon fractions because the reference method for the demonstration and the
project-specific procedures implemented for soil sample
• Such a definition is used in only a few states. preparation and analysis using the reference method are
detailed in Chapter 5.
• Variations exist among the sample fractionation and
analysis procedures used in different states.

10
 Chapter 2
Description of Infrared Analysis and the OCMA-350

Measurement of TPH in soil by field measurement devices specified value (for example, the reporting limit or an
generally involves extraction of PHCs from soil using an action level).
appropriate solvent followed by measurement of the TPH
concentration in the extract using an optical method. An The OCMA-350 is a field measurement device capable of
extraction solvent is selected that will not interfere with the providing quantitative TPH measurement results. Optical
optical measurement of TPH in the extract. Some field measurements made using the OCMA-350 are based on
measurement devices use light in the visible wavelength infrared analysis, which is described in Section 2.1.
range, and others use light outside the visible wavelength Section 2.2 describes the OCMA-350 itself, and
range (for example, infrared radiation). Section 2.3 provides Horiba contact information. The
technology and device descriptions presented below are
The optical measurements made by field measurement not intended to provide complete operating procedures for
devices may involve absorbance, reflectance, or measuring TPH concentrations in soil using the
fluorescence. In general, the optical measurement for a OCMA-350. Detailed operating procedures for the device,
soil extract is compared to a calibration curve in order to including soil extraction, TPH measurement, and TPH
determine the TPH concentration. Calibration curves may concentration calculation procedures, are available from
be developed by (1) using a series of calibration standards Horiba. Supplemental information provided by Horiba is
selected based on the type of PHCs being measured at a presented in the appendix.
site or (2) establishing a correlation between off-site
laboratory measurements and field measurements for 2.1 Description of Infrared Analysis
selected, site-specific soil samples.
This section describes the technology, infrared analysis,
Field measurement devices may be categorized as upon which the OCMA-350 is based. This technology is
quantitative, semiquantitative, and qualitative. These suitable for measuring aromatic and aliphatic hydrocarbons
categories are explained below. independent of their carbon range. TPH measurement
using infrared analysis involves extraction of PHCs in soil
• A quantitative measurement device measures TPH using an organic solvent. Light in the infrared range is
concentrations ranging from its reporting limit through used to irradiate the extract and measure its TPH
its linear range. The measurement result is reported as concentration.
a single, numerical value that has an established
precision and accuracy. Infrared spectrophotometry generally covers the 1- to
15-µm wavelength region. All organic molecules and
• A semiquantitative measurement device measures some inorganic ions absorb light energy in this region.
TPH concentrations above its reporting limit. The Absorbance of infrared energy results in changes in
measurement result may be reported as a concentration vibrational motion in a molecule. The molecular
range with lower and upper limits. vibrations observed may be divided into two types,
stretching and bending. Stretching is the rhythmic
• A qualitative measurement device indicates the movement of the atoms back and forth along the bond
presence or absence of PHCs above or below a axis, whereas bending involves a change in bond angle

11
between two atoms that are bonded to a third atom or the Table 2-1. Infrared Absorbance Values of CH, CH2, and CH3 Groups
movement of a group of atoms with respect to the rest of Absorbance of 16-Milligram per Liter
the molecule. Based on the unique absorbance and Sample Sample in Carbon Tetrachloride
vibrational motion associated with each compound, the Waste oils
type of compound in a sample can be identified using From kerosene treating area 0.424
infrared analysis (Fritz and Schenk 1987). From gasoline treating area 0.384
From pipe stills and gasoline 0.374
desulfurization area
The energy associated with shorter or near-infrared
From solvent extraction area 0.415
wavelengths (less than 4 µm) used for TPH measurement
From thermal cracking area 0.318
causes mostly stretching vibrations of bonds between From catalytic cracking area 0.355
hydrogen and heavier atoms. TPH measurement using From wax refining area 0.399
infrared analysis involves absorbance measurement From crude oil handling area 0.409
because the carbon-hydrogen bonds in the hydrocarbons Refinery products
absorb infrared light. During infrared analysis, Light lubricating oil 0.427
absorbances associated with CH, CH2, and CH3 Heavy lubricating oil 0.491
configurations are measured at a wavelength close to 3,400 Light Refugio crude oil 0.385
nanometers (nm). Specifically, infrared devices that Furnace oil from catalytic 0.339
operate in the 3,380- to 3,500-nm wavelength range should cracking
be able to measure CH (3,380 nm), CH2 (3,420 nm), and No. 6 fuel oil 0.287
White oil (medicinal) 0.417
CH3 (3,500 nm) configurations (Simard and others 1951).
Kerosene 0.440
Gasoline base stock 0.387
Table 2-1 shows the absorbance values of a series of waste
Pure compounds
oils, refinery products, and pure compounds in samples
Cetane 0.615
collected from a wide variety of locations at a petroleum Isooctane 0.404
refinery. The absorbance variations shown in Table 2-1 n-Heptane 0.613
are not great enough to seriously affect sample analytical p-Di-tert-butyl cyclohexane 0.396
results when TPH concentrations below 10 milligrams per Ethyl cyclohexane 0.543
liter (mg/L) are being measured unless high concentrations Cyclohexane 0.703
of the lower boiling point aromatic hydrocarbons are 1-Tetradecene 0.427
present. Based on this information, the most serious Decene 0.414
shortcoming of infrared analysis is likely its inability to Diisobutylene 0.208
detect the lower homologs of the aromatic hydrocarbon High molecular weight alkyl 0.155
series. Because the aromatic C-H absorption is relatively benzene
Cumene 0.109
weak, only aromatic hydrocarbons with appreciable
Mixed xylenes 0.070
paraffin or cycloparaffin side chains exhibit normal
Benzene 0.000
behavior during TPH measurement (Simard and others
1951).
Source: Simard and others 1951
During infrared analysis, a sample extract is placed in a
glass or quartz cuvette that is then inserted into the
spectrophotometer and covered with an opaque light Some of the infrared radiation emitted by the source is
shield. A beam of infrared light is then passed through absorbed by compounds in the sample extract, and the rest
the sample extract. Infrared sources are generally of the radiation passes through the extract. Absorbance,
continuum sources, which emit radiation at intensities that which is defined as the logarithm of the ratio of the radiant
vary smoothly over ranges of wavelengths. A typical power of the light source to that of the light that passes
example of an infrared source for near-infrared through the sample extract, is measured by a photoelectric
instruments used for TPH measurement is a tungsten lamp detector in the spectrophotometer (Fritz and Schenk 1987).
(Fritz and Schenk 1987; Ewing 1969). Absorbance can be calculated using Equation 2-1.

12
 A = log (I0/I) (2-1) 2.2 Description of OCMA-350
where
The OCMA-350 was developed by Horiba and has been
A = Absorbance commercially available since 1995. This section describes
I0 = Intensity of light source the device and summarizes its operating procedure.

I = Intensity of light that passes through the 2.2.1 Device Description

sample extract
Infrared analysis using the OCMA-350 involves use of a
Therefore, the intensity of the light that passes through the single-beam, fixed-wavelength, nondispersive infrared
sample extract is inversely proportional to the (NDIR) spectrophotometer to determine the concentration
concentration of target compounds in the extract, or the of PHCs in a liquid sample extract. NDIR spectro-
intensity of the light absorbed by the extract is directly photometers offer several advantages over conventional,
proportional to the concentration of target compounds in scanning infrared spectrophotometers that disperse infrared
the extract. The absorbance of a sample extract thus light using a diffraction grating component. Whereas
measured is directly proportional to the concentration of scanning infrared spectrophotometers take about 1 to 3
PHCs present in the extract in accordance with minutes to scan a sample and have moderate sensitivity
Beer-Lambert’s law, which allows Equation 2-1 to be and stability, NDIR spectrophotometers can achieve a
expressed as shown in Equation 2-2. stable reading in about 5 seconds and have greater
sensitivity and stability (Fritz and Schenk 1987).
A = 0bc (2-2)
where In the OCMA-350, infrared radiation from a tungsten lamp
is transmitted through a cylindrical, quartz cuvette
A = Absorbance
containing a sample extract. The radiation that has passed
0 = Molar absorptivity (centimeter [cm] per mole through the extract enters a detector containing a filter that
per L) isolates analytical wavelengths in the 3,400- to 3,500-nm
range. According to Horiba, the OCMA-350 can measure
b = Light path length (cm)
both aromatic and aliphatic hydrocarbons independent of
c = Concentration of absorbing species (mole their carbon range. The device’s response to aliphatic
per L) hydrocarbons is greater than its response to aromatic
hydrocarbons.
Thus, according to Beer-Lambert’s law, the absorbance of
hydrocarbons is directly proportional to the concentrations According to Horiba, several solvents can be used to
of the absorbing hydrocarbons and the path length of the complete extraction of soil samples for OCMA-350
infrared radiation that is not absorbed by the sample analysis, including Horiba’s proprietary S-316 extraction
extract and passes through the extract. In Equation 2-2, solvent, Freon 113, tetrachloroethene, and carbon
the molar absorptivity is a proportionality constant, which tetrachloride. For the demonstration, Horiba used its
is a characteristic of the absorbing hydrocarbons and proprietary S-316 extraction solvent to extract soil
changes as the wavelength of the light irradiating the samples. Horiba recommends use of the S-316 extraction
sample extract changes. Therefore, Beer-Lambert’s law solvent because it has a higher boiling point (134 °C) and
applies only to monochromatic light (light energy of one lower freezing point (-143 °C) than other extraction
wavelength). solvents. In addition, the S-316 extraction solvent is
nonflammable, nontoxic, and relatively nonvolatile
After the absorbance of the sample extract is measured, the because of its low vapor pressure.
TPH concentration in the extract can be determined by
comparing the absorbance reading to a calibration curve of The OCMA-350 can be used to measure PHC
absorbance values and corresponding hydrocarbon concentrations in soil. Because hydrocarbons absorb
concentrations for a series of known standards selected infrared radiation, the OCMA-350 responds to their
based on the type of PHCs being measured at a site. concentrations in sample extracts. Standards of known
concentrations can be used to develop a calibration curve

13
of absorbance versus TPH concentration, that can in turn Table 2-2. OCMA-350 Components and Supplies
be used to calculate the TPH concentrations in actual
Spectrophotometer and accessories
samples. According to Horiba, the OCMA-350 can • Infrared spectrophotometer
achieve a method detection limit (MDL) of 1 mg/kg for • Proprietary, 10-mm, quartz cuvette with Teflon® cap
• 25-µL microsyringe
TPH and is linear up to 1,000 mg/kg in soil. Horiba also • 10-mL syringe
claims that the device can achieve repeatability of plus or • 10 mL of B-heavy oil
minus (±) 2 mg/kg from 0 to 99.9 mg/kg; ±4 mg/kg from • Three 40-mL, volatile organic analysis vials
• Three 11-centimeter-diameter, No. 40 Whatman filter papers
100 to 200 mg/kg; and ±10 mg/kg from 201 to • Two 10-mL, disposable, glass pipettes
1,000 mg/kg. No information is currently available from • Instruction manual and simplified operating instruction sheet
Horiba regarding the accuracy of the device. An Supplies available from Horiba
evaluation of the MDL, accuracy, and precision achieved • S-316 extraction solvent (1.5- or 7-kg bottle)
• Model VC-50 ultrasonic mixera
by the OCMA-350 during the demonstration is presented • Model SR-300 solvent reclaimer
in Chapter 7. • Centronics printer cable
Supplies not available from Horiba
According to Horiba, the OCMA-350 has an operating • Anhydrous sodium sulfate, 10-60 mesh
temperature range of 0 to 40 °C and humidity range of 0 to • Printer
• Balance
90 percent. Horiba does not specify a particular storage • Stainless-steel spatulas
temperature for the device. • Filter forceps
• Glass funnels
• Glass beakers
Table 2-2 lists components of the OCMA-350 and supplies • Pipette bulb
that may or may not be required for measuring TPH in soil • 10-µL microsyringe
• Bottle-top dispenser
using the device. The supplies are categorized according • Test tube rack
to whether or not they are available from Horiba. • Funnel rack and stand

Notes:
Supplies associated with TPH measurement using the
OCMA-350 may also be categorized according to whether µL = Microliter mL = Milliliter
they are expendable or reusable. Expendable supplies kg = Kilogram mm = Millimeter

include 10 milliliters (mL) of B-heavy oil that comes with a

During the demonstration, Horiba used the Model GE-50 ultrasonic
the OCMA-350; S-316 extraction solvent; anhydrous mixer, which is no longer available from the developer. According
to Horiba, the Model GE-50 and VC-50 ultrasonic mixers are
sodium sulfate; 40-mL, volatile organic analysis (VOA) functionally the same.
vials; 11-cm-diameter, No. 40 Whatman filter papers; and
10-mL, disposable, glass pipettes. Horiba generally
recommends use of B-heavy oil as the default calibration mixer, which is no longer available from the developer.
standard when the hydrocarbon content of soil is unknown. According to Horiba, the Model VC-50 ultrasonic mixer
According to Horiba, B-heavy oil may be replaced with that is currently available is functionally the same as
diesel as the calibration standard based on the Model GE-50.
contamination at a site.
The OCMA-350 infrared spectrophotometer and its
Reusable supplies include the infrared spectrophotometer accessories come in an optional, hard-plastic carrying case
and all its accessories except B-heavy oil, Model VC-50 and weigh 36 pounds. The carrying case is 22 inches long,
ultrasonic mixer, Model SR-300 solvent reclaimer, 16 inches wide, and 15 inches high. The device can be
Centronics printer cable, printer, balance, stainless-steel operated using a 110- or 220-volt alternating current (AC)
spatulas, filter forceps, glass funnels, glass beakers, pipette power source. It may also be operated using a direct
bulb, 10-microliter (µL) microsyringe, bottle-top current (DC) power source such as a 12-volt power outlet
dispenser, test tube rack, and funnel rack and stand. Of in an automobile along with a DC/AC power inverter.
these reusable supplies, items required for TPH analysis During the demonstration, Horiba operated the
using the OCMA-350 include the balance, stainless-steel OCMA-350 using AC power from the demonstration field
spatulas, filter forceps, glass funnels, glass beakers, pipette trailer.
bulb, test tube rack, and funnel rack and stand; Horiba
considers the other items to be optional. During the The spectrophotometer presents results in units selected by
demonstration, Horiba used the Model GE-50 ultrasonic the user during calibration, such as mg/kg in soil or

14
absorbance values. During the demonstration, Horiba is provided with the OCMA-350, as the default calibration
programmed the spectrophotometer to present results as standard when the hydrocarbon content of soil is unknown.
mg/kg in soil. The spectrophotometer is also equipped Based on the results of the predemonstration investigation,
with a parallel printer port and an RS232-C data port to Horiba used diesel as the calibration standard for the
allow transfer of data to a computer or other data logger. demonstration. Horiba conducted a three-point calibration
The spectrophotometer keeps a record of the time and date using S-316 extraction solvent as a blank and 100- and
of each measurement and a record of each data set that it 200-mg/L diesel standards at the beginning and end of
generates. Spectrophotometer printouts contain the time each day and after every batch of samples was analyzed.
and date of each measurement along with the concentration Concrete sand was also used as a sample blank for a
or absorbance value, which facilitates recordkeeping. calibration check once a day.

According to Horiba, about 20 samples can be analyzed by During the demonstration, Horiba dried soil by adding
one field technician using the OCMA-350 over an 8-hour anhydrous sodium sulfate. Extraction of a given soil
period. The device is relatively easy to use. Normal sample was typically performed by adding 20 mL of S-316
training for using the device is limited to reading the extraction solvent to 5.0 grams of the sample. The mixture
instruction manual and simplified operating instruction was agitated using the Model GE-50 ultrasonic mixer. The
sheet. Horiba offers a 1-day training course covering sample extract was decanted into a beaker through a filter-
operation, maintenance, and service of the OCMA-350, but lined funnel, and then the filtrate was poured into a quartz
according to the developer, purchasers of the device rarely cuvette. The cuvette was placed in the spectrophotometer
request this training. Horiba also provides technical for TPH measurement. Horiba pressed the “Run” button
support over the telephone during regular business hours and read the concentration on the digital display.
at no additional cost.
2.3 Developer Contact Information
According to Horiba, the OCMA-350 is innovative
because it can reuse proprietary S-316 extraction solvent Additional information about the OCMA-350 can be
that has been recycled by the Model SR-300 solvent obtained from the following source:
reclaimer. According to Horiba, the reuse of this
extraction solvent can reduce solvent costs by up to Horiba Instruments Incorporated
90 percent. Mr. Jim Vance
17671 Armstrong Avenue
2.2.2 Operating Procedure Irvine, CA 92614
Telephone: (800) 4HORIBA, extension 170
The OCMA-350 is calibrated using known standards. Fax: (949) 250-0924
Horiba generally recommends use of B-heavy oil, which E-mail: [email protected]
Internet: www.horiba.com

15
 Chapter 3
Demonstration Site Descriptions

This chapter describes the three sites selected for investigation was conducted. During this investigation,
conducting the demonstration. The first site is referred to samples were collected from the five candidate areas and
as the Navy BVC site; it is located in Port Hueneme, were analyzed for GRO and EDRO using SW-846
California, and contains three sampling areas. The second Method 8015B (modified) by the reference laboratory,
site is referred to as the Kelly AFB site; it is located in San Severn Trent Laboratories in Tampa, Florida (STL Tampa
Antonio, Texas, and contains one sampling area. The third East). The site descriptions in Sections 3.1 through 3.3 are
site is referred to as the PC site; it is located in north- based on data collected during predemonstration
central Indiana and contains one sampling area. After investigation sampling activities, data collected during
review of the information available on these and other demonstration sampling activities, and information
candidate sites, the Navy BVC, Kelly AFB, and PC sites provided by the site representatives. Physical
were selected based on the following criteria: characterization of samples was performed in the field by
a geologist during both predemonstration investigation and
• Site Diversity—Collectively, the three sites contained demonstration activities.
sampling areas with the different soil types and the
different levels and types of PHC contamination Some of the predemonstration investigation samples were
needed to evaluate the seven field measurement also analyzed by the OCMA-350 developer, Horiba, at its
devices selected for the demonstration. facility. Horiba used reference laboratory and OCMA-350
results to gain a preliminary understanding of the
• Access and Cooperation—The site representatives demonstration samples and to prepare for the
were interested in supporting the demonstration by demonstration.
providing site access for collection of soil samples
required for the demonstration. In addition, the field Table 3-1 summarizes key site characteristics, including
measurement devices were to be demonstrated at the the contamination type, sampling depth intervals, TPH
Navy BVC site using soil samples from all three sites, concentration ranges, and soil type in each sampling area.
and the Navy BVC site representatives were willing to The TPH concentration ranges and soil types presented in
provide the site support facilities required for the Table 3-1 and throughout this report are based on
demonstration and to support a visitors’ day during the reference laboratory TPH results for demonstration
demonstration. As a testing location for the samples and soil characterization completed during the
Department of Defense National Environmental demonstration, respectively. TPH concentration range and
Technology Test Site program, the Navy BVC site is soil type information obtained during the demonstration
used to demonstrate technologies and systems for was generally consistent with the information obtained
characterizing or remediating soil, sediment, and during the predemonstration investigation except for the
groundwater contaminated with fuel hydrocarbons or B-38 Area at Kelly AFB. Additional information on
waste oil. differences between demonstration and predemonstration
investigation activities and results is presented in
To ensure that the sampling areas were selected based on Section 3.2.
current site characteristics, a predemonstration

16
Table 3-1. Summary of Site Characteristics

Approximate
Sampling Depth
Interval TPH Concentration
Site Sampling Area Contamination Typea (foot bgs) Range (mg/kg) Type of Soil
b
Navy Base Fuel Farm Area EDRO (weathered diesel with Upper layer 44.1 to 93.7 Medium-grained sand
Ventura carbon range from n-C10
b
County through n-C40) Lower layer 8,090 to 15,000

Naval Exchange GRO and EDRO (fairly 7 to 8 28.1 to 280 Medium-grained sand
Service Station weathered gasoline with carbon
Area range from n-C6 through n-C14) 8 to 9 144 to 2,570
9 to 10 617 to 3,030
10 to 11 9.56 to 293
Phytoremediation EDRO (heavy lubricating oil 1.5 to 2.5 1,130 to 2,140 Silty sand
Area with carbon range from n-C14
through n-C40+)
Kelly Air B-38 Area GRO and EDRO (fresh 23 to 25 43.8 to 193 Sandy clay or silty sand and gravel
Force gasoline and diesel or in upper depth interval and clayey
Base weathered gasoline and trace sand and gravel in deeper depth
amounts of lubricating oil with 25 to 27 41.5 to 69.4 interval
carbon range from n-C6 through
n-C40)
Petroleum Slop Fill Tank GRO and EDRO (combination 2 to 4 6.16 to 3,300 Silty clay with traces of sand and
company Area of slightly weathered gasoline, gravel in deeper depth intervals
kerosene, JP-5, and diesel with 4 to 6 37.1 to 3,960
carbon range from n-C5 through 6 to 8 43.9 to 1,210
n-C32)
8 to 10 52.4 to 554

Notes:

bgs = Below ground surface

mg/kg = Milligram per kilogram
a
The beginning or end point of the carbon range identified as “n-Cx” represents an alkane marker consisting of “x” carbon atoms on a gas
chromatogram.
b
Because of soil conditions encountered in the Fuel Farm Area, the sampling depth intervals could not be accurately determined. Sample collection
was initiated approximately 10 feet bgs, and attempts were made to collect 4-foot-long soil cores. This approach resulted in varying degrees of
core tube penetration up to 17 feet bgs. At each location in the area, the sample cores were divided into two samples based on visual observations.
The upper layer of the soil core, which consisted of yellowish-brown, medium-grained sand, made up one sample, and the lower layer of the soil
core, which consisted of grayish-black, medium-grained sand and smelled of hydrocarbons, made up the second sample.

3.1 Navy Base Ventura County Site the Navy BVC site. Tank No. 5114 along the south edge
of the FFA was used to store marine diesel. After Tank
The Navy BVC site in Port Hueneme, California, covers No. 5114 was deactivated in 1991, corroded pipelines
about 1,600 acres along the south California coast. Three leading into and out of the tank leaked and contaminated
areas at the Navy BVC site were selected as sampling areas the surrounding soil with diesel.
for the demonstration: (1) the Fuel Farm Area (FFA),
(2) the Naval Exchange (NEX) Service Station Area, and The horizontal area of contamination in the FFA was
(3) the Phytoremediation Area (PRA). These areas are estimated to be about 20 feet wide and 90 feet long.
briefly described below. Demonstration samples were collected within several
inches of the three predemonstration investigation
3.1.1 Fuel Farm Area sampling locations in the FFA using a Geoprobe®.
Samples were collected at the three locations from east to
The FFA is a tank farm in the southwest corner of the west and about 5 feet apart. During the demonstration, soil
Navy BVC site. The area contains five tanks and was in the area was found to generally consist of medium-
constructed to refuel ships and to supply heating fuel for grained sand, and the soil cores contained two distinct

17
layers. The upper layer consisted of yellowish-brown, to 11-foot bgs depth interval. During the predemonstration
medium-grained sand with no hydrocarbon odor and TPH investigation, the TPH concentrations in the (1) top two
concentrations ranging from 44.1 to 93.7 mg/kg; the upper depth intervals (7 to 8 and 8 to 9 feet bgs) ranged from 25
layer’s TPH concentration range during the to 65 mg/kg and (2) bottom depth interval (10 to 11 feet
predemonstration investigation was 38 to 470 mg/kg. The bgs) ranged from 24 to 300 mg/kg.
lower layer consisted of grayish-black, medium-grained
sand with a strong hydrocarbon odor and TPH Gas chromatograms from the predemonstration
concentrations ranging from 8,090 to 15,000 mg/kg; the investigation and the demonstration showed that NEX
lower layer’s TPH concentration range during the Service Station Area soil samples contained (1) fairly
predemonstration investigation was 7,700 to weathered gasoline with a high aromatic hydrocarbon
11,000 mg/kg. content and (2) hydrocarbons in the n-C6 through n-C14
carbon range. Benzene, toluene, ethylbenzene, and xylene
Gas chromatograms from the predemonstration (BTEX) analytical results for predemonstration
investigation and the demonstration showed that FFA soil investigation samples from the 9- to 10-foot bgs depth
samples contained (1) weathered diesel, (2) hydrocarbons interval at the middle sampling location revealed a
in the n-C10 through n-C28 carbon range with the concentration of 347 mg/kg; BTEX made up 39 percent of
hydrocarbon hump maximizing at n-C17 , and the total GRO and 27 percent of the TPH at this location.
(3) hydrocarbons in the n-C12 through n-C40 carbon range During the predemonstration investigation, BTEX analyses
with the hydrocarbon hump maximizing at n-C20. were conducted at the request of a few developers to
estimate the aromatic hydrocarbon content of the GRO;
3.1.2 Naval Exchange Service Station Area such analyses were not conducted for demonstration
samples.
The NEX Service Station Area lies in the northeast portion
of the Navy BVC site. About 11,000 gallons of regular 3.1.3 Phytoremediation Area
and unleaded gasoline was released from UST lines in this
area between September 1984 and March 1985. Although The PRA lies north of the FFA and west of the NEX
the primary soil contaminant in this area is gasoline, Service Station Area at the Navy BVC site. The PRA
EDRO is also of concern because (1) another spill north of consists of soil from a fuel tank removal project conducted
the area may have resulted in a commingled plume of at the Naval Weapons Station in Seal Beach, California.
gasoline and diesel and (2) a significant portion of The area is contained within concrete railings and is
weathered gasoline is associated with EDRO. 60 feet wide, 100 feet long, and about 3 feet deep. It
consists of 12 cells of equal size (20 by 25 feet) that have
The horizontal area of contamination in the NEX Service three different types of cover: (1) unvegetated cover, (2) a
Station Area was estimated to be about 450 feet wide and grass and legume mix, and (3) a native grass mix. There
750 feet long. During the demonstration, samples were are four replicate cells of each cover type.
collected at the three predemonstration investigation
sampling locations in the NEX Service Station Area from In the PRA, demonstration samples were collected from
south to north and about 60 feet apart using a Geoprobe®. the 1.5- to 2.5-foot bgs depth interval within several inches
Soil in the area was found to generally consist of of the six predemonstration investigation sampling
(1) brownish-black, medium-grained sand in the locations using a split-core sampler. During the
uppermost depth interval and (2) grayish-black, medium- demonstration, soil at four adjacent sampling locations
grained sand in the three deeper depth intervals. Traces of was found to generally consist of dark yellowish-brown,
coarse sand were also present in the deepest depth interval. silty sand with some clay and no hydrocarbon odor. Soil
Soil samples collected from the area had a strong at the two remaining adjacent sampling locations primarily
hydrocarbon odor. The water table in the area was consisted of dark yellowish-brown, clayey sand with no
encountered at about 9 feet below ground surface (bgs). hydrocarbon odor, indicating the absence of volatile
During the demonstration, TPH concentrations ranged PHCs. The TPH concentrations in the demonstration
from 28.1 to 280 mg/kg in the 7- to 8-foot bgs depth samples ranged from 1,130 to 2,140 mg/kg; the TPH
interval; 144 to 3,030 mg/kg in the 8- to 9- and 9- to 10- concentrations in the predemonstration investigation
foot bgs depth intervals; and 9.56 to 293 mg/kg in the 10- samples ranged from 1,500 to 2,700 mg/kg.

18
Gas chromatograms from the predemonstration accessing the fourth location sampled during the
investigation and the demonstration showed that PRA soil predemonstration investigation.
samples contained (1) heavy lubricating oil and
(2) hydrocarbons in the n-C14 through n-C40+ carbon range During the demonstration, soil in the area was found to
with the hydrocarbon hump maximizing at n-C32. generally consist of (1) sandy clay or silty sand and gravel
in the upper depth interval with a TPH concentration
3.2 Kelly Air Force Base Site between 43.8 and 193 mg/kg and (2) clayey sand and
gravel in the deeper depth interval with TPH
The Kelly AFB site covers approximately 4,660 acres and concentrations between 41.5 and 69.4 mg/kg. Soil samples
is about 7 miles from the center of San Antonio, Texas. collected in the area had little or no hydrocarbon odor.
One area at Kelly AFB, the B-38 Area, was selected as a Gas chromatograms from the demonstration showed that
sampling area for the demonstration. The B-38 Area lies B-38 Area soil samples contained either (1) fresh gasoline,
along the east boundary of Kelly AFB and is part of an diesel, and hydrocarbons in the n-C6 through n-C25 carbon
active UST farm that serves the government vehicle range with the hydrocarbon hump maximizing at n-C17;
refueling station at the base. In December 1992, (2) weathered gasoline with trace amounts of lubricating
subsurface soil contamination resulting from leaking diesel oil and hydrocarbons in the n-C6 through n-C30 carbon
and gasoline USTs and associated piping was discovered range with a hydrocarbon hump representing the
in this area during UST removal and upgrading activities. lubricating oil between n-C20 and n-C30; or (3) weathered
gasoline with trace amounts of lubricating oil
The B-38 Area was estimated to be about 150 square feet and hydrocarbons in the n-C6 through n-C40 carbon range
in size. Based on discussions with site representatives, with a hydrocarbon hump representing the lubricating oil
predemonstration investigation samples were collected in maximizing at n-C31.
the 13- to 17- and 29- to 30-foot bgs depth intervals at four
locations in the area using a Geoprobe®. Based on 3.3 Petroleum Company Site
historical information, the water table in the area fluctuates
between 16 and 24 feet bgs. During the One area at the PC site in north-central Indiana, the Slop
predemonstration investigation, soil in the area was found Fill Tank (SFT) Area, was selected as a sampling area for
to generally consist of (1) clayey silt in the upper depth the demonstration. The SFT Area lies in the west-central
interval above the water table with a TPH concentration of portion of the PC site and is part of an active fuel tank
9 mg/kg and (2) sandy clay with significant gravel in the farm. Although the primary soil contaminant in this area
deeper depth interval below the water table with TPH is gasoline, EDRO is also of concern because of a heating
concentrations ranging from 9 to 18 mg/kg. Gas oil release that occurred north of the area.
chromatograms from the predemonstration investigation
showed that B-38 Area soil samples contained (1) heavy The SFT Area was estimated to be 20 feet long and 20 feet
lubricating oil and (2) hydrocarbons in the n-C24 through wide. In this area, demonstration samples were collected
n-C30 carbon range. from 2 to 10 feet bgs at 2-foot depth intervals within
several inches of the five predemonstration investigation
Based on the low TPH concentrations and the type of sampling locations using a Geoprobe®. Four of the
contamination detected during the predemonstration sampling locations were spaced 15 feet apart to form the
investigation as well as discussions with site corners of a square, and the fifth sampling location was at
representatives who indicated that most of the contam- the center of the square. During the demonstration, soil in
ination in the B-38 Area can be found at or near the water the area was found to generally consist of brown to
table, demonstration samples were collected near the water brownish-gray, silty clay with traces of sand and gravel in
table. During the demonstration, the water table was the deeper depth intervals. Demonstration soil samples
24 feet bgs. Therefore, the demonstration samples were collected in the area had little or no hydrocarbon odor.
collected in the 23- to 25- and 25- to 27-foot bgs depth During the demonstration, soil in the three upper depth
intervals at three locations in the B-38 Area using a intervals had TPH concentrations ranging from 6.16 to
Geoprobe®. Air Force activities in the area during the 3,960 mg/kg, and soil in the deepest depth interval had
demonstration prevented the sampling team from TPH concentrations ranging from 52.4 to 554 mg/kg.
During the predemonstration investigation, soils in the

19
three upper depth intervals and the deepest depth interval BTEX analytical results for predemonstration
had TPH concentrations ranging from 27 to 1,300 mg/kg investigation samples from the deepest depth interval
and from 49 to 260 mg/kg, respectively. revealed concentrations of 26, 197, and 67 mg/kg at the
northwest, center, and southwest sampling locations,
Gas chromatograms from the predemonstration respectively. At the northwest location, BTEX made up
investigation and the demonstration showed that SFT Area 13 percent of the total GRO and 5 percent of the TPH. At
soil samples contained (1) slightly weathered gasoline, the center location, BTEX made up 16 percent of the total
kerosene, JP-5, and diesel and (2) hydrocarbons in the GRO and 7 percent of the TPH. At the southwest location,
n-C5 through n-C20 carbon range. There was also evidence BTEX made up 23 percent of the total GRO and
of an unidentified petroleum product containing 18 percent of the TPH. BTEX analyses were not
hydrocarbons in the n-C24 through n-C32 carbon range. conducted for demonstration samples.

20
 Chapter 4
Demonstration Approach

This chapter presents the objectives (Section 4.1), design P5. Measure the time required for TPH measurement
(Section 4.2), and sample preparation and management
procedures (Section 4.3) for the demonstration. P6. Estimate costs associated with TPH measurement

4.1 Demonstration Objectives The secondary objectives for the demonstration of the
individual field measurement devices were as follows:
The primary goal of the SITE MMT Program is to develop
reliable performance and cost data on innovative, field- S1. Document the skills and training required to properly
ready technologies. A SITE demonstration must provide operate the device
detailed and reliable performance and cost data so that
potential technology users have adequate information to S2. Document health and safety concerns associated with
make sound judgments regarding an innovative operating the device
technology’s applicability to a specific site and to compare
the technology to conventional technologies. S3. Document the portability of the device

The demonstration had both primary and secondary S4. Evaluate the durability of the device based on its
objectives. Primary objectives were critical to the materials of construction and engineering design
technology evaluation and required the use of quantitative
results to draw conclusions regarding a technology’s S5. Document the availability of the device and associated
performance. Secondary objectives pertained to spare parts
information that was useful but did not necessarily require
the use of quantitative results to draw conclusions The objectives for the demonstration were developed based
regarding a technology’s performance. on input from MMT Program stakeholders, general user
expectations of field measurement devices, characteristics
The primary objectives for the demonstration of the of the demonstration areas, the time available to complete
individual field measurement devices were as follows: the demonstration, and device capabilities that the
developers intended to highlight.
P1. Determine the MDL
4.2 Demonstration Design
P2. Evaluate the accuracy and precision of TPH
measurement for a variety of contaminated soil A predemonstration sampling and analysis investigation
samples was conducted to assess existing conditions and confirm
available information on physical and chemical
P3. Evaluate the effect of interferents on TPH characteristics of soil in each demonstration area. Based
measurement on information from the predemonstration investigation as
well as available historical data, a demonstration design
P4. Evaluate the effect of soil moisture content on TPH was developed to address the demonstration objectives.
measurement Input regarding the demonstration design was obtained

21
from the developers and demonstration site comparisons of field measurement device and reference
representatives. The demonstration design is summarized method results.
below.
To facilitate effective use of available information on both
The demonstration involved analysis of soil environmental the environmental and PE samples during the
samples, soil performance evaluation (PE) samples, and demonstration, the developers and reference laboratory
liquid PE samples. The environmental samples were were informed of (1) whether each sample was an
collected from three contaminated sites, and the PE environmental or PE sample, (2) the area where each
samples were obtained from a commercial provider, environmental sample was collected, and (3) the
Environmental Resource Associates (ERA) in Arvada, contamination type and concentration range of each
Colorado. Collectively, the environmental and PE samples sample. This information was included in each sample
provided the different matrix types and the different levels identification number. Each sample was identified as
and types of PHC contamination needed to perform a having a low (less than 100 mg/kg), medium (100 to
comprehensive demonstration. 1,000 mg/kg), or high (greater than 1,000 mg/kg) TPH
concentration range. The concentration ranges were based
The environmental samples were soil core samples primarily on predemonstration investigation results or the
collected from the demonstration areas at the Navy BVC, amount of weathered gasoline or diesel added during PE
Kelly AFB, and PC sites described in Chapter 3. The soil sample preparation. The concentration ranges were meant
core samples collected at the Kelly AFB and PC sites were to be used only as a guide by the developers and reference
shipped to the Navy BVC site 5 days prior to the start of laboratory. The gasoline used for PE sample preparation
the field analysis activities. Each soil core sample was 50 percent weathered; the weathering was achieved by
collected from a specific depth interval at a particular bubbling nitrogen gas into a known volume of gasoline
sampling location in a given area was homogenized and until the volume was reduced by 50 percent. Some PE
placed in individual sample containers. Soil samples were samples also contained interferents specifically added to
then provided to the developers and reference laboratory. evaluate the effect of interferents on TPH measurement.
In addition, the PE samples were obtained from ERA for The type of contamination and expected TPH concen-
distribution to the developers and reference laboratory. tration ranges were identified; however, the specific
Field analysis of all environmental and PE samples was compounds used as interferents were not identified. All
conducted near the PRA at the Navy BVC site. PE samples were prepared in triplicate as separate, blind
samples.
The field measurement devices were evaluated based
primarily on how they compared with the reference During the demonstration, a Horiba field technician
method selected for the demonstration. PE samples were operated the OCMA-350, and EPA representatives made
used to verify that reference method performance was observations to evaluate the device. All the developers
acceptable. However, for the comparison with the device were given the opportunity to choose not to analyze
results, the reference method results were not adjusted samples collected in a particular area or a particular class
based on the recoveries observed during analysis of the PE of samples, depending on the intended uses of their
samples. devices. Horiba chose to analyze all the demonstration
samples.
The sample collection and homogenization procedures
may have resulted in GRO losses of up to one order of Details of the approach used to address the primary and
magnitude in environmental samples. Despite any such secondary objectives for the demonstration are presented
losses, the homogenized samples were expected to contain in Sections 4.2.1 and 4.2.2, respectively.
sufficient levels of GRO to allow demonstration objectives
to be achieved. Moreover, the environmental sample 4.2.1 Approach for Addressing Primary
collection and homogenization procedures implemented Objectives
during the demonstration ensured that the developers and
reference laboratory received the same sample material for This section presents the approach used to address each
analysis, which was required to allow meaningful primary objective.

22
Primary Objective P1: Method Detection Limit were analyzed. The evaluation of analytical accuracy was
based on the assumption that a field measurement device
To determine the MDL for each field measurement device, may be used to (1) determine whether the TPH
low-concentration-range soil PE samples containing concentration in a given area exceeds an action level or
weathered gasoline or diesel were to be analyzed. The (2) perform a preliminary characterization of soil in a
low-range PE samples were prepared using Freon 113, given area. To evaluate whether the TPH concentration in
which facilitated preparation of homogenous samples. The a soil sample exceeded an action level, the developers and
target concentrations of the PE samples were set to meet reference laboratory were asked to determine whether TPH
the following criteria: (1) at the minimum acceptable concentrations in a given area or PE sample type exceeded
recoveries set by ERA, the samples contained measurable the action levels listed in Table 4-1. The action levels
TPH concentrations, and (2) when feasible, the sample chosen for environmental samples were based on the
TPH concentrations were generally between 1 and predemonstration investigation analytical results and state
10 times the MDLs claimed by the developers and the action levels. The action levels chosen for the PE samples
reference laboratory, as recommended by 40 Code of were based in part on the ERA acceptance limits for PE
Federal Regulations (CFR) Part 136, Appendix B, samples; therefore, each PE sample was expected to have
Revision 1.1.1. Horiba and the reference laboratory at least the TPH concentration indicated in Table 4-1.
analyzed seven weathered gasoline and seven diesel PE However, because of the problems associated with
samples to statistically determine the MDLs for GRO and preparation of the low-concentration-range weathered
EDRO soil samples. However, during the preparation of gasoline PE samples, the results for these samples could
low-range weathered gasoline PE samples, significant not be used to address primary objective P2.
volatilization of PHCs occurred because of the matrix used
for preparing these samples. Because of the problems In addition, neat (liquid) samples of weathered gasoline
associated with preparation of low-range weathered and diesel were analyzed by the developers and reference
gasoline PE samples, the results for these samples could laboratory to evaluate accuracy and precision. Because
not be used to determine the MDLs. extraction of the neat samples was not necessary, the
results for these samples provided accuracy and precision
Primary Objective P2: Accuracy and Precision information strictly associated with the analyses and were
not affected by extraction procedures.
To estimate the accuracy and precision of each field
measurement device, both environmental and PE samples

Table 4-1. Action Levels Used to Evaluate Analytical Accuracy

Site Area Typical TPH Concentration Rangea Action Level (mg/kg)

Navy Base Ventura County Fuel Farm Area Low and high 100
NEX Service Station Area Low to high 50
Phytoremediation Area High 1,500
Kelly Air Force Base B-38 Area Low 100
Petroleum company Slop Fill Tank Area Medium 500
Performance evaluation samples (GRO analysis) Medium 200
High 2,000
Performance evaluation samples (EDRO analysis) Low 15
Medium 200
High 2,000

Notes:

mg/kg = Milligram per kilogram

a
The typical TPH concentration ranges shown cover all the depth intervals in each area. Table 4-2 shows the depth intervals that were sampled
in each area and the typical TPH concentration range for each depth interval. The action level for each area was used as the basis for evaluating
sample analytical results regardless of the typical TPH concentration ranges for the various depth intervals.

23
Sample TPH results obtained using each field precision because TPH concentrations in environmental
measurement device and the reference method were samples collected during the demonstration sometimes
compared to the action levels presented in Table 4-1 in differed from the analytical results for predemonstration
order to determine whether sample TPH concentrations investigation samples. The low- and medium-range PE
were above the action levels. The results obtained using samples were prepared using Freon 113 as a carrier, which
the device and reference method were compared to facilitated preparation of homogenous samples.
determine how many times the device’s results agreed with
those of the reference method for a particular area or Additional information regarding analytical precision was
sample type. In addition, the ratio of the TPH results of a collected by having the developers and reference
given device to the TPH results of the reference method laboratory analyze extract duplicates. Extract duplicates
was calculated. The ratio was used to develop a frequency were prepared by extracting a soil sample once and
distribution in order to determine how many of the device collecting two aliquots of the extract. For environmental
and reference method results were within 30 percent, samples, one sample from each depth interval was
within 50 percent, and outside the 50 percent window. designated as an extract duplicate. Each sample
designated as an extract duplicate was collected from a
To complete a preliminary characterization of soil in a location where field triplicates were collected. To
given area using a field measurement device, the user may evaluate a given field measurement device’s ability to
have to demonstrate to a regulatory agency that (1) no precisely measure TPH, the relative standard deviation
statistically significant difference exists between the results (RSD) of the device and reference method TPH results for
of the laboratory method selected for the project (the triplicate samples was calculated. In addition, to evaluate
reference method) and the device results, indicating that the analytical precision of the device and reference
the device may be used as a substitute for the laboratory method, the relative percent difference (RPD) was
method, or (2) a consistent correlation exists between the calculated using the TPH results for extract duplicates.
device and laboratory method results, indicating that the
device results can be adjusted using the established Primary Objective P3: Effect of Interferents
correlation.
To evaluate the effect of interferents on each field
To evaluate whether a statistically significant difference measurement device’s ability to accurately measure TPH,
existed between a given field measurement device and the high-concentration-range soil PE samples containing
reference method results, a two-tailed, paired Student’s t- weathered gasoline or diesel with or without an interferent
test was performed. To determine whether a consistent were analyzed. As explained in Chapter 1, the definition
correlation existed between the TPH results of a given field of TPH is quite variable. For the purposes of addressing
measurement device and the reference method, a linear primary objective P3, the term “interferent” is used in a
regression was performed to estimate the square of the broad sense and is applied to both PHC and non-PHC
correlation coefficient (R2), the slope, and the intercept of compounds. The six different interferents evaluated
each regression equation. Separate regression equations during the demonstration were MTBE; tetrachloroethene
were developed for each demonstration area and for the PE (PCE); Stoddard solvent; turpentine (an alpha and beta
samples that did not contain interferents. The reliability of pinene mixture); 1,2,4-trichlorobenzene; and humic acid.
the regression equations was tested using the F-test; the The boiling points and vapor pressures of (1) MTBE and
regression equation probability derived from the F-test was PCE are similar to those of GRO; (2) Stoddard solvent and
used to evaluate whether the correlation between the TPH turpentine are similar to those of GRO and EDRO; and
results of the device and the reference method occurred (3) 1,2,4-trichlorobenzene and humic acid are similar to
merely by chance. those of EDRO. The solubility, availability, and cost of
the interferents were also considered during interferent
To evaluate analytical precision, one set of blind field selection. Specific reasons for the selection of the six
triplicate environmental samples was collected from each interferents are presented below.
depth interval at one location in each demonstration area
except the B-38 Area, where site conditions allowed • MTBE is an oxygenated gasoline additive that is
collection of triplicates in the top depth interval only. detected in the GRO analysis during TPH
Blind triplicate low-, medium-, and high-concentration- measurement using a GC.
range PE samples were also used to evaluate analytical

24
• PCE is not a petroleum product but is detected in the (liquid) samples of these interferents were prepared and
GRO analysis during TPH measurement using a GC. used as quasi-control samples to evaluate the effect of
PCE may also be viewed as a typical halogenated each interferent on the field measurement device and
solvent that may be present in some environmental reference method results. Each PE sample was prepared
samples. in triplicate and submitted to the developers and reference
laboratory as blind triplicate samples.
• Stoddard solvent is an aliphatic naphtha compound
with a carbon range of n-C8 through n-C14 and is partly To evaluate the effects of interferents on a given field
detected in both the GRO and EDRO analyses during measurement device’s ability to accurately measure TPH
TPH measurement using a GC. under primary objective P3, the means and standard
deviations of the TPH results for triplicate PE samples
• Turpentine is not a petroleum product but has a carbon were calculated. The mean for each group of samples was
range of n-C9 through n-C15 and is partly detected in qualitatively evaluated to determine whether the data
both the GRO and EDRO analyses during TPH showed any trend—that is, whether an increase in the
measurement using a GC. Turpentine may also be interferent concentration resulted in an increase or
viewed as a substance that behaves similarly to a decrease in the measured TPH concentration. A one-way
typical naturally occurring oil or grease during TPH analysis of variance was performed to determine whether
measurement using a GC. the group means were the same or different.

• The compound 1,2,4-trichlorobenzene is not a Primary Objective P4: Effect of Soil Moisture Content
petroleum product but is detected in the EDRO
analysis. This compound may also be viewed as a To evaluate the effect of soil moisture content, high-
typical halogenated semivolatile organic compound concentration-range soil PE samples containing weathered
that behaves similarly to a chlorinated pesticide or gasoline or diesel were analyzed. PE samples containing
PCB during TPH measurement using a GC. weathered gasoline were prepared at two moisture levels:
9 percent moisture and 16 percent moisture. PE samples
• Humic acid is a hydrocarbon mixture that is containing diesel were also prepared at two moisture
representative of naturally occurring organic carbon in levels: negligible moisture (less than 1 percent) and
soil and was suspected to be detected during EDRO 9 percent moisture. All the moisture levels were selected
analysis. based on the constraints associated with sample
preparation. For example, 9 percent moisture represents
Based on the principles of operation of the field the minimum moisture level for containerizing samples in
measurement devices, several of the interferents were EnCores and 16 percent moisture represents the saturation
suspected to be detected by the devices. level of the soil used to prepare PE samples. Diesel
samples with negligible moisture could be prepared
The PE samples containing MTBE and PCE were not because they did not require EnCores for containerization;
prepared with diesel and the PE samples containing based on vapor pressure data for diesel and weathered
1,2,4-trichlorobenzene and humic acid were not prepared gasoline, 4-ounce jars were considered to be appropriate
with weathered gasoline because these interferents were for containerizing diesel samples but not for containerizing
not expected to impact the analyses and because practical weathered gasoline samples. Each PE sample was
difficulties such as solubility constraints were associated prepared in triplicate.
with preparation of such samples.
To measure the effect of soil moisture content on a given
Appropriate control samples were also prepared and field measurement device’s ability to accurately measure
analyzed to address primary objective P3. These samples TPH under primary objective P4, the means and standard
included processed garden soil, processed garden soil and deviations of the TPH results for triplicate PE samples
weathered gasoline, processed garden soil and diesel, and containing weathered gasoline and diesel at two moisture
processed garden soil and humic acid samples. Because of levels were calculated. A two-tailed, two-sample
solubility constraints, control samples containing MTBE; Student’s t-test was performed to determine whether the
PCE; Stoddard solvent; turpentine; or 1,2,4- device and reference method results were impacted by
trichlorobenzene could not be prepared. Instead, neat moisture—that is, to determine whether an increase in

25
moisture resulted in an increase or decrease in the TPH 4.2.2 Approach for Addressing Secondary
concentrations measured. Objectives
Primary Objective P5: Time Required for TPH Secondary objectives were addressed based on field
Measurement observations made during the demonstration. Specifically,
EPA representatives observed TPH measurement activities
The sample throughput (the number of TPH measurements and documented them in a field logbook. Each developer
per unit of time) was determined for each field was given the opportunity to review the field logbook at
measurement device by measuring the time required for the end of each day of the demonstration. The approach
each activity associated with TPH measurement, including used to address each secondary objective for each field
device setup, sample extraction, sample analysis, and data measurement device is discussed below.
package preparation. The EPA provided each developer
with investigative samples stored in coolers. The • The skills and training required for proper device
developer unpacked the coolers and checked the chain-of- operation (secondary objective S1) were evaluated by
custody forms to verify that it had received the correct observing and noting the skills required to operate the
samples. Time measurement began when the developer device and prepare the data package during the
began to set up its device. The total time required to demonstration and by discussing necessary user
complete analysis of all investigative samples was training with developer personnel.
recorded. Analysis was considered to be complete and
time measurement stopped when the developer provided • Health and safety concerns associated with device
the EPA with a summary table of results, a run log, and operation (secondary objective S2) were evaluated by
any supplementary information that the developer chose. observing and noting possible health and safety
The summary table listed all samples analyzed and their concerns during the demonstration, such as the types
respective TPH concentrations. of hazardous substances handled by developer
personnel during analysis, the number of times that
For the reference laboratory, the total analytical time hazardous substances were transferred from one
began to be measured when the laboratory received all the container to another during the analytical procedure,
investigative samples, and time measurement continued and direct exposure of developer personnel to
until the EPA representatives received a complete data hazardous substances.
package from the laboratory.
• The portability of the device (secondary objective S3)
Primary Objective P6: Costs Associated with TPH was evaluated by observing and noting the weight and
Measurement size of the device and additional equipment required
for TPH measurement as well as how easily the device
To estimate the costs associated with TPH measurement was set up for use during the demonstration.
for each field measurement device, the following five cost
categories were identified: capital equipment, supplies, • The durability of the device (secondary objective S4)
support equipment, labor, and investigation-derived waste was evaluated by noting the materials of construction
(IDW) disposal. Chapter 8 of this ITVR discusses the of the device and additional equipment required for
costs estimated for the OCMA-350 based on these cost TPH measurement. In addition, EPA representatives
categories. noted likely device failures or repairs that may be
necessary during extended use of the device.
Table 4-2 summarizes the demonstration approach used to Downtime required to make device repairs during the
address the primary objectives and includes demonstration demonstration was also noted.
area characteristics, approximate sampling depth intervals,
and the rationale for the analyses performed by the • The availability of the device and associated spare
reference laboratory. parts (secondary objective S5) was evaluated by
discussing the availability of replacement devices with
developer personnel and determining whether spare
parts were available in retail stores or only from the

26
 Table 4-2. Demonstration Approach

Approximate Typical TPH

Sampling Depth Objective Concentration Rationale for Analyses
Site Area Interval (foot bgs) Addresseda Soil Characteristics Contamination Type Rangeb by Reference Laboratory
Navy FFA Upper layerc P2 Medium-grained sand Weathered diesel with carbon range from Low Only EDRO because samples did not
BVC c n-C10 through n-C40 contain PHCs in gasoline range
Lower layer High
NEX 7 to 8 Medium-grained sand Fairly weathered gasoline with carbon range Low to GRO and EDRO because samples
Service from n-C6 through n-C14 medium contained PHCs in both gasoline and
Station diesel ranges
8 to 9 Medium to
Area
high
9 to 10 High
10 to 11 Low
PRA 1.5 to 2.5 Silty sand Heavy lubricating oil with carbon range from High Only EDRO because samples did not
n-C14 through n-C40 contain PHCs in gasoline range
Kelly B-38 23 to 25 Sandy clay or silty sand and Fresh gasoline and diesel or weathered Low GRO and EDRO because samples
AFB Area gravel in upper depth interval and gasoline and trace amounts of lubricating oil contained PHCs in both gasoline and
25 to 27 clayey sand and gravel in deeper with carbon range from n-C6 through n-C40 diesel ranges
depth interval
PC SFT 2 to 4 Silty clay with traces of sand in Combination of slightly weathered gasoline, Medium
Area deeper depth intervals kerosene, JP-5, and diesel with carbon range
4 to 6
from n-C5 through n-C32

27
6 to 8
8 to 10

Typical TPH
Objective Concentration Rationale for Analyses
Sample Matrix Addresseda Soil Characteristics Contamination Type rangeb by Reference Laboratory
Ottawa sand P1, P2 Fine-grained sand Weathered gasolined Low GRO and EDRO because weathered
(PE sample) gasoline contains significant amounts of
PHCs in both gasoline and diesel
ranges
Diesel Only EDRO because diesel does not
contain PHCs in gasoline range
Processed garden soil (PE sample) P2 Silty sand Weathered gasoline Medium and GRO and EDRO because weathered
high gasoline contains significant amounts of
PHCs in both gasoline and diesel
ranges
Diesel Only EDRO because diesel does not
contain PHCs in gasoline range
 Table 4-2. Demonstration Approach (Continued)

Typical TPH
Objective Concentration Rationale for Analyses
Sample Matrix Addresseda Soil Characteristics Contamination Type rangeb by Reference Laboratory
Not applicable (neat liquid PE P2 Not applicable Weathered gasoline High GRO and EDRO because weathered
sample) (Continued) gasoline contains significant amounts of
PHCs in both gasoline and diesel
ranges
Diesel High Only EDRO because diesel does not
contain PHCs in gasoline range
Processed garden soil (PE sample) P3 Silty sand Blank soil (control sample) Trace GRO and EDRO because processed
garden soil may contain trace
concentrations of PHCs in both gasoline
and diesel ranges
Weathered gasoline High GRO and EDRO because weathered
gasoline contains significant amounts of
Weathered gasoline and MTBE (1,100 mg/kg), PHCs in both gasoline and diesel
PCE (2,810 mg/kg), Stoddard solvent ranges
(2,900 mg/kg), or turpentine (2,730 mg/kg)
Weathered gasoline and MTBE (1,700 mg/kg),
PCE (13,100 mg/kg), Stoddard solvent
(15,400 mg/kg), or turpentine (12,900 mg/kg)

28
Diesel Only EDRO because diesel does not
contain PHCs in gasoline range
Diesel and Stoddard solvent (3,650 mg/kg) or GRO and EDRO because (1) Stoddard
turpentine (3,850 mg/kg) solvent contains PHCs in both gasoline
and diesel ranges and (2) turpentine
Diesel and Stoddard solvent (18,200 mg/kg) interferes with both analyses
or turpentine (19,600 mg/kg)

Diesel and 1,2,4-trichlorobenzene Only EDRO because 1,2,4-

(3,350 mg/kg) or humic acid (3,940 mg/kg) trichlorobenzene and humic acid do not
interfere with GRO analysis
Diesel and 1,2,4-trichlorobenzene
(16,600 mg/kg) or humic acid (19,500 mg/kg)
Humic acid (3,940 mg/kg) Trace Only EDRO because humic acid does
not interfere with GRO analysis

The contribution of trace concentrations

(less than 15 mg/kg) GRO found in
Humic acid (19,500 mg/kg) processed garden soil during the
predemonstration investigation was
considered to be insignificant evaluation
of the effect of humic acid interference,
which occurs in the diesel range.
 Table 4-2. Demonstration Approach (Continued)

Typical TPH
Objective Concentration Rationale for Analyses
Sample Matrix Addresseda Soil Characteristics Contamination Type rangeb by Reference Laboratory
Not applicable (neat liquid PE P3 Not applicable Weathered gasoline High GRO and EDRO because weathered
sample) (Continued) gasoline contains significant amounts of
PHCs in both gasoline and diesel
ranges
Diesel Only EDRO because diesel does not
contain PHCs in gasoline range
MTBE Only GRO because MTBE and PCE do
not interfere with EDRO analysis
PCE Not
applicable
Stoddard solvent High GRO and EDRO because Stoddard
solvent contains PHCs in both gasoline
and diesel ranges
Turpentine Not GRO and EDRO because turpentine
applicable interferes with both analyses
1,2,4-Trichlorobenzene Only EDRO because 1,2,4-
trichlorobenzene does not interfere with
GRO analysis
Processed garden soil (PE sample) P4 Silty sand Weathered gasoline (samples prepared at High GRO and EDRO because weathered

29
9 and 16 percent moisture levels) gasoline contains significant amounts of
PHCs in both gasoline and diesel
ranges
Diesel (samples prepared at negligible [less Only EDRO because diesel does not
than 1 percent] and 9 percent moisture levels) contain PHCs in gasoline range

Notes:

AFB = Air Force Base FFA = Fuel Farm Area NEX = Naval Exchange PE = Performance evaluation
bgs = Below ground surface mg/kg = Milligram per kilogram PC = Petroleum company PHC = Petroleum hydrocarbon
BVC = Base Ventura County MTBE = Methyl-tert-butyl ether PCE = Tetrachloroethene PRA = Phytoremediation Area
SFT = Slop Fill Tank
a
Field observations of all sample analyses conducted during the demonstration were used to address primary objectives P5 and P6 and the secondary objectives.
b
The typical TPH concentration range was based on reference laboratory results for the demonstration. The typical low, medium, and high ranges indicate TPH concentrations of less than
100 mg/kg; 100 to 1,000 mg/kg; and greater than 1,000 mg/kg, respectively.
c
Because of soil conditions encountered in the FFA during the demonstration, the sampling depth intervals could not be accurately determined. Sample collection was initiated approximately
10 feet bgs, and attempts were made to collect 4-foot-long soil cores. For each sampling location in the area, the sample cores were divided into two samples based on visual observations.
The upper layer of the soil core made up one sample, and the lower layer of the soil core made up the second sample.
d
Because of problems that arose during preparation of PE samples with low concentrations of weathered gasoline, the results for these samples were not used to evaluate the field measurement
devices.
 developer. In addition, the availability of spare parts spoon or gloved hands until the sample was visibly
required during the demonstration was noted. homogeneous. During or immediately following
homogenization, any free water was poured from the
Field observations of the analyses of all the samples stainless-steel bowl containing the soil sample into a
described in Table 4-2 were used to address the secondary container designated for IDW. During the demonstration,
objectives for the demonstration. the field sampling team used only nitrile gloves to avoid
the possibility of phthalate contamination from handling
4.3 Sample Preparation and Management samples with plastic gloves. Such contamination had
occurred during the predemonstration investigation.
This section presents sample preparation and management
procedures used during the demonstration. Specifically, After sample homogenization, the samples were placed in
this section describes how samples were collected, (1) EnCores of approximately 5-gram capacity for GRO
containerized, labeled, stored, and shipped during the analysis; (2) 4-ounce, glass jars provided by the reference
demonstration. Additional details about the sample laboratory for EDRO and percent moisture analyses; and
preparation and management procedures are presented in (3) EnCores of approximately 25-gram capacity for TPH
the demonstration plan (EPA 2000). analysis. Using a quartering technique, each sample
container was filled by alternately spooning soil from one
4.3.1 Sample Preparation quadrant of the mixing bowl and then from the opposite
quadrant until the container was full. The 4-ounce, glass
The sample preparation procedures for both environmental jars were filled after all the EnCores for a given sample
and PE samples are described below. had been filled. After a sample container was filled, it was
immediately closed to minimize volatilization of
Environmental Samples contaminants. To minimize the time required for sample
homogenization and filling of sample containers, these
For the demonstration, environmental samples were activities were simultaneously conducted by four
collected in the areas that were used for the personnel.
predemonstration investigation: (1) the FFA, NEX Service
Station Area, and PRA at the Navy BVC site; (2) the B-38 Because of the large number of containers being filled,
Area at the Kelly AFB site; and (3) the SFT Area at the PC some time elapsed between the filling of the first EnCore
site. Samples were collected in all areas except the PRA and the filling of the last. An attempt was made to
using a Geoprobe®; in the PRA, samples were collected eliminate any bias by alternating between filling EnCores
using a Split Core Sampler. for the developers and filling EnCores for the reference
laboratory. Table 4-3 summarizes the demonstration
The liners containing environmental samples were sampling depth intervals, numbers of environmental and
transported to the sample management trailer at the Navy QA/QC samples collected, and numbers of environmental
BVC site, where the liners were cut open longitudinally. sample analyses associated with the demonstration of the
A geologist then profiled the samples based on soil OCMA-350.
characteristics to determine where the soil cores had to be
sectioned. The soil characterization performed for each Performance Evaluation Samples
demonstration area is summarized in Chapter 3.
All PE samples for the demonstration were prepared by
Each core sample section was then transferred to a ERA and shipped to the sample management trailer at the
stainless-steel bowl. The presence of any unrepresentative Navy BVC site. PE samples consisted of both soil samples
material such as sticks, roots, and stones was noted in a and liquid samples. ERA prepared soil PE samples using
field logbook, and such material was removed to the extent two soil matrixes: Ottawa sand and processed garden soil
possible using gloved hands. Any lump of clay in the (silty sand).
sample that was greater than about 1/8 inch in diameter
was crushed between gloved fingers before To prepare the soil PE samples, ERA spiked the required
homogenization. Each soil sample was homogenized by volume of soil based on the number of PE samples and the
stirring it for at least 2 minutes using a stainless-steel quantity of soil per PE sample requested. ERA then

30
Table 4-3. Environmental Samples

Number of Analyses
Total Number of Samples, by Reference
Depth Number of Including Field Triplicates, Number of Number of Number of Laboratoryd
Interval Sampling to Horiba and Reference MS/MSDb Extract TPH Analyses
Site Area (foot bgs) Locations Laboratorya Pairs Duplicatesc by Horiba GRO EDRO
Navy FFA Upper layer 3 5 1 1 6 0 8
BVC
Lower layer 3 5 1 1 5 0 8
NEX 7 to 8 3 5 1 1 6 8 8
Service
8 to 9 3 5 1 1 5 8 8
Station
Area 9 to 10 3 5 1 1 5 8 8
10 to 11 3 5 1 1 6 8 8
PRA 1.5 to 2.5 6 (4 vegetated 8 1 1 9 0 11
and
2 unvegetated)
Kelly B-38 23 to 25 3 5 1 1 6 8 8
AFB Area
25 to 27 3 3 1 1 4 6 6
PC SFT 2 to 4 5 7 1 1 8 10 10
Area
4 to 6 5 7 1 1 8 10 10
6 to 8 5 7 1 1 8 10 10
8 to 10 5 7 1 1 7 10 10
Total 74 13 13 83 86 113

Notes:

AFB = Air Force Base FFA = Fuel Farm Area PC = Petroleum company
bgs = Below ground surface MS/MSD = Matrix spike and matrix spike duplicate PRA = Phytoremediation Area
BVC = Base Ventura County NEX = Naval Exchange SFT = Slop Fill Tank
a
Field triplicates were collected at a frequency of one per depth interval in each sampling area except the B-38 Area. Because of conditions in the
B-38 Area, triplicates were collected in the top depth interval only. Three separate, blind samples were prepared for each field triplicate.
b
MS/MSD samples were collected at a frequency of one per depth interval in each sampling area for analysis by the reference laboratory. MS/MSD
samples were not analyzed by Horiba.
c
Because of site conditions, Horiba did not analyze extract duplicates for the lower layer in the FFA, the 8- to 9- and the 9- to 10-foot bgs depth
intervals in the NEX Service Station Area, and the 8- to 10-foot bgs depth interval in the SFT Area. Therefore, Horiba analyzed only nine extract
duplicates.
d
All environmental samples were also analyzed for moisture content by the reference laboratory.

homogenized the soil by manually mixing it. ERA used concentration expected to be present. Whenever possible,
weathered gasoline or diesel as the spiking material, and the interferents were added at levels that best represented
spiking was done at three levels to depict the three TPH real-world conditions. ERA analyzed the samples
concentration ranges: low, medium, and high. A containing weathered gasoline before shipping them to the
low-range sample was spiked to correspond to a TPH Navy BVC site. The analytical results were used to
concentration of less than 100 mg/kg; a medium-range confirm sample concentrations.
sample was spiked to correspond to a TPH concentration
range of 100 to 1,000 mg/kg; and a high-range sample was Liquid PE samples consisted of neat materials. Each
spiked to correspond to a TPH concentration of more than liquid PE sample consisted of approximately 2 mL of
1,000 mg/kg. To spike each low- and medium-range soil liquid in a flame-sealed, glass ampule. During the
sample, ERA used Freon 113 as a “carrier” to distribute the demonstration, the developers and reference laboratory
contaminant evenly throughout the sample. Soil PE were given a table informing them of the amount of liquid
samples were spiked with interferents at two different sample to be used for analysis.
levels ranging from 50 to 500 percent of the TPH

31
ERA grouped like PE samples together in a resealable bag sample designation also identified the expected
and placed all the PE samples in a cooler containing ice for contaminant type and range, whether the sample was soil
overnight shipment to the Navy BVC site. When the PE or liquid, and the sample number.
samples arrived at the site, the samples were labeled with
the appropriate sample identification numbers and placed Sample custody began when samples were placed in iced
in appropriate coolers for transfer to the developers on site coolers in the possession of the designated field sample
or for shipment to the reference laboratory as summarized custodian. Demonstration samples were divided into two
in Section 4.3.2. Table 4-4 summarizes the contaminant groups to allow adequate time for the developers and
types and concentration ranges as well as the numbers of reference laboratory to extract and analyze samples within
PE samples and analyses associated with the demonstration the method-specified holding times presented in Table 4-5.
of the OCMA-350. The two groups of samples for reference laboratory
analysis were placed in coolers containing ice and chain-
4.3.2 Sample Management of-custody forms and were shipped by overnight courier to
the reference laboratory on the first and third days of the
Following sample containerization, each environmental demonstration. The two groups of samples for developer
sample was assigned a unique sample designation defining analysis were placed in coolers containing ice and chain-
the sampling area, expected type of contamination, of-custody forms and were hand-delivered to the
expected concentration range, sampling location, sample developers at the Navy BVC site on the same days that the
number, and QC identification, as appropriate. Each reference laboratory received its two groups of samples.
sample container was labeled with the unique sample During the demonstration, each developer was provided
designation, date, time, preservative, initials of personnel with a tent to provide shelter from direct sunlight during
who had filled the container, and analysis to be performed. analysis of demonstration samples. In addition, at the end
Each PE sample was also assigned a unique sample of each day, the developer placed any samples or sample
designation that identified it as a PE sample. Each PE extracts in its custody in coolers, and the coolers were
stored in a refrigerated truck.

32
Table 4-4. Performance Evaluation Samples

Number of
Total Number of Analyses by Reference
Samples to Laboratoryc
Typical TPH Horiba and Number of Number of
Concentration Reference MS/MSDb Analyses by
Sample Type Rangea Laboratory Pairs Horiba GRO EDRO
Soil Samples (Ottawa Sand)
Weathered gasoline Low 7 0 7 7 7
Diesel 7 0 7 0 7
Soil Samples (Processed Garden Soil)
Weathered gasoline Medium 3 0 3 3 3
High 3 1 3 5 5
Diesel Medium 3 0 3 0 3
High 3 1 3 0 5
Blank soil (control sample) Trace 3 1 3 5 5
MTBE (1,100 mg/kg) and weathered gasoline High 3 0 3 3 3
MTBE (1,700 mg/kg) and weathered gasoline 3 0 3 3 3
PCE (2,810 mg/kg) and weathered gasoline 3 0 3 3 3
PCE (13,100 mg/kg) and weathered gasoline 3 0 3 3 3
Stoddard solvent (2,900 mg/kg) and 3 0 3 3 3
weathered gasoline
Stoddard solvent (15,400 mg/kg) and 3 0 3 3 3
weathered gasoline
Turpentine (2,730 mg/kg) and weathered 3 0 3 3 3
gasoline
Turpentine (12,900 mg/kg) and weathered 3 0 3 3 3
gasoline
Stoddard solvent (3,650 mg/kg) and diesel 3 0 3 3 3
Stoddard solvent (18,200 mg/kg) and diesel 3 0 3 3 3
Turpentine (3,850 mg/kg) and diesel 3 0 3 3 3
Turpentine (19,600 mg/kg) and diesel 3 0 3 3 3
1,2,4-Trichlorobenzene (3,350 mg/kg) and 3 0 3 0 3
diesel
1,2,4-Trichlorobenzene (16,600 mg/kg) and 3 0 3 0 3
diesel
Humic acid (3,940 mg/kg) and diesel 3 0 3 0 3
Humic acid (19,500 mg/kg) and diesel 3 0 3 0 3
Humic acid (3,940 mg/kg) Trace 3 0 3 0 3
Humic acid (19,500 mg/kg) 3 0 3 0 3
Weathered gasoline at 16 percent moisture High 3 1 3 5 5
Diesel at negligible moisture (less than 3 1 3 0 5
1 percent)
Liquid Samples (Neat Material)
Weathered gasoline High 3 1 3 5 5
Diesel 3 0 3 0 3
MTBE 6 0 6 6 0
PCE Not applicable 6 0 6 6 0

33
Table 4-4. Performance Evaluation Samples (Continued)

Number of
Total Number of Analyses by Reference
Samples to Laboratoryc
Typical TPH Horiba and Number of Number of
Concentration Reference MS/MSDb Analyses by
Sample Type Rangea Laboratory Pairs Horiba GRO EDRO
Liquid Samples (Neat Material) (Continued)
Stoddard solvent High 6 0 6 6 6
Turpentine Not applicable 6 0 6 6 6
1,2,4-Trichlorobenzene 6 0 6 0 6
Total 125 6 125 90 125

Notes:

mg/kg = Milligram per kilogram MTBE = Methyl-tert-butyl ether

MS/MSD = Matrix spike and matrix spike duplicate PCE = Tetrachloroethene
a
The typical TPH concentration range was based on reference laboratory results for the demonstration. The typical low, medium, and high ranges
indicate TPH concentrations of less than 100 mg/kg; 100 to 1,000 mg/kg; and greater than 1,000 mg/kg, respectively. The typical TPH
concentration range for the liquid sample concentrations was based on the definition of TPH used for the demonstration and knowledge of the
sample (neat material).
b
MS/MSD samples were analyzed only by the reference laboratory.
c
All soil performance evaluation samples were also analyzed for moisture content by the reference laboratory.

34
Table 4-5. Sample Container, Preservation, and Holding Time Requirements

Holding Time (days)

a
Parameter Medium Container Preservation Extraction Analysis
b
GRO Soil Two 5-gram EnCores 4 ± 2 °C 2 14
b
EDRO Soil Two 4-ounce, glass jars with Teflon™-lined lids 4 ± 2 °C 14 40
Percent moisture Soil Two 4-ounce, glass jars with Teflon™-lined lids 4 ± 2 °C Not applicable 7
TPH Soil One 25-gram EnCore 4 ± 2 °C Performed on sitec
GRO and EDRO Liquid One 2-milliliter ampule for each analysis Not applicable See note d

Notes:

± = Plus or minus
a
The reference laboratory measured percent moisture using part of the soil sample from the container designated for EDRO analysis.
b
The extraction holding time started on the day that samples were shipped.
c
If GRO analysis of a sample was to be completed by the reference laboratory, the developers completed on-site extraction of the corresponding
sample within 2 days. Otherwise, all on-site extractions and analyses were completed within 7 days.
d
The reference laboratory cracked open each ampule and immediately added the specified aliquot of the sample to methanol for GRO analysis and
to methylene chloride for EDRO analysis. This procedure was performed in such a way that the final volumes of the extracts for GRO and EDRO
analyses were 5.0 milliliters and 1.0 milliliter, respectively. Once the extracts were prepared, the GRO and EDRO analyses were performed within
14 and 40 days, respectively.

35
 Chapter 5
Confirmatory Process

The performance results for each field measurement device listed criteria are illustrated in a flow diagram in
were compared to those for an off-site laboratory Figure 5-1. The reference method selection process is
measurement method—that is, a reference method. This discussed below.
chapter describes the rationale for the selection of the
reference method (Section 5.1) and reference laboratory Analytical methods considered for the demonstration were
(Section 5.2) and summarizes project-specific sample identified based on a review of SW-846, “Methods for
preparation and analysis procedures associated with the Chemical Analysis of Water and Wastes” (MCAWW),
reference method (Section 5.3). ASTM, API, and state-specific methods. The analytical
methods considered collectively represent six different
5.1 Reference Method Selection measurement technologies. Of the methods reviewed,
those identified as field screening methods, such as SW-
During the demonstration, environmental and PE samples 846 Method 4030, were eliminated from further
were analyzed for TPH by the reference laboratory using consideration in the reference method selection process.
SW-846 Method 8015B (modified). This section
describes the analytical methods considered for the A literature review was conducted to determine whether
demonstration and provides a rationale for the reference the remaining methods are widely used and accepted in the
method selected. United States (Association for Environmental Health and
Sciences [AEHS] 1999). As a result of this review, state-
The reference method used was selected based on the specific methods such as the Massachusetts Extractable
following criteria: Petroleum Hydrocarbon (EPH) and Volatile Petroleum
Hydrocarbon (VPH) Methods (Massachusetts Department
• It is not a field screening method. of Environmental Protection 2000), the Florida Petroleum
Range Organic (PRO) Method (Florida Department of
• It is widely used and accepted. Environmental Protection 1996), and Texas Method 1005
(Texas Natural Resource Conservation Commission 2000)
• It measures light (gasoline) to heavy (lubricating oil) were eliminated from the selection process. Also
fuel types. eliminated were the gravimetric and infrared methods
except for MCAWW Method 418.1 (EPA 1983). The use
• It can provide separate measurements of GRO and and acceptability of MCAWW Method 418.1 will likely
EDRO fractions of TPH. decline because the extraction solvent used in this method
is Freon 113, a chlorofluorocarbon (CFC), and use of
• It meets project-specific reporting limit requirements. CFCs will eventually be phased out under the Montreal
Protocol. However, because several states still accept the
The analytical methods considered for the demonstration use of MCAWW Method 418.1 for measuring TPH, the
and the reference method selected based on the above- method was retained for further consideration in the
selection process (AEHS 1999).

36
37
Notes:

API = American Petroleum Institute, ASTM = American Society for Testing and Materials, DRO = diesel range organics, EPH = extractable petroleum hydrocarbon, GC/FID = gas chromatograph/flame
ionization detector, MCAWW = “Methods for Chemical Analysis of Water and Wastes,” PHC = petroleum hydrocarbon, PRO = petroleum range organics, SW-846 = “Test Methods for Evaluating
Solid Waste,” VPH = volatile petroleum hydrocarbon
a
SW-846 Method 8015B provides separate GRO and DRO measurements and, when modified, can also provide EDRO measurements.

Figure 5-1. Reference method selection process.

Of the remaining methods, MCAWW Method 418.1, the 5.2 Reference Laboratory Selection
API PHC Method, and SW-846 Method 8015B can all
measure light (gasoline) to heavy (lubricating oil) fuel This section provides the rationale for the selection of the
types. However, GRO and EDRO fractions cannot be reference laboratory. STL Tampa East was selected as the
measured separately using MCAWW Method 418.1. As reference laboratory because it (1) has been performing
a result, this method was eliminated from the selection TPH analyses for many years, (2) has passed many
process. external audits by successfully implementing a variety of
TPH analytical methods, and (3) agreed to implement
Both the API PHC Method and SW-846 Method 8015B project-specific analytical requirements. In January 2000,
can be used to separately measure the GRO and DRO a project-specific audit of the laboratory was conducted
fractions of TPH. These methods can also be modified to and determined that STL Tampa East satisfactorily
extend the DRO range to EDRO by using a calibration implemented the reference method during the
standard that includes even-numbered alkanes in the predemonstration investigation. In addition, STL Tampa
EDRO range. East successfully analyzed double-blind PE samples and
blind field triplicates for GRO and EDRO during the
Based on a review of state-specific action levels for TPH, predemonstration investigation. Furthermore, in 1998 STL
a TPH reporting limit of 10 mg/kg was used for the Tampa East was one of four recipients and in 1999 was
demonstration. Because the TPH reporting limit for the one of six recipients of the Seal of Excellence Award
API PHC Method (50 to 100 mg/kg) is greater than issued by the American Council of Independent
10 mg/kg, this method was eliminated from the selection Laboratories. In each instance, this award was issued
process (API 1994). SW-846 Method 8015B (modified) based on the results of PE sample analyses and client
met the reporting limit requirements for the demonstration. satisfaction surveys. Thus, the selection of the reference
For GRO, SW-846 Method 8015B (modified) has a laboratory was based primarily on performance and not
reporting limit of 5 mg/kg, and for EDRO, this method has cost.
a reporting limit of 10 mg/kg. Therefore, SW-846
Method 8015B (modified) satisfied all the criteria 5.3 Summary of Reference Method
established for selecting the reference method. As an
added benefit, because this is a GC method, it also The laboratory sample preparation and analytical methods
provides a fingerprint (chromatogram) of TPH used for the demonstration are summarized in Table 5-1.
components. The SW-846 methods listed in Table 5-1 for GRO and

Table 5-1. Laboratory Sample Preparation and Analytical Methods

Parameter Method Reference (Step) Method Title

GRO Based on SW-846 Method 5035 (extraction) Closed-System Purge-and-Trap and Extraction for Volatile Organics
in Soil and Waste Samples
Based on SW-846 Method 5030B (purge-and-trap) Purge-and-Trap for Aqueous Samples
Based on SW-846 Method 8015B (analysis) Nonhalogenated Volatile Organics by Gas Chromatography

EDRO Based on SW-846 Method 3540C (extraction) Soxhlet Extraction

Based on SW-846 Method 8015B (analysis) Nonhalogenated Volatile Organics by Gas Chromatography

Percent moisture Based on MCAWW Method 160.3a Residue, Total (Gravimetric, Dried at 103-105 °C)

Notes:

MCAWW = “Methods for Chemical Analysis of Water and Wastes”

SW-846 = “Test Methods for Evaluating Solid Waste”
a
MCAWW Method 160.3 was modified to include calculation and reporting of percent moisture in soil samples.

38
EDRO analyses were tailored to meet the definition of benzene or n-C10 peak, whichever occurs later, and the
TPH for the project (see Chapter 1). Project-specific n-octacosane peak; however, an additional quantitation
procedures for soil sample preparation and analysis for was performed to sum the areas of all chromatographic
GRO and EDRO are summarized in Tables 5-2 and 5-3, peaks eluting from the end of the n-octacosane peak
respectively. Project-specific procedures were applied through the tetracontane peak in order to meet
(1) if a method used offered choices (for example, SW-846 demonstration objectives).
Method 5035 for GRO extraction states that samples may
be collected with or without use of a preservative solution), Before analyzing a liquid PE sample, STL Tampa East
(2) if a method used did not provide specific details (for added an aliquot of the liquid PE sample to the extraction
example, SW-846 Method 5035 for GRO extraction does solvent used for soil samples. A specified aliquot of the
not specify how unrepresentative material should be liquid PE sample was diluted in methanol for GRO
handled during sample preparation), or (3) if a analysis and in methylene chloride for EDRO analysis
modification to a method used was required in order to such that the final volume of the solution for GRO and
meet demonstration objectives (for example, SW-846 EDRO analyses was 5.0 and 1.0 mL, respectively. The
Method 8015B for EDRO analysis states that quantitation solution was then analyzed for GRO and EDRO using the
is performed by summing the areas of all chromatographic same procedures as are used for soil sample extracts.
peaks eluting between the end of the 1,2,4-trimethyl

39
Table 5-2. Summary of Project-Specific Procedures for GRO Analysis

SW-846 Method Reference (Step) Project-Specific Procedures

5035 (Extraction)
Low-level (0.5 to 200 micrograms per kilogram) or high-level (greater Because the project-specific reporting limit for GRO was 5 milligrams
than 200 micrograms per kilogram) samples may be prepared. per kilogram, all samples analyzed for GRO were prepared using
procedures for high-level samples.
Samples may be collected with or without use of a preservative Samples were collected without use of a preservative.
solution.
A variety of sample containers, including EnCores, may be used when Samples were containerized in EnCores.
high-level samples are collected without use of a preservative.
Samples collected in EnCores should be transferred to vials containing Samples were weighed and extracted within 2 calendar days of their
the extraction solvent as soon as possible or analyzed within 48 hours. shipment. The holding time for analysis was 14 days after extraction. A
full set of quality control samples (method blanks, MS/MSDs, and
LCS/LCSDs) was prepared within this time.
For samples not preserved in the field, a solubility test should be Because the reference laboratory obtained acceptable results for
performed using methanol, polyethylene glycol, and hexadecane to performance evaluation samples extracted with methanol during the
determine an appropriate extraction solvent. predemonstration investigation, samples were extracted with methanol.
Removal of unrepresentative material from the sample is not discussed. During sample homogenization, field sampling technicians attempted to
remove unrepresentative material such as sticks, roots, and stones if
present in the sample; the reference laboratory did not remove any
remaining unrepresentative material.
Procedures for adding surrogates to the sample are inconsistently The soil sample was ejected into a volatile organic analysis vial, an
presented. Section 2.2.1 indicates that surrogates should be added to appropriate amount of surrogate solution was added to the sample, and
an aliquot of the extract solution. Section 7.3.3 indicates that soil then methanol was quickly added.
should be added to a vial containing both the extraction solvent
(methanol) and surrogate spiking solution.
Nine mL of methanol should be added to a 5-gram (wet weight) soil Five mL of methanol was added to the entire soil sample contained in a
sample. 5-gram EnCore.
When practical, the sample should be dispersed to allow contact with The sample was dispersed using a stainless-steel spatula to allow
the methanol by shaking or using other mechanical means for 2 min contact with the methanol. The volatile organic analysis vial was then
without opening the sample container. When shaking is not practical, capped and shaken vigorously until the soil was dispersed in methanol,
the sample should be dispersed with a narrow, metal spatula, and the and the soil was allowed to settle.
sample container should be immediately resealed.
5030B (Purge-and-Trap)
Screening of samples before the purge-and-trap procedure is Samples were screened with an automated headspace sampler (see
recommended using one of the two following techniques: SW-846 Method 5021) connected to a GC equipped with a flame
ionization detector.
Use of an automated headspace sampler (see SW-846 Method 5021)
connected to a GC equipped with a photoionization detector in series
with an electrolytic conductivity detector

Extraction of the samples with hexadecane (see SW-846 Method 3820)

and analysis of the extracts using a GC equipped with a flame
ionization detector or electron capture detector
SW-846 Method 5030B indicates that contamination by carryover can According to the reference laboratory, a sample extract concentration
occur whenever high-level and low-level samples are analyzed in equivalent to 10,000 ng on-column is the minimum concentration of
sequence. Where practical, analysis of samples with unusually high GRO that could result in carryover. Therefore, if a sample extract had a
concentrations of analytes should be followed by an analysis of organic- concentration that exceeded the minimum concentration for carryover,
free reagent water to check for cross-contamination. Because the trap the next sample in the sequence was evaluated as follows: (1) if the
and other parts of the system are subject to contamination, frequent sample was clean (had no chromatographic peaks), no carryover had
bake-out and purging of the entire system may be required. occurred; (2) if the sample had detectable analyte concentrations
(chromatographic peaks), it was reanalyzed under conditions in which
carryover did not occur.

40
Table 5-2. Summary of Project-Specific Procedures for GRO Analysis (Continued)

SW-846 Method Reference (Step) Project-Specific Procedures

5030B (Purge-and-Trap) (Continued)
The sample purge device used must demonstrate adequate A Tekmar 2016 autosampler and a Tekmar LSC 2000 concentrator
performance. were used. Based on quality control sample results, the reference
laboratory had demonstrated adequate performance using these
devices.
Purge-and-trap conditions for high-level samples are not clearly The purge-and-trap conditions that were used are listed below. These
specified. According to SW-846, manufacturer recommendations for conditions were based on manufacturer recommendations for the purge
the purge-and-trap devices should be considered when the method is device specified above and the VOCARB 3000 trap.
implemented. The following general purge-and-trap conditions are
recommended for samples that are water-miscible (methanol extract):
Purge gas: nitrogen or helium Purge gas: helium
Purge gas flow rate: 20 mL/min Purge gas flow rate: 35 mL/min
Purge time: 15 ± 0.1 min Purge time: 8 min with 2-min dry purge
Purge temperature: 85 ± 2 °C Purge temperature: ambient temperature
Desorb time: 1.5 min Desorb time: 1 min
Desorb temperature: 180 °C Desorb temperature: 250 °C
Backflush inert gas flow rate: 20 to 60 mL/min Backflush inert gas flow rate: 35 mL/min
Bake time: not specified Bake time: 7 min
Bake temperature: not specified Bake temperature: 270 °C
Multiport valve and transfer line temperatures: not specified Multiport valve and transfer line temperatures: 115 and 120 °C
8015B (Analysis)
GC Conditions
The following GC conditions are recommended: The HP 5890 Series II was used as the GC. The following GC
conditions were used based on manufacturer recommendations:
Column: 30-meter x 0.53-millimeter-inside diameter, fused-silica Column: 30-meter x 0.53-millimeter-inside diameter, fused-silica
capillary column chemically bonded with 5 percent methyl capillary column chemically bonded with 5 percent methyl
silicone, 1.5-micrometer field thickness silicone, 1.5-micrometer field thickness
Carrier gas: helium Carrier gas: helium
Carrier gas flow rate: 5 to 7 mL/min Carrier gas flow rate: 15 mL/min
Makeup gas: helium Makeup gas: helium
Makeup gas flow rate: 30 mL/min Makeup gas flow rate: 15 mL/min
Injector temperature: 200 °C Injector temperature: 200 °C
Detector temperature: 340 °C Detector temperature: 200 °C
Temperature program: Temperature program:
Initial temperature: 45 °C Initial temperature: 25 °C
Hold time: 1 min Hold time: 3 min
Program rate: 45 to 100 °C at 5 °C/min Program rate: 25 to 120 °C at 25 °C/min
Program rate: 100 to 275 °C at 8 °C/min Hold time: 4 min
Hold time: 5 min Program rate: 120 to 245 °C at 25 °C/min
Overall time: 38.9 min Hold time: 5 min
Overall time: 20.4 min
Calibration
The chromatographic system may be calibrated using either internal or The chromatographic system was calibrated using external standards
external standards. with a concentration range equivalent to 100 to 10,000 ng on-column.
The reference laboratory acceptance criterion for initial calibration was a
relative standard deviation less than or equal to 20 percent of the
average response factor or a correlation coefficient for the least-
squares linear regression greater than or equal to 0.990.
Calibration should be performed using samples of the specific fuel type Calibration was performed using a commercially available,
contaminating the site. When such samples are not available, recently 10-component GRO standard that contained 35 percent aliphatic
purchased, commercially available fuel should be used. hydrocarbons and 65 percent aromatic hydrocarbons.

41
Table 5-2. Summary of Project-Specific Procedures for GRO Analysis (Continued)

SW-846 Method Reference (Step) Project-Specific Procedures

8015B (Analysis) (Continued)
Calibration (Continued)
Initial calibration verification is not required. Initial calibration verification was performed using a second-source
standard that contained a 10-component GRO standard made up of
35 percent aliphatic hydrocarbons and 65 percent aromatic
hydrocarbons at a concentration equivalent to 2,000 ng on-column. The
reference laboratory acceptance criterion for initial calibration
verification was an instrument response within 25 percent of the
response obtained during initial calibration.
CCV should be performed at the beginning of every 12-hour work shift CCV was performed at the beginning of each analytical batch, after
and at the end of an analytical sequence. CCV throughout the 12-hour every tenth analysis, and at the end of the analytical batch. The
shift is also recommended; however, the frequency is not specified. reference laboratory acceptance criteria for CCV were instrument
responses within 25 percent (for the closing CCV) and 15 percent (for
all other CCVs) of the response obtained during initial calibration.
CCV should be performed using a fuel standard. CCV was performed using a commercially available, 10-component
GRO standard that contained 35 percent aliphatic hydrocarbons and
65 percent aromatic hydrocarbons.
According to SW-846 Method 8000, CCV should be performed at the CCV was performed at a concentration equivalent to 2,000 ng
same concentration as the midpoint concentration of the initial on-column.
calibration curve; however, the concentration of each calibration point is
not specified.
A method sensitivity check is not required. A method sensitivity check was performed daily using a calibration
standard with a concentration equivalent to 100 ng on-column. The
reference laboratory acceptance criterion for the method sensitivity
check was detection of the standard.
Retention Time Windows
The retention time range (window) should be established using The retention time range was established using the opening CCV
2-methylpentane and 1,2,4-trimethylbenzene during initial calibration. specific to each analytical batch. The first eluter, 2-methylpentane, and
Three measurements should be made over a 72-hour period; the results the last eluter, 1,2,4-trimethylbenzene, of the GRO standard were used
should be used to determine the average retention time. As a minimum to establish each day’s retention time range.
requirement, the retention time should be verified using a midlevel
calibration standard at the beginning of each 12-hour shift. Additional
analysis of the standard throughout the 12-hour shift is strongly
recommended.
Quantitation
Quantitation is performed by summing the areas of all chromatographic Quantitation was performed by summing the areas of all
peaks eluting within the retention time range established using chromatographic peaks from 2-methylpentane through
2-methylpentane and 1,2,4-trimethylbenzene. Subtraction of the 1,2,4-trimethylbenzene. This range includes n-C10. Baseline rise
baseline rise for the method blank resulting from column bleed is subtraction was not performed.
generally not required.
Quality Control
Spiking compounds for MS/MSDs and LCSs are not specified. The spiking compound mixture for MS/MSDs and LCSs was the 10-
component GRO calibration standard.
According to SW-846 Method 8000, spiking levels for MS/MSDs are MS/MSD spiking levels were targeted to be between 50 and
determined differently for compliance and noncompliance monitoring 150 percent of the unspiked sample concentration. The reference
applications. For noncompliance applications, the laboratory may spike laboratory used historical information to adjust spike amounts or to
the sample (1) at the same concentration as the reference sample adjust sample amounts to a preset spike amount. The spiked samples
(LCS), (2) at 20 times the estimated quantitation limit for the matrix of and unspiked samples were prepared such that the sample mass and
interest, or (3) at a concentration near the middle of the calibration extract volume used for analysis were the same.
range.

42
Table 5-2. Summary of Project-Specific Procedures for GRO Analysis (Continued)

SW-846 Method Reference (Step) Project-Specific Procedures

8015B (Analysis) (Continued)
Quality Control (Continued)
According to SW-846 Method 8000, in-house laboratory acceptance The reference laboratory acceptance criteria for MS/MSDs and LCSs
criteria for MS/MSDs and LCSs should be established. As a general were a relative percent difference less than or equal to 25 with 33 to
rule, the recoveries of most compounds spiked into a sample should fall 115 percent recovery. The acceptance criteria were based on
within the range of 70 to 130 percent, and this range should be used as laboratory historical information. These acceptance criteria are similar
a guide in evaluating in-house performance. to those of the methods cited in Figure 5-1.
The LCS should consist of an aliquot of a clean (control) matrix that is The LCS/LCSD matrix was Ottawa sand.
similar to the sample matrix.
No LCSD is required. The spiking compound mixture for LCSDs was the 10-component GRO
calibration standard.
The surrogate compound and spiking concentration are not specified. The surrogate compound was 4-bromofluorobenzene. The reference
According to SW-846 Method 8000, in-house laboratory acceptance laboratory acceptance criterion for surrogates was 39 to 163 percent
criteria for surrogate recoveries should be established. recovery.
The method blank matrix is not specified. The method blank matrix was Ottawa sand. The reference laboratory
acceptance criterion for the method blank was less than or equal to the
project-specific reporting limit.
The extract duplicate is not specified. The extract duplicate was analyzed. The reference laboratory
acceptance criterion for the extract duplicate was a relative percent
difference less than or equal to 25.

Notes:

± = Plus or minus min = Minute

CCV = Continuing calibration verification mL = Milliliter
GC = Gas chromatograph MS = Matrix spike
LCS = Laboratory control sample MSD = Matrix spike duplicate
LCSD = Laboratory control sample duplicate ng = Nanogram
SW-846 = “Test Methods for Evaluating Solid Waste”

43
Table 5-3. Summary of Project-Specific Procedures for EDRO Analysis

SW-846 Method Reference (Step) Project-Specific Procedures

3540C (Extraction)
Any free water present in the sample should be decanted and During sample homogenization, field sampling technicians attempted to
discarded. The sample should then be thoroughly mixed, and any remove unrepresentative material such as sticks, roots, and stones. In
unrepresentative material such as sticks, roots, and stones should be addition, the field sampling technicians decanted any free water present
discarded. in the sample. The reference laboratory did not decant water or remove
any unrepresentative material from the sample. The reference
laboratory mixed the sample with a stainless-steel tongue depressor.
Ten grams of soil sample should be blended with 10 grams of Thirty grams of sample was blended with at least 30 grams of
anhydrous sodium sulfate. anhydrous sodium sulfate. For medium- and high-level samples, 6 and
2 grams of soil were used for extraction, respectively, and proportionate
amounts of anhydrous sodium sulfate were added. The amount of
anhydrous sodium sulfate used was not measured gravimetrically but
was sufficient to ensure that free moisture was effectively removed from
the sample.
Extraction should be performed using 300 mL of extraction solvent. Extraction was performed using 200 mL of extraction solvent.
Acetone and hexane (1:1 volume per volume) or methylene chloride Methylene chloride was used as the extraction solvent.
and acetone (1:1 volume per volume) may be used as the extraction
solvent.

Note: Methylene chloride and acetone are not constant-boiling

solvents and thus are not suitable for the method. Methylene
chloride was used as an extraction solvent for method
validation.
The micro Snyder column technique or nitrogen blowdown technique Kuderna Danish and nitrogen evaporation were used as the
may be used to adjust (concentrate) the soil extract to the required final concentration techniques.
volume.
Procedures for addressing contamination carryover are not specified. According to the reference laboratory, a sample extract concentration of
100,000 micrograms per mL is the minimum concentration of EDRO
that could result in carryover. Therefore, if a sample extract had a
concentration that exceeded the minimum concentration for carryover,
the next sample in the sequence was evaluated as follows: (1) if the
sample was clean (had no chromatographic peaks), no carryover
occurred; (2) if the sample had detectable analyte concentrations
(chromatographic peaks), it was reanalyzed under conditions in which
carryover did not occur.
8015B (Analysis)
GC Conditions
The following GC conditions are recommended: An HP 6890 GC was used with the following conditions:

Column: 30-meter x 0.53-millimeter-inside diameter, fused-silica Column: 30-meter x 0.53-millimeter-inside diameter, fused-silica
capillary column chemically bonded with 5 percent methyl capillary column chemically bonded with 5 percent methyl
silicone, 1.5-micrometer field thickness silicone, 1.5-micrometer field thickness
Carrier gas: helium Carrier gas: hydrogen
Carrier gas flow rate: 5 to 7 mL/min Carrier gas flow rate: 1.9 mL/min
Makeup gas: helium Makeup gas: hydrogen
Makeup gas flow rate: 30 mL/min Makeup gas flow rate: 23 mL/min
Injector temperature: 200 °C Injector temperature: 250 °C
Detector temperature: 340 °C Detector temperature: 345 °C
Temperature program: Temperature program:
Initial temperature: 45 °C Initial temperature: 40 °C
Hold time: 3 min Hold time: 2 min
Program rate: 45 to 275 °C at 12 °C/min Program rate: 40 to 345 °C at 30 °C/min
Hold time: 12 min Hold time: 5 min
Overall time: 34.2 min Overall time: 17.2 min

44
Table 5-3. Summary of Project-Specific Procedures for EDRO Analysis (Continued)

SW-846 Method Reference (Step) Project-Specific Procedures

8015B (Analysis) (Continued)
Calibration
The chromatographic system may be calibrated using either internal or The chromatographic system was calibrated using external standards
external standards. with a concentration range equivalent to 75 to 7,500 ng on-column. The
reference laboratory acceptance criterion for initial calibration was a
relative standard deviation less than or equal to 20 percent of the
average response factor or a correlation coefficient for the least-
squares linear regression greater than or equal to 0.990.
Calibration should be performed using samples of the specific fuel type Calibration was performed using a commercially available standard that
contaminating the site. When such samples are not available, recently contained even-numbered alkanes from C10 through C40.
purchased, commercially available fuel should be used.
ICV is not required. ICV was performed using a second-source standard that contained
even-numbered alkanes from C10 through C40 at a concentration
equivalent to 3,750 ng on-column. The reference laboratory
acceptance criterion for ICV was an instrument response within
25 percent of the response obtained during initial calibration.
CCV should be performed at the beginning of every 12-hour work shift CCV was performed at the beginning of each analytical batch, after
and at the end of an analytical sequence. CCV throughout the 12-hour every tenth analysis, and at the end of the analytical batch. The
shift is also recommended; however, the frequency is not specified. reference laboratory acceptance criteria for CCV were instrument
responses within 25 percent (for the closing CCV) and 15 percent (for
all other CCVs) of the response obtained during initial calibration.
CCV should be performed using a fuel standard. CCV was performed using a standard that contained only even-
numbered alkanes from C10 through C40.
According to SW-846 Method 8000, CCV should be performed at the CCV was performed at a concentration equivalent to 3,750 ng
same concentration as the midpoint concentration of the initial on-column.
calibration curve; however, the concentration of each calibration point is
not specified.
A method sensitivity check is not required. A method sensitivity check was performed daily using a calibration
standard with a concentration equivalent to 75 ng on-column. The
reference laboratory acceptance criterion for the method sensitivity
check was detection of the standard.
Retention Time Windows
The retention time range (window) should be established using Two retention time ranges were established using the opening CCV for
C10 and C28 alkanes during initial calibration. Three measurements each analytical batch. The first range, which was labeled diesel range
should be made over a 72-hour period; the results should be used to organics, was marked by the end of the 1,2,4-trimethylbenzene or n-C10
determine the average retention time. As a minimum requirement, the peak, whichever occurred later, through the n-octacosane peak. The
retention time should be verified using a midlevel calibration standard at second range, which was labeled oil range organics, was marked by the
the beginning of each 12-hour shift. Additional analysis of the standard end of the n-octacosane peak through the tetracontane peak.
throughout the 12-hour shift is strongly recommended.
Quantitation
Quantitation is performed by summing the areas of all chromatographic Quantitation was performed by summing the areas of all
peaks eluting between n-C10 and n-octacosane. chromatographic peaks from the end of the 1,2,4-trimethylbenzene or
n-C10 peak, whichever occurred later, through the n-octacosane peak.
A separate quantitation was also performed to sum the areas of all
chromatographic peaks from the end of the n-octacosane peak through
the tetracontane peak. Separate average response factors for the
carbon ranges were used for quantitation. The quantitation results were
then summed to determine the total EDRO concentration.

All calibrations, ICVs, CCVs, and associated batch quality control

measures were controlled for the entire EDRO range using a single
quantitation performed over the entire EDRO range.

45
Table 5-3. Summary of Project-Specific Procedures for EDRO Analysis (Continued)

SW-846 Method Reference (Step) Project-Specific Procedures

8015B (Analysis) (Continued)
Quantitation (Continued)
Subtraction of the baseline rise for the method blank resulting from The reference laboratory identified occurrences of baseline rise in the
column bleed is appropriate. data package. The baseline rise was evaluated during data validation
and subtracted when appropriate based on analyst discretion.
Because phthalate esters contaminate many types of products Phthalate peaks were not noted during analysis.
commonly found in the laboratory, consistent quality control should be
practiced.
Quality Control
Spiking compounds for MS/MSDs and LCSs are not specified. The spiking compound for MS/MSDs and LCSs was an EDRO standard
that contained even-numbered alkanes from C10 through C40.
According to SW-846 Method 8000, spiking levels for MS/MSDs are MS/MSD spiking levels were targeted to be between 50 and
determined differently for compliance and noncompliance monitoring 150 percent of the unspiked sample concentration. The reference
applications. For noncompliance applications, the laboratory may spike laboratory used historical information to adjust spike amounts or to
the sample (1) at the same concentration as the reference sample adjust sample amounts to a preset spike amount. The spiked samples
(LCS), (2) at 20 times the estimated quantitation limit for the matrix of and unspiked samples were prepared such that the sample mass and
interest, or (3) at a concentration near the middle of the calibration extract volume used for analysis were the same.
range.
According to SW-846 Method 8000, in-house laboratory acceptance The reference laboratory acceptance criteria for MS/MSDs and LCSs
criteria for MS/MSDs and LCSs should be established. As a general were a relative percent difference less than or equal to 45 with 46 to
rule, the recoveries of most compounds spiked into a sample should fall 124 percent recovery. The acceptance criteria were based on
within the range of 70 to 130 percent, and this range should be used as laboratory historical information. These acceptance criteria are similar
a guide in evaluating in-house performance. to those of the methods cited in Figure 5-1.
The LCS should consist of an aliquot of a clean (control) matrix that is The LCS/LCSD matrix was Ottawa sand.
similar to the sample matrix.
No LCSD is required. The spiking compound for LCSDs was the EDRO standard that
contained even-numbered alkanes from C10 through C40.
The surrogate compound and spiking concentration are not specified. The surrogate compound was o-terphenyl. The reference laboratory
According to SW-846 Method 8000, in-house laboratory acceptance acceptance criterion for surrogates was 45 to 143 percent recovery.
criteria for surrogate recoveries should be established.
The method blank matrix is not specified. The method blank matrix was Ottawa sand. The reference laboratory
acceptance criterion for the method blank was less than or equal to the
project-specific reporting limit.
The extract duplicate is not specified. The extract duplicate was analyzed. The reference laboratory
acceptance criterion for the extract duplicate was a relative percent
difference less than or equal to 45.

Notes:

CCV = Continuing calibration verification mL = Milliliter

GC = Gas chromatograph MS = Matrix spike
ICV = Initial calibration verification MSD = Matrix spike duplicate
LCS = Laboratory control sample n-Cx = Alkane with “x” carbon atoms
LCSD = Laboratory control sample duplicate ng = Nanogram
min = Minute SW-846 = “Test Methods for Evaluating Solid Waste”

46
 Chapter 6
Assessment of Reference Method Data Quality

This chapter assesses reference method data quality based EDRO did not include a preparation step, surrogates,
on QC check results and PE sample results. A summary of MS/MSDs, and LCS/LCSDs were not analyzed; however,
reference method data quality is included at the end of this an instrument blank was analyzed as a method blank
chapter. equivalent. The results for the QC checks were compared
to project-specific acceptance criteria. These criteria were
To ensure that the reference method results were of known based on the reference laboratory’s historical QC limits
and adequate quality, EPA representatives performed a and its experience in analyzing the predemonstration
predemonstration audit and an in-process audit of the investigation samples using the reference method. The
reference laboratory. The predemonstration audit findings reference laboratory’s QC limits were established as
were used in developing the predemonstration design. The described in SW-846 and were within the general
in-process audit was performed when the laboratory had acceptance criteria recommended by SW-846 for organic
analyzed a sufficient number of demonstration samples for analytical methods.
both GRO and EDRO and had prepared its first data
package. During the audit, EPA representatives Laboratory duplicates were also analyzed to evaluate the
(1) verified that the laboratory had properly implemented precision associated with percent moisture analysis of soil
the EPA-approved demonstration plan and (2) performed samples. The acceptance criterion for the laboratory
a critical review of the first data package. All issues duplicate results was an RPD less than or equal to 20. All
identified during the audit were fully addressed by the laboratory duplicate results met this criterion. The results
laboratory before it submitted the subsequent data for the laboratory duplicates are not separately discussed
packages to the EPA. The laboratory also addressed issues in this ITVR because soil sample TPH results were
identified during the EPA final review of the data compared on a wet weight basis except for those used to
packages. Audit findings are summarized in the DER for address primary object P4 (effect of soil moisture content).
the demonstration.
6.1.1 GRO Analysis
6.1 Quality Control Check Results
This section summarizes the results for QC checks used by
This section summarizes QC check results for GRO and the reference laboratory during GRO analysis, including
EDRO analyses performed using the reference method. method blanks, surrogates, MS/MSDs, extract duplicates,
The QC checks associated with soil sample analyses for and LCS/LCSDs. A summary of the QC check results is
GRO and EDRO included method blanks, surrogates, presented at the end of the section.
matrix spikes and matrix spike duplicates (MS/MSD), and
laboratory control samples and laboratory control sample Method Blanks
duplicates (LCS/LCSD). In addition, extract duplicates
were analyzed for soil environmental samples. The QC Method blanks were analyzed to verify that steps in the
checks associated with liquid PE sample analysis for GRO analytical procedure did not introduce contaminants that
included method blanks, surrogates, MS/MSDs, and affected analytical results. Ottawa sand and deionized
LCS/LCSDs. Because liquid PE sample analyses for water were used as method blanks for soil and liquid

47
samples, respectively. These blanks underwent all the environmental samples and because the surrogate
procedures required for sample preparation. The results recoveries for QC samples met the acceptance criterion,
for all method blanks met the acceptance criterion of being the reference laboratory did not reanalyze the
less than or equal to the required project-specific reporting environmental samples with high surrogate recoveries.
limit (5 mg/kg). Based on method blank results, the GRO Calculations performed to evaluate whether the coelution
analysis results were considered to be valid. resulted in underreporting of GRO concentrations
indicated an insignificant impact of less than 3 percent.
Surrogates Based on the surrogate results for environmental and
associated QC samples, the GRO analysis results for
Each soil investigative and QC sample for GRO analysis environmental samples were considered to be valid.
was spiked with a surrogate, 4-bromofluorobenzene,
before extraction to determine whether significant matrix A total of 42 surrogate measurements were made during
effects existed within the sample and to estimate the the analysis of soil PE and associated QC samples.
efficiency of analyte recovery during sample preparation Thirty-four of these samples were analyzed at a dilution
and analysis. A diluted, liquid PE sample was also spiked factor less than or equal to four. The surrogate recoveries
with the surrogate during sample preparation. The initial for these 34 samples ranged from 87 to 108 percent with a
surrogate spiking levels for soil and liquid PE samples mean recovery of 96 percent and a median recovery of
were 2 mg/kg and 40 µg/L, respectively. The acceptance 95 percent. The surrogate recoveries for all 34 samples
criterion was 39 to 163 percent surrogate recovery. For met the acceptance criterion. Based on the surrogate
samples analyzed at a dilution factor greater than four, the results for soil PE and associated QC samples, the GRO
surrogate concentration was diluted to a level below the analysis results for soil PE samples were considered to be
reference laboratory’s reporting limit for the reference valid.
method; therefore, surrogate recoveries for these samples
were not used to assess impacts on data quality. A total of 37 surrogate measurements were made during
the analysis of liquid PE and associated QC samples. Six
A total of 101 surrogate measurements were made during of these samples were analyzed at a dilution factor less
analysis of environmental and associated QC samples. than or equal to four. All six samples were QC samples
Fifty-six of these samples were analyzed at a dilution (method blanks and LCS/LCSDs). The surrogate
factor less than or equal to four. The surrogate recoveries recoveries for these six samples ranged from 81 to
for these 56 samples ranged from 43 to 345 percent with a 84 percent, indicating a small negative bias. However, the
mean recovery of 150 percent and a median recovery of surrogate recoveries for all six samples met the acceptance
136 percent. Because the mean and median recoveries criterion. Based on the surrogate results for liquid PE and
were greater than 100 percent, an overall positive bias was associated QC samples, the GRO analysis results for liquid
indicated. PE samples were considered to be valid.

The surrogate recoveries for 16 of the 56 samples did not Matrix Spikes and Matrix Spike Duplicates
meet the acceptance criterion. In each case, the surrogate
was recovered at a concentration above the upper limit of MS/MSD results were evaluated to determine the accuracy
the acceptance criterion. Examination of the gas and precision of the analytical results with respect to the
chromatograms for the 16 samples revealed that some effects of the sample matrix. For GRO analysis, each soil
PHCs or naturally occurring interferents present in these sample designated as an MS or MSD was spiked with the
environmental samples coeluted with the surrogate, GRO calibration standard at an initial spiking level of
resulting in higher surrogate recoveries. Such coelution is 20 mg/kg. MS/MSDs were also prepared for liquid PE
typical for hydrocarbon-containing samples analyzed using samples. Each diluted, liquid PE sample designated as an
a GC/FID technique, which was the technique used in the MS or MSD was spiked with the GRO calibration standard
reference method. The surrogate recoveries for QC at an initial spiking level of 40 µg/L. The acceptance
samples such as method blanks and LCS/LCSDs met the criteria for MS/MSDs were 33 to 115 percent recovery and
acceptance criterion, indicating that the laboratory sample an RPD less than or equal to 25. When the MS/MSD
preparation and analysis procedures were in control. percent recovery acceptance criterion was not met, instead
Because the coelution was observed only for of attributing the failure to meet the criterion to an

48
inappropriate spiking level, the reference laboratory Four sample pairs collected in the SFT Area were
respiked the sample at a more appropriate and practical designated as MS/MSDs. The sample matrix in this area
spiking level. Information on the selection of the spiking primarily consisted of silty clay. The percent recoveries
level and calculation of percent recoveries for MS/MSD for the MS/MSD samples ranged from 0 to 127 with RPDs
samples is provided below. ranging from 4 to 21. Of the four sample pairs, two
sample pairs met the percent recovery acceptance criterion,
According to Provost and Elder (1983), for percent one sample pair exhibited percent recoveries less than the
recovery data to be reliable, spiking levels should be at lower acceptance limit, and one sample pair exhibited
least five times the unspiked sample concentration. For percent recoveries greater than the upper acceptance limit.
the demonstration, however, a large number of the For the two sample pairs that did not meet the percent
unspiked sample concentrations were expected to range recovery acceptance criterion, the RPD acceptance
between 1,000 and 10,000 mg/kg, so use of such high criterion for the MS/MSDs and the percent recovery and
spiking levels was not practical. Therefore, a target RPD acceptance criteria for the LCS/LCSDs associated
spiking level of 50 to 150 percent of the unspiked sample with the analytical batches for these samples were met.
concentration was used for the demonstration. Provost and Because of the varied percent recoveries for the MS/MSD
Elder (1983) also present an alternate approach for sample pairs, it was not possible to conclude whether the
calculating percent recoveries for MS/MSD samples (100 GRO analysis results for the SFT Area samples had a
times the ratio of the measured concentration in a spiked negative or positive bias. Although one-half of the
sample to the calculated concentration in the sample). MS/MSD results did not meet the percent recovery
However, for the demonstration, percent recoveries were acceptance criterion, the out-of-control situations alone did
calculated using the traditional approach (100 times the not constitute adequate grounds for rejection of any of the
ratio of the amount recovered to the amount spiked) GRO analysis results for the SFT Area samples. The out-
primarily because the alternate approach is not commonly of-control situations may have been associated with
used. inadequate spiking levels (0.7 to 2.8 times the unspiked
sample concentrations compared to the minimum
For environmental samples, a total of 10 MS/MSD pairs recommended value of 5 times the concentrations).
were analyzed. Four sample pairs collected in the NEX
Service Station Area were designated as MS/MSDs. The Three soil PE sample pairs were designated as MS/MSDs.
sample matrix in this area primarily consisted of medium- The sample matrix for these samples consisted of silty
grained sand. The percent recoveries for all but one of the sand. The percent recoveries for these samples ranged
MS/MSD samples ranged from 67 to 115 with RPDs from 88 to 103 with RPDs ranging from 4 to 6. The
ranging from 2 to 14. Only one MS sample with a percent recoveries and RPDs for these samples met the
162 percent recovery did not meet the percent recovery acceptance criteria. Based on the MS/MSD results, the
acceptance criterion; however, the RPD acceptance GRO analysis results for the soil PE samples were
criterion for the MS/MSD and the percent recovery and considered to be valid.
RPD acceptance criteria for the LCS/LCSD associated
with the analytical batch for this sample were met. Based Two liquid PE sample pairs were designated as
on the MS/MSD results, the GRO analysis results for the MS/MSDs. The percent recoveries for these samples
NEX Service Station Area samples were considered to be ranged from 77 to 87 with RPDs of 1 and 5. The percent
valid. recoveries and RPDs for these samples met the acceptance
criteria. Based on the MS/MSD results, the GRO analysis
Two sample pairs collected in the B-38 Area were results for the liquid PE samples were considered to be
designated as MS/MSDs. The sample matrix in this area valid.
primarily consisted of sand and clay. The percent
recoveries for the MS/MSD samples ranged from 60 to 94 Extract Duplicates
with RPDs of 1 and 13. Therefore, the percent recoveries
and RPDs for these samples met the acceptance criteria. For GRO analysis, after soil sample extraction, extract
Based on the MS/MSD results, the GRO analysis results duplicates were analyzed to evaluate the precision
for the B-38 Area samples were considered to be valid. associated with the reference laboratory’s analytical
procedure. The reference laboratory sampled duplicate

49
aliquots of the GRO extracts for analysis. The acceptance The project-specific percent recovery acceptance criteria
criterion for extract duplicate precision was an RPD less were met for most environmental samples and all PE
than or equal to 25. Two or more environmental samples samples. As expected, the percent recovery ranges were
collected in each demonstration area whose samples were broader for the environmental samples than for the PE
analyzed for GRO (the NEX Service Station, B-38, and samples. As indicated by the mean and median percent
SFT Areas) were designated as extract duplicates. A total recoveries, the QC check results generally indicated a
of 10 samples designated as extract duplicates were slight negative bias (up to 20 percent) in the GRO
analyzed for GRO. The RPDs for these samples ranged concentration measurements; the exceptions were the
from 0.5 to 11. Therefore, the RPDs for all the extract surrogate recoveries for environmental samples and the
duplicates met the acceptance criterion. Based on the LCS/LCSD recoveries for soil PE samples. The observed
extract duplicate results, the GRO analysis results were bias did not exceed the generally acceptable bias
considered to be valid. (± 30 percent) stated in SW-846 for organic analyses and
is typical for most organic analytical methods for
Laboratory Control Samples and Laboratory environmental samples. Because the percent recovery
Control Sample Duplicates ranges were sometimes above and sometimes below 100,
the observed bias did not appear to be systematic.
For GRO analysis, LCS/LCSD results were evaluated to
determine the accuracy and precision associated with The project-specific RPD acceptance criterion was met for
control samples prepared by the reference laboratory. To all samples. As expected, the RPD range and the mean and
generate a soil LCS or LCSD, Ottawa sand was spiked median RPDs for MS/MSDs associated with the soil
with the GRO calibration standard at a spiking level of environmental samples were greater than those for other
20 mg/kg. To generate an LCS or LCSD for liquid PE QC checks and matrixes listed in Table 6-1. The low
sample analysis, deionized water was spiked with the GRO RPDs observed indicated good precision in the GRO
calibration standard at a spiking level of 40 µg/L. The concentration measurements made during the
acceptance criteria for LCS/LCSDs were 33 to 115 percent demonstration.
recovery and an RPD less than or equal to 25. The
LCS/LCSD acceptance criteria were based on the 6.1.2 EDRO Analysis
reference laboratory’s historical data.
This section summarizes the results for QC checks used by
Ten pairs of soil LCS/LCSD samples were prepared and the reference laboratory during EDRO analysis, including
analyzed. The percent recoveries for these samples ranged method and instrument blanks, surrogates, MS/MSDs,
from 87 to 110 with RPDs ranging from 2 to 14. In extract duplicates, and LCS/LCSDs. A summary of the
addition, two pairs of liquid LCS/LCSD samples were QC check results is presented at the end of the section.
prepared and analyzed. The percent recoveries for these
samples ranged from 91 to 92 with RPDs equal to 0 and 1. Method and Instrument Blanks
Therefore, the percent recoveries and RPDs for the soil and
liquid LCS/LCSD samples met the acceptance criteria, Method and instrument blanks were analyzed to verify that
indicating that the GRO analysis procedure was in control. steps in the analytical procedures did not introduce
Based on the LCS/LCSD results, the GRO analysis results contaminants that affected analytical results. Ottawa sand
were considered to be valid. was used as a method blank for soil samples. The method
blanks underwent all the procedures required for sample
Summary of Quality Control Check Results preparation. For liquid PE samples, the extraction solvent
(methylene chloride) was used as an instrument blank.
Table 6-1 summarizes the QC check results for GRO The results for all method and instrument blanks met the
analysis. Based on the QC check results, the conclusions acceptance criterion of being less than or equal to the
presented below were drawn regarding the accuracy and required project-specific reporting limit (10 mg/kg).
precision of GRO analysis results for the demonstration. Based on the method and instrument blank results, the
EDRO analysis results were considered to be valid.

50
 Table 6-1. Summary of Quality Control Check Results for GRO Analysis

Accuracy (Percent Recovery) Precision (Relative Percent Difference)

No. of No. of No. of
Measurements Measurements Measurements
Matrix Used to Meeting Meeting
Associated Evaluate Data Acceptance Actual Acceptance Acceptance Actual Acceptance
QC Checka with QC Check Quality Criterion Range Criterion Mean Median Criterion Range Criterion Mean Median
Surrogate Soil 56 39 to 163 43 to 345 40 150 136
environmental
samples
Soil PE 34 87 to 108 34 96 95 Not applicable
samples
Liquid PE 6 81 to 84 6 83 84
samples
MS/MSD Soil 20 (10 pairs) 33 to 115 0 to 162 15 81 80 #25 1 to 21 10 pairs 11 12
environmental
samples
Soil PE 6 (3 pairs) 88 to 103 6 94 92 4 to 6 3 pairs 5 5
samples
Liquid PE 4 (2 pairs) 77 to 87 4 83 85 1 to 5 2 pairs 3 3
samples

51
Extract Soil 10 pairs 0.5 to 11 10 pairs 5 4
duplicate environmental Not applicable
samples
LCS/LCSD Soil 10 pairs 33 to 115 87 to 110 20 100 100 2 to 14 10 pairs 6 6
environmental
and PE
samples
Liquid PE 2 pairs 91 to 92 4 92 92 0 to 1 2 pairs 0.5 0.5
samples

Notes:

# = Less than or equal to

LCS/LCSD = Laboratory control sample and laboratory control sample duplicate
MS/MSD = Matrix spike and matrix spike duplicate
PE = Performance evaluation
QC = Quality control
a
During the demonstration, 12 method blanks (10 for soil samples and 2 for liquid samples) were analyzed. The method blank results met the project-specific acceptance criteria.
Surrogates LCS/LCSDs. The reference laboratory reanalyzed the
three soil PE samples and the LCS/LCSD pair as well as
Each soil investigative and QC sample for EDRO analysis all the other samples in the QC lot associated with the
was spiked with a surrogate, o-terphenyl, before extraction LCS/LCSDs; during the reanalyses, all surrogate
to determine whether significant matrix effects existed recoveries met the acceptance criterion. The surrogate
within the sample and to estimate the efficiency of analyte recoveries for all results reported ranged from 46 to
recovery during sample preparation and analysis. For a 143 percent with mean and median recoveries of
30-gram sample, the spike concentration was 3.3 mg/kg. 76 percent, indicating an overall negative bias. The
For samples with higher EDRO concentrations, for which surrogate recoveries for all reported sample results met the
smaller sample amounts were used during extraction, the acceptance criterion. Based on the surrogate results for
spiking levels were proportionately higher. The soil PE and associated QC samples, the EDRO analysis
acceptance criterion was 45 to 143 percent surrogate results were considered to be valid.
recovery. Liquid PE samples for EDRO analysis were not
spiked with a surrogate because the analysis did not Matrix Spikes and Matrix Spike Duplicates
include a sample preparation step.
MS/MSD results were evaluated to determine the accuracy
A total of 185 surrogate measurements were made during and precision of the analytical results with respect to the
analysis of environmental and associated QC samples. Six effects of the sample matrix. For EDRO analysis, each soil
of these samples did not meet the percent recovery sample designated as an MS or MSD was spiked with the
acceptance criterion. Four of the six samples were EDRO calibration standard at an initial spiking level of
environmental samples. When the reference laboratory 50 mg/kg when a 30-gram sample was used during
reanalyzed the four samples, the surrogate recoveries for extraction. The initial spiking levels were proportionately
the samples met the acceptance criterion; therefore, the higher when smaller sample amounts were used during
reference laboratory reported the EDRO concentrations extraction. The acceptance criteria for MS/MSDs were 46
measured during the reanalyses. The remaining two to 124 percent recovery and an RPD less than or equal to
samples for which the surrogate recoveries did not meet 45. When the MS/MSD percent recovery acceptance
the acceptance criterion were LCS/LCSD samples; these criterion was not met, instead of attributing the failure to
samples had low surrogate recoveries. According to the meet the criterion to an inappropriate spiking level, the
reference laboratory, these low recoveries were due to the reference laboratory respiked the samples at a target
extracts going dry during the extract concentration spiking level between 50 and 150 percent of the unspiked
procedure. Because two samples were laboratory QC sample concentration. Additional information on spiking
samples, the reference laboratory reanalyzed them as well level selection for MS/MSDs is presented in Section 6.1.1.
as all the other samples in the QC lot; during the No MS/MSDs were prepared for liquid PE samples for
reanalyses, all surrogate recoveries met the acceptance EDRO analysis because the analysis did not include a
criterion. The surrogate recoveries for all results reported sample preparation step.
ranged from 45 to 143 percent with mean and median
recoveries of 77 percent, indicating an overall negative For environmental samples, a total of 13 MS/MSD pairs
bias. The surrogate recoveries for all reported sample were analyzed. Two sample pairs collected in the FFA
results met the acceptance criterion. Based on the were designated as MS/MSDs. The sample matrix in this
surrogate results for environmental and associated QC area primarily consisted of medium-grained sand. The
samples, the EDRO analysis results were considered to be percent recoveries for the MS/MSD samples ranged from
valid. 0 to 183 with RPDs of 0 and 19. One of the two sample
pairs exhibited percent recoveries less than the lower
A total of 190 surrogate measurements were made during acceptance limit. In the second sample pair, one sample
analysis of soil PE and associated QC samples. Five of exhibited a percent recovery less than the lower
these samples did not meet the percent recovery acceptance limit, and one sample exhibited a percent
acceptance criterion. In each case, the surrogate was recovery greater than the upper acceptance limit. For both
recovered at a concentration below the lower limit of the sample pairs, the RPD acceptance criterion for the
acceptance criterion. Three of the five samples were soil MS/MSDs and the percent recovery and RPD acceptance
PE samples, and the remaining two samples were criteria for the LCS/LCSDs associated with the analytical

52
batches for these samples were met. Because of the varied primarily consisted of sand and clay. The percent
percent recoveries for the MS/MSD sample pairs, it was recoveries for the MS/MSD samples ranged from 25 to 77
not possible to conclude whether the EDRO analysis with RPDs of 6 and 11. Of the two sample pairs, one
results for the FFA samples had a negative or positive sample pair met the percent recovery acceptance criterion,
bias. Although the MS/MSD results did not meet the and one sample pair exhibited percent recoveries less than
percent recovery acceptance criterion, the out-of-control the lower acceptance limit. For the sample pair that did
situations alone did not constitute adequate grounds for not meet the percent recovery acceptance criterion, the
rejection of any of the EDRO analysis results for the FFA RPD acceptance criterion for the MS/MSDs and the
samples. The out-of-control situations may have been percent recovery and RPD acceptance criteria for the
associated with inadequate spiking levels (0.1 to 0.5 times LCS/LCSDs associated with the analytical batch for the
the unspiked sample concentrations compared to the sample pair were met. Although the percent recoveries for
minimum recommended value of 5 times the one MS/MSD sample pair indicated a negative bias,
concentrations). because the percent recoveries for the other sample pair
were acceptable, it was not possible to conclude that the
Four sample pairs collected in the NEX Service Station EDRO analysis results for the B-38 Area samples had a
Area were designated as MS/MSDs. The sample matrix in negative bias. Although one-half of the MS/MSD results
this area primarily consisted of medium-grained sand. The did not meet the percent recovery acceptance criterion, the
percent recoveries for the MS/MSD samples ranged from out-of-control situations alone did not constitute adequate
81 to 109 with RPDs ranging from 4 to 20. The percent grounds for rejection of any of the EDRO analysis results
recoveries and RPDs for these samples met the acceptance for the B-38 Area samples. The out-of-control situations
criteria. Based on the MS/MSD results, the EDRO may have been associated with inadequate spiking levels
analysis results for the NEX Service Station Area samples (1.4 times the unspiked sample concentrations compared
were considered to be valid. to the minimum recommended value of 5 times the
concentrations).
One sample pair collected in the PRA was designated as an
MS/MSD. The sample matrix in this area primarily Four sample pairs collected in the SFT Area were
consisted of silty sand. The percent recoveries for the designated as MS/MSDs. The sample matrix in this area
MS/MSD samples were 20 and 80 with an RPD equal to primarily consisted of silty clay. The percent recoveries
19. One sample exhibited a percent recovery less than the for the MS/MSD samples ranged from 0 to 223 with RPDs
lower acceptance limit, whereas the percent recovery for ranging from 8 to 50. Of the four sample pairs, three
the other sample met the acceptance criterion. The RPD sample pairs had one sample each that exhibited a percent
acceptance criterion for the MS/MSD and the percent recovery less than the lower acceptance limit and one
recovery and RPD acceptance criteria for the LCS/LCSD sample pair had one sample that exhibited a percent
associated with the analytical batch for this sample pair recovery greater than the upper acceptance limit. The RPD
were met. Although the percent recoveries for the acceptance criterion was met for all but one of the
MS/MSD sample pair may indicate a negative bias, MS/MSDs. The percent recovery and RPD acceptance
because the MS/MSD results for only one sample pair criteria for the LCS/LCSDs associated with the analytical
were available, it was not possible to conclude that the batches for these samples were met. Because of the varied
EDRO analysis results for the PRA samples had a negative percent recoveries for the MS/MSD sample pairs, it was
bias. Although one of the percent recoveries for the not possible to conclude whether the EDRO analysis
MS/MSD did not meet the acceptance criterion, the out-of- results for the SFT Area samples had a negative or positive
control situation alone did not constitute adequate grounds bias. Although one-half of the MS/MSD results did not
for rejection of any of the EDRO analysis results for the meet the percent recovery acceptance criterion and one of
PRA samples. The out-of-control situation may have been the four sample pairs did not meet the RPD acceptance
associated with inadequate spiking levels (0.4 times the criterion, the out-of-control situations alone did not
unspiked sample concentration compared to the minimum constitute adequate grounds for rejection of any of the
recommended value of 5 times the concentration). EDRO analysis results for the SFT Area samples. The out-
of-control situations may have been associated with
Two sample pairs collected in the B-38 Area were inadequate spiking levels (0.4 to 0.7 times the unspiked
designated as MS/MSDs. The sample matrix in this area

53
sample concentrations compared to the minimum control samples prepared by the reference laboratory. To
recommended value of 5 times the concentrations). generate a soil LCS or LCSD, Ottawa sand was spiked
with the EDRO calibration standard at a spiking level of
Five soil PE sample pairs were designated as MS/MSDs. 50 mg/kg. The acceptance criteria for LCS/LCSDs were
The sample matrix for these samples primarily consisted of 46 to 124 percent recovery and an RPD less than or equal
silty sand. The percent recoveries for these samples to 45. The LCS/LCSD acceptance criteria were based on
ranged from 0 to 146 with RPDs ranging from 3 to 17. Of the reference laboratory’s historical data. No LCS/LCSDs
the five sample pairs, three sample pairs met the percent were prepared for liquid PE samples for EDRO analysis
recovery acceptance criterion, one sample pair exhibited because the analysis did not include a sample preparation
percent recoveries less than the lower acceptance limit, and step.
one sample pair exhibited percent recoveries greater than
the upper acceptance limit. For the two sample pairs that Twenty-two pairs of LCS/LCSD samples were prepared
did not meet the percent recovery acceptance criterion, the and analyzed. The percent recoveries for these samples
RPD acceptance criterion for the MS/MSDs and the ranged from 47 to 88 with RPDs ranging from 0 to 29.
percent recovery and RPD acceptance criteria for the Therefore, the percent recoveries and RPDs for these
LCS/LCSDs associated with the analytical batches for samples met the acceptance criteria, indicating that the
these samples were met. Because of the varied percent EDRO analysis procedure was in control. Based on the
recoveries for the MS/MSD sample pairs, it was not LCS/LCSD results, the EDRO analysis results were
possible to conclude whether the EDRO analysis results considered to be valid.
for the soil PE samples had a negative or positive bias.
Although the percent recoveries for two of the five sample Summary of Quality Control Check Results
MS/MSD pairs did not meet the acceptance criterion, the
out-of-control situations alone did not constitute adequate Table 6-2 summarizes the QC check results for EDRO
grounds for rejection of any of the EDRO analysis results analysis. Based on the QC check results, the conclusions
for the soil PE samples. presented below were drawn regarding the accuracy and
precision of EDRO analysis results for the demonstration.
Extract Duplicates
The project-specific percent recovery acceptance criteria
For EDRO analysis, after soil sample extraction, extract were met for all surrogates and LCS/LCSDs. About
duplicates were analyzed to evaluate the precision one-half of the MS/MSDs did not meet the percent
associated with the reference laboratory’s analytical recovery acceptance criterion. As expected, the MS/MSD
procedure. The reference laboratory sampled duplicate percent recovery range was broader for environmental
aliquots of the EDRO extracts for analysis. The samples than for PE samples. The mean and median
acceptance criterion for extract duplicate precision was an percent recoveries for all the QC check samples indicated
RPD less than or equal to 45. One or more environmental a negative bias (up to 33 percent) in the EDRO
samples collected in each demonstration area were concentration measurements. Although the observed bias
designated as extract duplicates. A total of 13 samples was slightly greater than the generally acceptable bias
designated as extract duplicates were analyzed for EDRO. (±30 percent) stated in SW-846 for organic analyses, the
The RPDs for these samples ranged from 0 to 11 except for observed recoveries were not atypical for most organic
one extract duplicate pair collected in the SFT Area that analytical methods for environmental samples. Because
had an RPD equal to 34. The RPDs for all the extract the percent recovery ranges were sometimes above and
duplicates met the acceptance criterion. Based on the sometimes below 100, the observed bias did not appear to
extract duplicate results, all EDRO results were considered be systematic.
to be valid.
The project-specific RPD acceptance criterion was met for
Laboratory Control Samples and Laboratory all samples except one environmental MS/MSD sample
Control Sample Duplicates pair. As expected, the RPD range and the mean and
median RPDs for MS/MSDs associated with the soil
For EDRO analysis, LCS/LCSD results were evaluated to environmental samples were greater than those for other
determine the accuracy and precision associated with QC checks and matrixes listed in Table 6-2. The low

54
 Table 6-2. Summary of Quality Control Check Results for EDRO Analysis

Accuracy (Percent Recovery) Precision (Relative Percent Difference)

No. of No. of No. of
Measurements Measurements Measurements
Matrix Used to Meeting Meeting
Associated Evaluate Data Acceptance Actual Acceptance Acceptance Actual Acceptance
QC Checka with QC Check Quality Criterion Range Criterion Mean Median Criterion Range Criterion Mean Median
Surrogate Soil 179 45 to 143 45 to 143 179 77 77
environmental
samples Not applicable
Soil PE 185 46 to 143 185 76 76
samples
MS/MSD Soil 26 (13 pairs) 46 to 124 0 to 223 14 67 79 #45 0 to 50 12 pairs 17 16
environmental
samples
Soil PE 10 (5 pairs) 0 to 146 6 75 78 3 to 17 5 pairs 7 4
samples
Extract Soil 13 pairs 0 to 34 13 pairs 6 2
duplicate environmental Not applicable
samples
LCS/LCSD Soil 44 (22 pairs) 46 to 124 47 to 88 44 77 80 0 to 29 22 pairs 6 5

55
environmental
and PE
samples

Notes:

# = Less than or equal to

LCS/LCSD = Laboratory control sample and laboratory control sample duplicate
MS/MSD = Matrix spike and matrix spike duplicate
PE = Performance evaluation
QC = Quality control
a
During the demonstration, 22 method blanks for soil samples and 2 instrument blanks for liquid samples were analyzed. The blank results met the project-specific acceptance criteria.
RPDs observed indicated good precision in the EDRO method results were based on mean TPH results for
concentration measurements made during the triplicate samples analyzed by ERA using a GC/FID
demonstration. method. ERA extracted the PE samples on the day that PE
samples were shipped to the Navy BVC site for
6.2 Selected Performance Evaluation Sample distribution to the reference laboratory and developers.
Results The reference laboratory completed methanol extraction of
the demonstration samples within 2 days of receiving
Soil and liquid PE samples were analyzed during the them. Between 5 and 7 days elapsed between the time that
demonstration to document the reference method’s ERA and the time that the reference laboratory completed
performance in analyzing samples prepared under methanol extractions of the demonstration samples. The
controlled conditions. The PE sample results coupled with difference in extraction times is not believed to have had
the QC check results were used to establish the reference a significant effect on the reference method’s TPH results
method’s performance in such a way that the overall because the samples for GRO analysis were containerized
assessment of the reference method would support in EPA-approved EnCores and were stored at 4 ± 2 °C to
interpretation of the OCMA-350’s performance, which is minimize volatilization. After methanol extraction of the
discussed in Chapter 7. Soil PE samples were prepared by PE samples, both ERA and the reference laboratory
adding weathered gasoline or diesel to Ottawa sand or analyzed the sample extracts within the appropriate
processed garden soil. For each sample, an amount of holding times for the extracts.
weathered gasoline or diesel was added to the sample
matrix in order to prepare a PE sample with a low (less For soil samples containing diesel, the certified values
than 100 mg/kg), medium (100 to 1,000 mg/kg), or high were established by calculating the TPH concentrations
(greater than 1,000 mg/kg) TPH concentration. Liquid PE based on the amounts of diesel spiked into known
samples consisted of neat materials. Triplicate samples of quantities of soil; these samples were not analyzed by
each type of PE sample were analyzed by the reference ERA. Similarly, the densities of the neat materials were
laboratory except for the low-concentration-range PE used as the certified values for the liquid PE samples.
samples, for which seven replicate samples were analyzed.
The performance acceptance limits for soil PE samples
As described in Section 4.2, some PE samples also were based on ERA’s historical data on percent recoveries
contained interferents. Section 6.2 does not discuss the and RSDs from multiple laboratories that had analyzed
reference method results for PE samples containing similarly prepared ERA PE samples using a GC method.
interferents because the results address a specific The performance acceptance limits were determined at the
demonstration objective. To facilitate comparisons, the 95 percent confidence level using Equation 6-1.
reference method results that directly address
demonstration objectives are discussed along with the Performance Acceptance Limits = Certified Value x
OCMA-350 results in Chapter 7. Section 6.2 presents a (Average Percent Recovery + 2(Average RSD)) (6-1)
comparison of the reference method’s mean TPH results
for selected PE samples to the certified values and According to SW-846, the 95 percent confidence limits
performance acceptance limits provided by ERA, a should be treated as warning limits, whereas the 99 percent
commercial PE sample provider that prepared the PE confidence limits should be treated as control limits. The
samples for the demonstration. Although the reference 99 percent confidence limits are calculated by using three
laboratory reported sample results for GRO and EDRO times the average RSD in Equation 6-1 instead of two
analyses separately, because ERA provided certified values times the average RSD.
and performance acceptance limits, the reference method’s
mean TPH results (GRO plus EDRO analysis results) were When establishing the performance acceptance limits,
used for comparison. ERA did not account for variables among the multiple
laboratories, such as different extraction and analytical
For soil samples containing weathered gasoline, the methods, calibration procedures, and chromatogram
certified values used for comparison to the reference integration ranges (beginning and end points). For this
reason, the performance acceptance limits should be used
with caution.

56
Performance acceptance limits for liquid PE samples were concentration-range soil PE samples listed in Table 6-3,
not available because ERA did not have historical the contribution of the processed garden soil to the TPH
information on percent recoveries and RSDs for the neat concentrations was insignificant and ranged between 0.5
materials used in the demonstration. and 5 percent.

Table 6-3 presents the PE sample types, TPH concentration The reference method’s mean TPH results for the soil PE
ranges, performance acceptance limits, certified values, samples listed in Table 6-3 were within the performance
reference method mean TPH concentrations, and ratios of acceptance limits except for the low-concentration-range
reference method mean TPH concentrations to certified diesel samples. For the low-range diesel samples, (1) the
values. individual TPH concentrations for all seven replicates were
less than the lower performance acceptance limit and
In addition to the samples listed in Table 6-3, three blank (2) the upper 95 percent confidence limit for TPH results
soil PE samples (processed garden soil) were analyzed to was also less than the lower performance acceptance limit.
determine whether the soil PE sample matrix contained a However, the reference method mean and individual TPH
significant TPH concentration. Reference method GRO results for the low-range diesel samples were within the
results for all triplicate samples were below the reporting 99 percent confidence interval of 10.8 to 54.6 mg/kg,
limit of 0.54 mg/kg. Reference method EDRO results indicating that the reference method results met the control
were calculated by adding the results for DRO and oil limits but not the warning limits. Collectively, these
range organics (ORO) analyses. For one of the triplicate observations indicated a negative bias in TPH
samples, both the DRO and ORO results were below the measurements for low-range diesel samples.
reporting limits of 4.61 and 5.10 mg/kg, respectively. For
the remaining two triplicates, the DRO and ORO results As noted above, Table 6-3 presents ratios of the reference
were 1.5 times greater than the reporting limits. Based on method mean TPH concentrations to the certified values
the TPH concentrations in the medium- and high- for PE samples. The ratios for weathered gasoline-

Table 6-3. Comparison of Soil and Liquid Performance Evaluation Sample Results

TPH Performance Reference Method Reference Method Mean

Concentration Acceptance Limits Mean TPH TPH Concentration/
Sample Typea Range (mg/kg) Certified Value Concentration Certified Value (percent)
Soil Sample (Ottawa Sand)
Diesel Low 18.1 to 47.4 37.3 mg/kg 14.7 mg/kg 39
Soil Samples (Processed Garden Soil)
Weathered gasoline Medium 196 to 781 550 mg/kg 344 mg/kg 62
High 1,110 to 4,430 3,120 mg/kg 2,030 mg/kg 65
Weathered gasoline at High 992 to 3,950 2,780 mg/kg 1,920 mg/kg 69
16 percent moisture
Diesel Medium 220 to 577 454 mg/kg 281 mg/kg 62
High 1,900 to 4,980 3,920 mg/kg 2,720 mg/kg 69
Diesel at less than 1 percent High 2,100 to 5,490 4,320 mg/kg 2,910 mg/kg 67
moisture
Liquid Samples
Weathered gasoline High Not available 814,100 mg/L 648,000 mg/L 80
Diesel High Not available 851,900 mg/L 1,090,000 mg/L 128

Notes:

mg/kg = Milligram per kilogram

mg/L = Milligram per liter
a
Soil samples were prepared at 9 percent moisture unless stated otherwise.

57
containing soil samples ranged from 62 to 69 percent and The positive bias observed for liquid samples did not
did not appear to depend on whether the samples were exceed the generally acceptable bias stated in SW-846.
medium- or high-range samples. The ratio for neat, The negative bias observed for high-concentration-range
weathered gasoline (liquid sample) was 80 percent, which soil samples exceeded the acceptable bias by an average of
was 11 to 18 percentage points greater than the ratios for 2 percentage points. However, the negative bias observed
the soil samples. The difference in the ratios may be for low- and medium-range samples exceeded the
attributed to (1) potential loss of volatiles during soil acceptable bias by 31 and 8 percentage points,
sample transport and storage and during soil sample respectively, indicating a negative bias.
handling when extractions were performed and (2) lower
analyte recovery during soil sample extraction. The less Because the reference method results exhibited a negative
than 100 percent ratios observed indicated a negative bias bias for soil PE samples when compared to ERA-certified
in TPH measurement for soil and liquid samples values, ERA’s historical data on percent recoveries and
containing weathered gasoline. The observed bias for the RSDs from multiple laboratories were examined.
liquid samples did not exceed the generally acceptable bias Table 6-4 compares ERA’s historical percent recoveries
(±30 percent) stated in SW-846 for most organic analyses. and RSDs to the reference method percent recoveries and
However, the bias for soil samples exceeded the acceptable RSDs obtained during the demonstration. Table 6-4 shows
bias by up to 8 percentage points. that ERA’s historical recoveries also exhibited a negative
bias for all sample types except weathered gasoline in
The ratios for diesel-containing soil samples ranged from water and that the reference method recoveries were less
39 to 69 percent and increased with increases in the TPH than ERA’s historical recoveries for all sample types
concentration range. The ratio for neat diesel (liquid except diesel in water. The ratios of reference method
sample) was 128 percent, which was substantially greater mean recoveries to ERA historical mean recoveries for
than the ratios for soil samples. Collectively, the negative weathered gasoline-containing samples indicated that the
bias observed for soil samples and the positive bias reference method TPH results were 26 percent less than
observed for liquid samples indicated a low analyte ERA’s historical recoveries. The reference method
recovery during soil sample extraction because the soil and recoveries for diesel-containing (1) soil samples were
liquid samples were analyzed using the same calibration 32 percent less than the ERA historical recoveries and
procedures but only the soil samples required extraction (2) water samples were 63 percent greater than the ERA
before analysis. The extraction procedure used during the historical recoveries. In all cases, the RSDs for the
demonstration is an EPA-approved method that is widely reference method were significantly lower than ERA’s
used by commercial laboratories in the United States. historical RSDs, indicating that the reference method
Details on the extraction procedure are presented in achieved significantly greater precision. The greater
Table 5-3 of this ITVR. precision observed for the reference method during the

Table 6-4. Comparison of Environmental Resource Associates Historical Results to Reference Method Results

ERA Historical Results Reference Method Results

Mean Relative Mean Reference Method Mean Mean Relative
Mean Recovery Standard Deviation Recoverya Recovery/ERA Historical Standard Deviationa
Sample Type (percent) (percent) (percent) Mean Recovery (percent) (percent)
Weathered gasoline in soil 88.7 26.5 65 74 8
Diesel in soil 87.7 19.6 59 68 7
Weathered gasoline in water 109 22.0 80 73 5
Diesel in water 78.5 22.8 128 163 6

Notes:

ERA = Environmental Resource Associates

a
The reference method mean recovery and mean relative standard deviation were based on recoveries and relative standard deviations observed
for all concentration ranges for a given type of performance evaluation sample.

58
demonstration may be associated with the fact that the 6.3 Data Quality
reference method was implemented by a single laboratory,
whereas ERA’s historical RSDs were based on results Based on the reference method’s performance in analyzing
obtained from multiple laboratories that may have used the QC check samples and selected PE samples, the
different analytical protocols. reference method results were considered to be of
adequate quality for the following reasons: (1) the
In summary, compared to ERA-certified values, the TPH reference method was implemented with acceptable
results for all PE sample types except neat diesel exhibited accuracy (±30 percent) for all samples except low- and
a negative bias to a varying degree; the TPH results for medium-concentration-range soil samples containing
neat diesel exhibited a positive bias of 28 percent. For diesel, which made up only 13 percent of the total number
weathered gasoline-containing soil samples, the bias was of samples analyzed during the demonstration, and (2) the
relatively independent of the TPH concentration range and reference method was implemented with good precision
exceeded the generally acceptable bias stated in SW-846 for all samples (the overall RPD range was 0 to 17). The
by up to 8 percentage points. For neat gasoline samples, reference method results generally exhibited a negative
the bias did not exceed the acceptable bias. For diesel- bias. However, the bias was considered to be significant
containing soil samples, the bias increased with decreases primarily for low- and medium-range soil samples
in the TPH concentration range, and the bias for low-, containing diesel because the bias exceeded the generally
medium-, and high-range samples exceeded the acceptable bias of ±30 percent stated in SW-846 by
acceptable bias by 31, 8, and 2 percentage points, 31 percentage points for low-range and 8 percentage
respectively. For neat diesel samples, the observed points for medium-range samples. The reference method
positive bias did not exceed the acceptable bias. The low recoveries observed were typical of the recoveries
RSDs (5 to 8 percent) associated with the reference obtained by most organic analytical methods for
method indicated good precision in analyzing both soil and environmental samples.
liquid samples. Collectively, these observations suggest
that caution should be exercised during comparisons of
OCMA-350 and reference method results for low- and
medium-range soil samples containing diesel.

59
 Chapter 7
Performance of the OCMA-350

To verify a wide range of performance attributes, the distributed to Horiba and the reference laboratory. The
demonstration had both primary and secondary objectives. numbers and types of environmental samples collected in
Primary objectives were critical to the technology each sampling area and the numbers and types of PE
evaluation and were intended to produce quantitative samples prepared are discussed in Chapter 4. Primary
results regarding a technology’s performance. Secondary objectives P1 through P4 were addressed using statistical
objectives provided information that was useful but did not and nonstatistical approaches, as appropriate. The
necessarily produce quantitative results regarding a statistical tests performed to address these objectives are
technology’s performance. This chapter discusses the illustrated in the flow diagram in Figure 7-1. Before a
performance of the OCMA-350 based on the primary parametric test was performed, the Wilk-Shapiro test was
objectives (excluding costs associated with TPH used to determine whether the OCMA-350 results and
measurement) and secondary objectives. Costs associated reference method results or, when appropriate, their
with TPH measurement (primary objective P6) are differences were normally distributed at a significance
presented in Chapter 8. The demonstration results for both level of 5 percent. If the results or their differences were
the primary and secondary objectives are summarized in not normally distributed, the Wilk-Shapiro test was
Chapter 9. performed on transformed results (for example, logarithm
and square root transformations) to verify the normality
7.1 Primary Objectives assumption. If the normality assumption was not met, a
nonparametric test was performed. Nonparametric tests
This section discusses the performance results for the are not as powerful as parametric tests because the
OCMA-350 based on primary objectives P1 through P5, nonparametric tests do not account for the magnitude of
which are listed below. the difference between sample results. Despite this
limitation, when the normality assumption was not met,
P1. Determine the MDL performing a nonparametric test was considered to be a
better alternative than performing no statistical
P2. Evaluate the accuracy and precision of TPH comparison.
measurement for a variety of contaminated soil
samples For the OCMA-350, when the TPH concentration in a
given sample was reported as below the reporting limit,
P3. Evaluate the effect of interferents on TPH one-half the reporting limit was used as the TPH
measurement concentration for that sample, as is commonly done, so that
necessary calculations could be performed without
P4. Evaluate the effect of soil moisture content on TPH rejecting the data. The same approach was used for the
measurement reference method except that the appropriate reporting
limits were used in calculating the TPH concentration
P5. Measure the time required for TPH measurement depending on which TPH measurement components
(GRO, DRO, and ORO) were reported at concentrations
To address primary objectives P1 through P5, samples below the reporting limits. Caution was exercised to
were collected from five different sampling areas. In ensure that these necessary data manipulations did not
addition, soil and liquid PE samples were prepared and alter the conclusions.

60
 TPH results
Method detection limit Accuracy Precision Effect of interferents Effect of soil moisture content
(primary objective P1) (primary objective P2) (primary objective P2) (primary objective P3) (primary objective P4)

Were Calculated relative

Were Were Were
TPH results standard deviation
TPH results TPH results TPH results
normally distributed? for field triplicate
normally distributed? for three sample groups of both sample groups
(Wilk-Shapiro TPH results
(Wilk-Shapiro normally distributed? normally distributed?
test) test) (Wilk-Shapiro (Wilk-Shapiro
Calculated relative test) test)
Yes Yes percent difference
for extract duplicate Yes
TPH results Yes
Determined method No Performed two-tailed, paired
detection limit using Student's t-test (parametric) No
approach recommended in to determine whether field Performed two-sample
40 Code of Federal measurement device and Were No Student's t-test
reference method TPH group variances (parametric) to determine
Regulations Part 136, No
results were statistically the equal? whether increase in
Appendix B, Revision 1.1.1
same (Bartlett's test) moisture content resulted
in increase or decrease in
Was unable to determine Performed Wilcoxon signed TPH results
method detection limit rank test (nonparametric) to
determine whether field Yes

61
measurement device and
reference method TPH Performed Kruskal-Wallis
results were statistically Performed one-way Performed Kruskal-Wallis one-way analysis of
analysis of variance one-way analysis of variance (nonparametric)
the same
(parametric) and Tukey variance (nonparametric) and Kruskal-Wallis
Performed linear regression (honest, significant and Kruskal-Wallis comparison of means
to determine whether difference) comparison of comparison of means (nonparametric) to
means (parametric) to (nonparametric) to determine whether
consistent correlation existed
between field measurement determine whether presence determine whether increase in moisture
device and reference method of interferents resulted in presence of interferents content resulted in
TPH results increase or decrease in resulted in increase or increase or decrease in
TPH results decrease in TPH results TPH results

Performed measurement
F-test to determine whether
correlation was merely by
chance

Figure 7-1. Summary of statistical analysis of TPH results.

The reference method GRO results were adjusted for Table 7-1. TPH Results for Low-Concentration-Range Diesel Soil
Performance Evaluation Samples
solvent dilution associated with the soil sample moisture
content because the method required use of methanol, a OCMA-350 Result (mg/kg) Reference Method Result (mg/kg)
water-miscible solvent, for extraction of soil samples. In 28.8 16.4
addition, based on discussions with Horiba and the 21.0 16.4
reference laboratory, all TPH results for the OCMA-350 30.6 13.2
and the reference method were rounded to three significant 24.2 16.0
figures.
33.4 14.2
23.2 14.1
7.1.1 Primary Objective P1: Method Detection
32.2 12.8
Limit MDL 15.2 4.79

To determine the MDLs for the OCMA-350 and reference Notes:

method, both Horiba and the reference laboratory analyzed
MDL = Method detection limit
seven low-concentration-range soil PE samples containing mg/kg = Milligram per kilogram
weathered gasoline and seven low-concentration-range soil
PE samples containing diesel. As discussed in Chapter 4,
problems arose during preparation of the low-range Based on the TPH results for the low-concentration-range
weathered gasoline samples; therefore, the results for the diesel soil PE samples, the MDLs were determined to be
soil PE samples containing weathered gasoline could not 15.2 and 4.79 mg/kg for the OCMA-350 and reference
be used to determine MDLs. method, respectively. Because the ORO concentrations in
all these samples were below the reference laboratory’s
Because the OCMA-350 and reference method results estimated reporting limit (5.1 mg/kg), the MDL for the
were both normally distributed, the MDLs for the soil PE reference method was also calculated using only DRO
samples containing diesel were calculated using results. The MDL for the reference method based on the
Equation 7-1 (40 CFR Part 136, Appendix B, DRO results was 4.79 mg/kg, which was the same as the
Revision 1.1.1). An MDL thus calculated is influenced by MDL for the reference method based on the EDRO results,
TPH concentrations because the standard deviation will indicating that the ORO concentrations below the
likely decrease with a decrease in TPH concentrations. As reporting limit did not impact the MDL for the reference
a result, the MDL will be lower when low-concentration method.
samples are used for MDL determination. Despite this
limitation, Equation 7-1 is commonly used and provides a The MDL of 15.2 mg/kg for the OCMA-350 was greater
reasonable estimate of the MDL. than the MDL of 1 mg/kg claimed by Horiba. The MDL
of 4.79 mg/kg for the reference method compared well
MDL = ( S) t (n −1, 1− α = 0 .99 ) (7-1) with the MDL of 4.72 mg/kg published in SW-846
where Method 8015C for diesel samples extracted using a
S = Standard deviation of replicate TPH results pressurized fluid extraction method and analyzed for
t (n− 1,1− α = 0 .99 )
DRO.
= Student’s t-value appropriate for a
99 percent confidence level and a 7.1.2 Primary Objective P2: Accuracy and
standard deviation estimate with n-1 Precision
degrees of freedom (3.143 for n = 7
replicates) This section discusses the ability of the OCMA-350 to
accurately and precisely measure TPH concentrations in a
Because GRO compounds were not expected to be present variety of contaminated soils. The OCMA-350 TPH
in the soil PE samples containing diesel, the reference results were compared to the reference method TPH
laboratory performed only EDRO analysis of these results. Accuracy and precision are discussed in
samples and reported the sums of the DRO and ORO Sections 7.1.2.1 and 7.1.2.2, respectively.
concentrations as the TPH results. The OCMA-350 and
reference method results for these samples are presented in
Table 7-1.

62
7.1.2.1 Accuracy environmental and soil PE samples. Section 4.2 of this
ITVR explains how the action levels were selected for the
The accuracy of OCMA-350 measurement of TPH was demonstration. Of the environmental samples, the
assessed by determining percentage of samples for which the conclusions agreed
ranged from 71 to 100. Of the PE samples, the percentage
• Whether the conclusion reached using the OCMA-350 of samples for which the conclusions agreed ranged from
agreed with that reached using the reference method 0 to 100. Overall, the conclusions were the same for
regarding whether the TPH concentration in a given 73 percent of the samples.
sampling area or soil type exceeded a specified action
level The least agreement observed for the environmental
samples was for those from the SFT Area (71 percent).
• Whether the OCMA-350 results were biased high or Regarding the PE samples, none of the OCMA-350 action
low compared to the reference method results level conclusions agreed with those of the reference
method for the medium-concentration-range weathered
• Whether the OCMA-350 results were different from gasoline and diesel samples and the high-concentration-
the reference method results at a statistical significance range diesel samples with 9 percent moisture content. The
level of 5 percent when a pairwise comparison was 0 percent agreement observed for these samples cannot be
made explained.

• Whether a significant correlation existed between the When the action level conclusions did not agree, the TPH
OCMA-350 and reference method results results were further interpreted to assess whether the
OCMA-350 conclusion was conservative. The OCMA-
During examination of these four factors, the data quality 350 conclusion was considered to be conservative when
of the reference method and OCMA-350 TPH results was the OCMA-350 result was above the action level and the
considered. For example, as discussed in Chapter 6, the reference method result was below the action level. A
reference method generally exhibited a low bias. regulatory agency would likely favor a field measurement
However, the bias observed for all samples except low- device whose results are conservative; however, the party
and medium-concentration-range diesel soil samples did responsible for a site cleanup might not favor a device that
not exceed the generally acceptable bias of ±30 percent is overly conservative because of the cost associated with
stated in SW-846 for organic analyses. Therefore, caution unnecessary cleanup. For the OCMA-350, 29 of
was exercised during comparison of the OCMA-350 and 107 action level conclusions did not agree with the
reference method results, particularly those for low- and reference method conclusions. Of the 29 OCMA-350
medium-range diesel soil samples. Caution was also conclusions, 11 of the 13 conclusions for environmental
exercised during interpretation of statistical test samples and 12 of the 16 conclusions for PE samples were
conclusions drawn based on a small number of samples. not conservative.
For example, only three samples were used for each type
of PE sample except the low-range diesel samples; the Measurement Bias
small number of samples used increased the probability
that the results being compared would be found to be To determine the measurement bias, the ratios of the
statistically the same. OCMA-350 TPH results to the reference method TPH
results were calculated. The observed bias values were
As discussed in Chapter 2, during the demonstration, the grouped to identify the number of OCMA-350 results
OCMA-350 was calibrated using diesel. The following within the following ranges of the reference method
sections discuss how the OCMA-350 results compared results: (1) greater than 0 to 30 percent, (2) greater than 30
with the reference method results by addressing each of the to 50 percent, and (3) greater than 50 percent.
four factors identified above.
Figure 7-2 shows the distribution of measurement bias for
Action Level Conclusions the environmental samples. Of the five sampling areas,
good agreement between the OCMA-350 and reference
Table 7-2 compares action level conclusions reached using method results was observed for samples collected from
the OCMA-350 and reference method results for the FFA and NEX Service Station Area; for these samples,

63
Table 7-2. Action Level Conclusions

Percentage of Samples for When Conclusions Did Not Agree,

Action Total Number Which OCMA-350 and Were OCMA-350 Conclusions
Level of Samples Reference Method Conservative or Not
Sampling Area or Sample Type (mg/kg) Analyzed Conclusions Agreed Conservative?a
Fuel Farm Area 100 10 100
Naval Exchange Service Station Area 50 20 95 Not conservative
Phytoremediation Area 1,500 8 75 Not conservative (one of two
conclusions for each area)
B-38 Area 100 8 75
Slop Fill Tank Area 500 28 71 Not conservative
PE sample Blank soil 10 3b 100
(9 percent moisture content)
PE sample Blank soil and humic acid 200 6 100
(9 percent moisture content)
Soil PE sample Medium-concentration range 200 3 0 Not conservative
containing (9 percent moisture content)
weathered
High-concentration range 2,000 3 33
gasoline in
(9 percent moisture content)
High-concentration range 2,000 3 67
(16 percent moisture content)
Soil PE sample Low-concentration range 15 7 43 Conservative
containing diesel in (9 percent moisture content)
Medium-concentration range 200 3 0 Not conservative
(9 percent moisture content)
High-concentration range 2,000 3 100
(less than 1 percent moisture
content)
High-concentration range 2,000 3 0 Not conservative
(9 percent moisture content)
Total 108 73

Notes:

mg/kg = Milligram per kilogram

PE = Performance evaluation
a
A conclusion was considered to be conservative when the OCMA-350 result was above the action level and the reference method result was below
the action level. A conservative conclusion may also be viewed as a false positive.
b
Action level conclusions could be drawn for only two of three samples; the OCMA-350 TPH result for the remaining sample was reported as a “less
than” value—specifically, less than 15.2 mg/kg, which was greater than the action level.

80 and 85 percent of the OCMA-350 results, respectively, The results for 70 percent of the samples from the FFA
were within 50 percent of the reference method results. were biased high, perhaps because of the significant
Moderate agreement between the device and reference negative bias associated with reference method results for
method results was observed for samples collected from diesel soil PE samples (see Chapter 6). The reason that
the PRA and B-38 Area; for these samples, 62 and most of the OCMA-350 results for the other sampling
50 percent of the OCMA-350 results, respectively, were areas were biased low was unclear.
within 50 percent of the reference method results. For
samples collected from the SFT Area, 28 percent of the Figure 7-3 shows the distribution of measurement bias for
OCMA-350 results were within 50 percent of the reference selected soil PE samples. Of the five sets of samples
method results. containing PHCs and the one set of blank samples,
moderate agreement between the OCMA-350 and
Most of the OCMA-350 results were biased low except reference method results was observed for the blank
those for the PRA and FFA samples. Low and high biases samples and the high-concentration-range weathered
were split equally for the samples collected from the PRA. gasoline and diesel samples; for these samples, 67, 50, and

64
 Fuel Farm Area B-38 Area
Total number of samples: 10 Total number of samples: 8
3

0
>0 to 30 >30 to 50 >50
Bias, percent

Naval Exchange Service Station Area Slop Fill Tank Area

Total number of samples: 20 Total number of samples: 28
20

15

10

0
>0 to 30 >30 to 50 >50 >0 to 30 >30 to 50 >50
Bias, percent Bias, percent

Phytoremediation Area
Total number of samples: 8
2

0
>0 to 30 >30 to 50 >50
Bias, percent

Figure 7-2. Measurement bias for environmental samples.

65
 Blank soil
Total number of samples: 3
2

0
>0 to 30 >30 to 50 >50 >0 to 30 >30 to 50 >50
Bias, percent Bias, percent

Weathered gasoline in
medium-concentration range Diesel in medium-concentration range
Total number of samples: 3 Total number of samples: 3
3

0
>0 to 30 >30 to 50 >50 >0 to 30 >30 to 50 >50
Bias, percent Bias, percent

Weathered gasoline in
Diesel in high-concentration range
high-concentration range
Total number of samples: 6
Total number of samples: 6

>0 to 30 >30 to 50 >50 >0 to 30 >30 to 50 >50

Bias, percent Bias, percent

Figure 7-3. Measurement bias for soil performance evaluation samples.

66
50 percent of the OCMA-350 results, respectively, were Table 7-4 shows that the OCMA-350 and reference
within 50 percent of the reference method results. For method results were statistically the same at a significance
medium-range diesel samples, 33 percent of the OCMA- level of 5 percent for blank soil PE samples and neat
350 results were within 50 percent of the reference method weathered gasoline PE samples. The OCMA-350 and
results. For the OCMA-350, only one of the seven low- reference method results for all other PE sample types
range diesel sample results was within 30 percent of the were statistically different. Based on a simple comparison
reference method result, and the remaining six sample of the results, these conclusions appeared to be reasonable,
results exhibited a bias of greater than 50 percent. All except for high-concentration-range weathered gasoline
three OCMA-350 results for medium-range weathered (16 percent moisture content) and high-concentration-
gasoline samples exhibited a bias of greater than range diesel (less than 1 percent moisture content).
50 percent. However, the statistical conclusions for high-range
weathered gasoline (16 percent moisture content) and
The OCMA-350 results were biased high for all PE diesel (less than 1 percent moisture content) are justified
samples except the high-concentration-range weathered considering that the OCMA-350 exhibited a consistent bias
gasoline samples, the medium-concentration-range diesel and that the differences between the OCMA-350 and
samples, and three high-concentration-range diesel reference method TPH results were considerably different
samples. The high bias observed for the OCMA-350 than zero.
results for low-range diesel samples might be explained by
the significant negative bias associated with the reference Of the OCMA-350 PE sample results that were statistically
method results for low-range diesel samples. However, the different from the reference method results, the
high bias of greater than 50 percent observed for the OCMA-350 results for (1) all soil samples containing low-
remaining OCMA-350 results cannot be explained based concentration-range diesel, and high-concentration-range
solely on the negative bias associated with the reference diesel (less than 1 percent moisture content) were biased
method (see Chapter 6). high by up to a factor of two; (2) all soil samples
containing medium- and high-concentration-range diesel
Pairwise Comparison of TPH Results (9 percent moisture content) and medium- and high-
concentration-range weathered gasoline were biased low
To evaluate whether a statistically significant difference by up to a factor of three; and (3) neat diesel samples were
existed between the OCMA-350 and reference method biased low by up to 35 percent. In addition, the OCMA-
TPH results, a parametric test (a two-tailed, paired 350 results for the liquid PE samples were biased low
Student’s t-test) or a nonparametric test (a Wilcoxon when compared to the sample densities. Specifically, the
signed rank test) was selected based on the approach OCMA-350 results were biased low by 32 percent for neat
presented in Figure 7-1. Tables 7-3 and 7-4 present weathered gasoline samples and by 13 percent for neat
statistical comparisons of the OCMA-350 and reference diesel samples.
method results for environmental and PE samples,
respectively. The tables present the OCMA-350 and Correlation of TPH Results
reference method results for each sampling area or PE
sample type, the statistical test performed and the To determine whether a significant correlation existed
associated null hypothesis used to compare the results, between the OCMA-350 and reference method TPH
whether the results were statistically the same or different, results, linear regression analysis was performed. A strong
and the probability that the results were the same. correlation between the OCMA-350 and reference method
results would indicate that the device results could be
Table 7-3 shows that the OCMA-350 and reference adjusted using the established correlation and that field
method results were statistically the same at a significance decisions could be made using the adjusted results in
level of 5 percent for all sampling areas except the SFT situations where the device results may not be the same as
Area. Based on a simple comparison of the results, this off-site laboratory results. Figures 7-4 and 7-5 show the
conclusion appeared to be reasonable for all sampling linear regression plots for environmental and soil PE
areas. For example, for the SFT Area, the OCMA-350 samples, respectively. Table 7-5 presents the regression
results were biased low by up to one order of magnitude model, square of the correlation coefficient (R2), and
for 26 of 28 samples, which justified the statistical test probability that the slope of the regression line is equal to
conclusion.

67
Table 7-3. Statistical Comparison of OCMA-350 and Reference Method TPH Results for Environmental Samples

TPH Result (mg/kg) Statistical Analysis Summary

Were OCMA-350 and Reference Probability of Null
Reference Statistical Test Method Results Statistically the Hypothesis Being
Sampling Area OCMA-350 Method and Null Hypothesis Same or Different? True (percent)
Fuel Farm Area 87.6 68.2 Statistical Test Same 10.54
14,600 15,000 Wilcoxon signed rank test
(nonparametric)
69.1 90.2
17,200 12,000 Null Hypothesis
The median of the differences
94.4 44.1 between the paired observations
15,300 13,900 (OCMA-350 and reference method
1,570 1,330 results) is equal to zero.

8,990 8,090
44.4 93.7
14,400 12,300
Naval Exchange 32.6 28.8 Statistical Test Same 72.75
Service Station 241 144 Two-tailed, paired Student’s t-test
Area (parametric)
777 617
360 293 Null Hypothesis
The mean of the differences
314 280 between the paired observations
1,440 1,870 (OCMA-350 and reference method
1,530 1,560 results) is equal to zero.

Less than 15.2 9.56

380 270
1,540 881
1,100 1,120
Less than 15.2 14.2
266 219
997 1,180
1,200 1,390
Less than 15.2 15.2
43.2 54.5
1,840 2,570
2,390 3,030
Less than 15.2 15.9
Phytoremediation 2,050 2,140 Statistical Test Same 65.14
Area 3,070 1,790 Two-tailed, paired Student’s t-test
(parametric)
2,840 1,390
786 1,420 Null Hypothesis
The mean of the differences
798 1,130 between the paired observations
1,590 1,530 (OCMA-350 and reference method
771 1,580 results) is equal to zero.

1,480 1,300

68
Table 7-3. Statistical Comparison of OCMA-350 and Reference Method TPH Results for Environmental Samples (Continued)

TPH Result (mg/kg) Statistical Analysis Summary

Were OCMA-350 and Reference Probability of Null
Reference Statistical Test Method Results Statistically the Hypothesis Being
Sampling Area OCMA-350 Method and Null Hypothesis Same or Different? True (percent)
B-38 Area 47.5 79.0 Statistical Test Same 14.99
31.4 41.5 Two-tailed, paired Student’s t-test
(parametric)
30.4 61.4
48.6 67.3 Null Hypothesis
The mean of the differences
80.6 193 between the paired observations
118 69.4 (OCMA-350 and reference method
28.8 43.8 results) is equal to zero.

20.6 51.6
Slop Fill Tank Less than 15.2 105 Statistical Test Different 0.00
Area 111 269 Two-tailed, paired Student’s t-test
(parametric)
92.0 397
271 339 Null Hypothesis
The mean of the differences
44.7 6.16 between the paired observations
Less than 15.2 37.1 (OCMA-350 and reference method
Less than 15.2 43.9 results) is equal to zero.
Less than 15.2 52.4
1,560 3,300
571 1,270
389 588
576 554
434 834
172 501
146 280
156 185
240 1,090
78.5 544
96.7 503
16.7 146
510 938
123 517
254 369
20.4 253
35.1 151
1,540 3,960
235 1,210
52.6 121

Note:

mg/kg = Milligram per kilogram

69
Table 7-4. Statistical Comparison of OCMA-350 and Reference Method TPH Results for Performance Evaluation Samples

TPH Result Statistical Analysis Summary

Were OCMA-350 and
Statistical Test Reference Method Probability of Null
Reference and Results Statistically the Hypothesis Being
Sample Type OCMA-350 Method Null Hypothesis Same or Different? True (percent)
Soil Samples (Processed Garden Soil) (TPH Results in Milligram per Kilogram)
Blank (9 percent moisture content) Less than 15.2 5.12 Statistical Test Same 7.83
20.9 13.1 Two-tailed, paired
Student’s t-test
18.7 13.5 (parametric)
Weathered Medium-concentration range 107 350 Different 0.02
gasoline (9 percent moisture content) 108 346 Null Hypothesis
The mean of the
104 336 differences between the
High-concentration range 657 1,880 paired observations Different 0.44
(9 percent moisture content) 595 2,020 (OCMA-350 and
reference method
638 2,180
results) is equal to zero.
High-concentration range 1,460 1,740 Different 0.40
(16 percent moisture 1,710 1,980
content)
1,720 2,050
Diesel Low-concentration range 28.8 16.4 Different 0.12
(9 percent moisture content) 21.0 16.4
30.6 13.2
24.2 16
33.4 14.2
23.2 14.1
32.2 12.8
Medium-concentration range 124 276 Different 0.25
(9 percent moisture content) 143 273
144 295
High-concentration range 992 2,480 Different 0.53
(9 percent moisture content) 995 2,890
958 2,800
High-concentration range 3,540 2,700 Different 4.16
(less than 1 percent moisture 3,570 2,950
content)
3,460 3,070
Liquid Samples (Neat Materials) (TPH Results in Milligram per Liter)
Weathered gasoline 541,000 656,000 Statistical Test Same 5.99
Two-tailed, paired
566,000 611,000 Student’s t-test
(parametric)
560,000 677,000
Null Hypothesis
Diesel 750,000 1,090,000 The mean of the Different 1.00
differences between the
737,000 1,020,000 paired observations
(OCMA-350 and
758,000 1,160,000 reference method
results) is equal to zero.

70
 Comparison of Fuel Farm Area results Comparison of B-38 Area results
20,000

15,000

10,000

5,000 2
R = 0.96

0
0 5,000 10,000 15,000 20,000
Reference method TPH result (mg/kg) Reference method TPH result (mg/kg)

Comparison of Naval Exchange Service Station Comparison of Slop Fill Tank Area results
Area results 1,600
3,000
2,500 1,200
2,000
2 800
1,500 R = 0.92
R2 = 0.90
1,000 400
500
0 0
0 1,000 2,000 3,000 4,000 0 1,000 2,000 3,000 4,000 5,000
Reference method TPH result (mg/kg) Reference method TPH result (mg/kg)

Comparison of Phytoremediation Area results

Reference method TPH result (mg/kg)

Figure 7-4. Linear regression plots for environmental samples.

71
 Comparison of weathered gasoline zero (F-test probability) for each sampling area and soil PE
performance evaluation sample results sample type.
2,000

Table 7-5 shows that R2 values for (1) environmental

1,500
samples except PRA and B-38 Area samples ranged from
R2 = 0.53
0.90 to 0.96 and (2) soil PE samples ranged from 0.53 to
1,000 0.68. The R2 values for the PRA and B-38 Area samples
were 0.19 and 0.23, respectively. The R2 values for
500 separate regression models for weathered gasoline and
diesel soil PE samples were lower and higher, respectively,
0 than the R2 value for a combined regression model for
0 500 1,000 1,500 2,000 2,500 these PE samples. For environmental samples, the
Reference method TPH result (mg/kg)
probabilities of the slopes of the regression lines being
equal to zero were 0.00 percent for the FFA, NEX Service
Station Area, and SFT Area samples; 27.92 percent for the
PRA samples; and 22.58 percent for the B-38 Area
Comparison of diesel samples. These probabilities indicated that there was (1)
performance evaluation sample results
4,000 a less than 5 percent probability for the FFA, NEX Service
Station Area, and SFT Area samples and (2) a greater than
3,000 5 percent probability for the PRA and B-38 Area samples
2
R = 0.68 that the OCMA-350 and reference method results
2,000 correlated only by chance. For soil PE samples, the
probabilities of the slopes of the regression lines being
1,000 equal to zero were 0.01 and 0.00 percent for the diesel
samples and the combined weathered gasoline and diesel
0 samples, respectively, and 62.68 percent for the weathered
0 500 1,000 1,500 2,000 2,500 3,000 gasoline samples. These probabilities indicated that there
Reference method TPH result (mg/kg) was (1) a less than 5 percent probability for the diesel
samples and the combined weathered gasoline and diesel
samples and (2) a greater than 5 percent probability for the
weathered gasoline samples that the OCMA-350 and
reference method results correlated only by chance.
Comparison of weathered gasoline and diesel
performance evaluation sample results Based on the R2 and probability values, the OCMA-350
4,000
and reference method results were considered to be (1)
highly correlated for FFA, NEX Service Station Area, and
3,000
SFT Area samples; (2) moderately correlated for diesel
R2 = 0.64 and combined weathered gasoline and diesel soil PE
2,000 samples; and (3) weakly correlated for PRA and B-38
Area samples and for weathered gasoline soil PE samples.
1,000

7.1.2.2 Precision
0
0 1,000 2,000 3,000 4,000
Both environmental and PE samples were analyzed to
Reference method TPH result (mg/kg) evaluate the precision associated with TPH measurements
using the OCMA-350 and reference method. The results
of this evaluation are summarized below.

Figure 7-5. Linear regression plots for soil performance evaluation

samples.

72
Table 7-5. Summary of Linear Regression Analysis Results

Regression Model Probability That Slope of

(y = OCMA-350 TPH result, Square of Correlation Regression Line Was Equal
Sampling Area or Sample Type x = reference method TPH result) Coefficient to Zero (percent)
Environmental Samples
Fuel Farm Area y = 1.13x + 128.27 0.96 0.00
Naval Exchange Service Station Area y = 0.77x + 123.21 0.92 0.00
Phytoremediation Area y = 1.28x - 286.80 0.19 27.92
B-38 Area y = 0.32x + 26.13 0.23 22.58
Slop Fill Tank Area y = 0.41x + 2.22 0.90 0.00
Soil Performance Evaluation Samples
Weathered gasoline y = 0.59x - 61.65 0.53 62.68
Diesel y = 0.82x - 33.84 0.68 0.01
Weathered gasoline and diesel y = 0.77x - 93.46 0.64 0.00

Environmental Samples reference method RSDs did not exhibit consistent trends
based on soil type, PHC contamination type, or TPH
Blind field triplicates were analyzed to evaluate the overall concentration.
precision of the sampling, extraction, and analysis steps
associated with TPH measurement. Each set of field Table 7-7 presents the TPH results and RPDs for 13 sets of
triplicates was collected from a well-homogenized sample. extract duplicates analyzed using the OCMA-350 and
Also, extract duplicates were analyzed to evaluate reference method. For the OCMA-350, the RPDs ranged
analytical precision only. Each set of extract duplicates from 0 to 3 with a median of 1. The RPDs for the
was collected by extracting a given soil sample and reference method ranged from 0 to 11 with a median of 4.
collecting two aliquots of the extract. Additional Comparison of the median RPDs for the OCMA-350 and
information on field triplicate and extract duplicate reference method indicated that the OCMA-350 achieved
preparation is included in Chapter 4. a higher level of precision than the reference method. The
OCMA-350 and reference method RPDs did not exhibit
Tables 7-6 and 7-7 present the OCMA-350 and reference consistent trends based on PHC contamination type or
method results for field triplicates and extract duplicates, TPH concentration. As expected, the median RPDs for
respectively. Precision was estimated using RSDs for field extract duplicates were less than the median RSDs for field
triplicates and RPDs for extract duplicates. triplicates for both the OCMA-350 and reference method.
These findings indicated that greater precision was
Table 7-6 presents the TPH results and RSDs for 12 sets achieved when only the analysis step could have
of field triplicates analyzed using the OCMA-350 and contributed to TPH measurement error than when all three
reference method. For the OCMA-350, the RSD steps (sampling, extraction, and analysis) could have
calculated for one set of field triplicates from the SFT contributed to such error.
Area (field triplicate set 12) was not considered in
evaluating the device’s precision because the TPH result Performance Evaluation Samples
for one of the three samples (156 mg/kg) was one order of
magnitude higher than the results for the other two Table 7-8 presents the OCMA-350 and reference method
samples and was thus considered to be an analytical TPH results and RSDs for eight sets of replicates for soil
outlier. The RSDs for the remaining 11 triplicate sets PE samples and two sets of triplicates for liquid PE
ranged from 0 to 49 percent with a median of 20 percent. samples.
For the reference method, the RSDs ranged from 4 to
39 percent with a median of 18 percent. Comparison of For the OCMA-350, the RSD calculated for the blank soil
the OCMA-350 and reference method median RSDs samples was not considered in evaluating the device’s
showed that the OCMA-350 exhibited less overall precision because one of the three blank soil sample
precision than the reference method. The OCMA-350 and results was below the MDL (15.2 mg/kg) and the

73
Table 7-6. Summary of OCMA-350 and Reference Method Precision for Field Triplicates of Environmental Samples

OCMA-350 Reference Method

Field Triplicate TPH Result Relative Standard TPH Result Relative Standard
Sampling Area Set (milligram per kilogram) Deviation (percent) (milligram per kilogram) Deviation (percent)
Fuel Farm Area 1 87.6 16 68.2 34
69.1 90.2
94.4 44.1
2 14,600 9 15,000 11
17,200 12,000
15,300 13,900
Naval Exchange Service 3 314 18 280 13
Station Area
380 270
267 219
4 1,440 22 1,870 39
1,540 881
997 1,180
5 1,530 18 1,560 16
1,100 1,120
1,200 1,390
6 Less than 15.2 0 9.56 23
Less than 15.2 14.2
Less than 15.2 15.2
Phytoremediation Area 7 2,050 20 2,140 21
3,070 1,790
2,840 1,390
B-38 Area 8 47.5 24 79 13
30.4 61.4
48.6 67.3
Slop Fill Tank Area 9 434 35 834 14
240 1,090
510 938
10 172 38 501 4
78.5 544
123 517
11 146 49 280 29
96.7 503
254 369
12 156 123 185 28
16.7 146
20.4 253

74
Table 7-7. Summary of OCMA-350 and Reference Method Precision for Extract Duplicates

OCMA-350 Reference Method

Extract
Duplicate TPH Result Relative Percent TPH Result Relative Percent
Sampling Area Set (milligram per kilogram) Difference (milligram per kilogram) Difference
Fuel Farm Area 1 94.6 0 44.1 0
94.2 44.1
2 15,300 Not calculateda 13,700 2
a
Not analyzed 14,000
Naval Exchange Service 3 266 0 226 6
Station Area
267 213
4 997 Not calculateda 1,190 2
a
Not analyzed 1,170
5 1,200 Not calculateda 1,420 4
Not analyzeda 1,360
6 Less than 15.2 0 15.5 4
Less than 15.2 14.9
Phytoremediation Area 7 3,090 1 1,710 8
3,060 1,860
B-38 Area 8 48.2 3 79.6 2
46.8 78.4
9 32.5 2 percentb 41.4 0
28.6 41.5
33.2
Slop Fill Tank Area 10 439 2 829 1
429 838
11 174 2 528 11
170 473
12 147 1 271 6
145 289
13 156 Not calculateda 189 4
a
Not analyzed 181

Notes:
a
The extract was disposed of before an extract duplicate sample was analyzed; therefore, a relative percent difference could not be calculated.
b
Two extract duplicates of the sample extract were analyzed. Therefore, the relative standard deviation is reported instead of the relative percent
difference.

75
Table 7-8. Comparison of OCMA-350 and Reference Method Precision for Replicate Performance Evaluation Samples

OCMA-350 Reference Method

Relative Standard Relative Standard
Sample Type Replicate Set TPH Result Deviation (percent) TPH Result Deviation (percent)
Soil Samples (Processed Garden Soil) (TPH Results in Milligram per Kilogram)
Blank (9 percent moisture content) 1 Less than 15.2 45 5.12 45
20.9 13.1
18.7 13.5
Weathered Medium-range TPH 2 107 2 350 2
gasoline concentration
108 346
(9 percent moisture
content) 104 336
High-range TPH 3 657 5 1,880 7
concentration
595 2,020
(9 percent moisture
content) 638 2,180
High-range TPH 4 1,460 9 1,740 8
concentration
1,710 1,980
(16 percent moisture
content) 1,720 2,050
Diesel Low-range TPH 5 28.8 17 16.4 10
concentration
21 16.4
(9 percent moisture
content) 30.6 13.2
24.2 16.0
33.4 14.2
23.2 14.1
32.2 12.8
Medium-range TPH 6 124 8 276 4
concentration
143 273
(9 percent moisture
content) 144 295
High-range TPH 7 992 2 2,480 8
concentration
995 2,890
(9 percent moisture
content) 958 2,800
High-range TPH 8 3,540 2 2,700 6
concentration (less
3,570 2,950
than 1 percent
moisture content) 3,460 3,070
Liquid Samples (Neat Materials) (TPH Results in Milligram per Liter)
Weathered 9 541,000 2 656,000 5
gasoline
566,000 611,000
560,000 677,000
Diesel 10 750,000 1 1,090,000 6
737,000 1,020,000
758,000 1,160,000

76
remaining two results were above the MDL. The RSDs for Chapter 4. The results for the quasi-control interferent
the remaining seven replicate sets ranged from 2 to samples are discussed first below, followed by the effects
17 percent with a median of 5 percent. The RSDs for the of the interferents on the TPH results for soil samples.
two triplicate sets of liquid samples were 1 and 2 percent
with a median of 1.5 percent. 7.1.3.1 Interferent Sample Results

For the reference method, the RSD calculated for the blank Table 7-9 presents the OCMA-350 and reference method
soil samples was not considered in evaluating the method’s TPH results, mean TPH results, and mean responses for
precision because one of the three blank soil sample results triplicate sets of liquid PE samples and soil PE samples
(5.12 mg/kg) was estimated by adding one-half the containing humic acid. Each mean response was
reporting limits for the GRO, DRO, and ORO components calculated by dividing the mean TPH result for a triplicate
of TPH measurement. The RSDs for the remaining seven set by the interferent concentration and multiplying by
replicate sets ranged from 2 to 10 percent with a median of 100. For liquid PE samples, the interferent concentration
7 percent. The RSDs for the two triplicate sets of liquid was estimated using its density and purity.
samples were 5 and 6 percent with a median of 5.5 percent.
Comparison of the OCMA-350 and reference method The mean responses for the OCMA-350 ranged from 0 to
median RSDs showed that the OCMA-350 exhibited better 94 percent for the liquid interferent samples; the mean
precision than the reference method for both soil and liquid response for humic acid was 0 percent. The TPH results
PE samples. Finally, for the reference method, the median for a given triplicate set and between the triplicate sets
RSD for the soil PE samples (7 percent) was less than that showed good agreement except for Stoddard solvent. The
for the environmental samples (18 percent), indicating that mean responses for MTBE (72.5 percent) and Stoddard
greater precision was achieved for the samples prepared solvent (86 percent) indicated that these compounds can be
under more controlled conditions (the PE samples). measured as TPH using the OCMA-350. The mean
Similarly, for the OCMA-350, the median RSD for the soil response for turpentine (85 percent) indicated that
PE samples (5 percent) was less than that for the turpentine would result in false positives during TPH
environmental samples (20 percent). measurement. The mean response of 0 percent for PCE;
1,2,4-trichlorobenzene; and humic acid indicated that these
7.1.3 Primary Objective P3: Effect of Interferents compounds would not result in either false positives or
false negatives during TPH measurement.
The effect of interferents on TPH measurement using the
OCMA-350 and reference method was evaluated through The mean responses for the reference method ranged from
analysis of high-concentration-range soil PE samples that 17 to 92 percent for the liquid interferent samples; the
contained weathered gasoline or diesel with or without an mean response for humic acid was 0 percent. The TPH
interferent. The six interferents used were MTBE; PCE; results for a given triplicate set and between the triplicate
Stoddard solvent; turpentine; 1,2,4-trichlorobenzene; and sets showed good agreement. The mean responses for
humic acid. In addition, neat (liquid) samples of each MTBE (39 percent) and Stoddard solvent (85 percent)
interferent except humic acid were used as quasi-control indicated that these compounds can be measured as TPH
samples to evaluate the effect of each interferent on the using the reference method. The mean responses for PCE
TPH results obtained using the OCMA-350 and the (17.5 percent); turpentine (52 percent); and
reference method. Liquid interferent samples were 1,2,4-trichlorobenzene (50 percent) indicated that these
submitted for analysis as blind triplicate samples. Horiba interferents will likely result in false positives during TPH
and the reference laboratory were provided with flame- measurement. The mean response of 0 percent for humic
sealed ampules of each interferent and were given specific acid indicated that humic acid would not result in either
instructions to prepare dilutions of the liquid interferents false positives or false negatives during TPH measurement.
for analysis. Two dilutions of each interferent were
prepared; therefore, there were six OCMA-350 and 7.1.3.2 Effects of Interferents on TPH Results for
reference method TPH results for each interferent. Blank Soil Samples
soil was mixed with humic acid at two levels to prepare
quasi-control samples for this interferent. Additional The effects of interferents on TPH measurement for soil
details regarding the interferents are provided in samples containing weathered gasoline or diesel were

77
Table 7-9. Comparison of OCMA-350 and Reference Method Results for Interferent Samples

OCMA-350 Reference Method

Mean TPH Mean Responseb Mean TPH Mean Responseb
Interferent and Concentrationa TPH Result Result (percent) TPH Result Result (percent)
Liquid Interferent Samples (TPH Results in Milligram per Liter)
Methyl-tert-butyl ether 544,000 530,000 72 309,000 284,000 38
(740,000 milligrams per liter) 526,000 272,000
520,000 270,000
547,000 540,000 73 303,000 299,000 40
510,000 313,000
562,000 282,000
Tetrachloroethene Less than 6,080 3,040 0 269,000 272,000 17
(1,621,000 milligrams per liter)
Less than 6,080 270,000
Less than 6,080 277,000
Less than 1,220 610 0 290,000 295,000 18
Less than 1,220 288,000
Less than 1,220 307,000
Stoddard solvent 511,000 730,000 94 561,000 598,000 78
(771,500 milligrams per liter) 824,000 628,000
847,000 606,000
463,000 600,000 78 703,000 708,000 92
762,000 Not reported
576,000 713,000
Turpentine 722,000 718,000 85 504,000 468,000 55
(845,600 milligrams per liter) 711,000 459,000
720,000 442,000
685,000 712,000 85 523,000 408,000 48
746,000 353,000
721,000 349,000
1,2,4-Trichlorobenzene Less than 6,080 3,040 0 711,000 688,000 48
(1,439,000 milligrams per liter) Less than 6,080 620,000
Less than 6,080 732,000
1,690 1,690 0 754,000 754,000 52
1,600 756,000
1,780 752,000
Interferent Samples (Processed Garden Soil) (TPH Results in Milligram per Kilogram)
Humic acid at 3,940 milligrams per Less than 15.2 7.6 0 8.99 9.00 0
kilogram Less than 15.2 8.96
Less than 15.2 8.12
Humic acid at 19,500 milligrams Less than 15.2 7.6 0 69.3 76.0 0
per kilogram
Less than 15.2 79.1
Less than 15.2 78.5

Notes:
a
A given liquid interferent concentration was estimated using its density and purity.
b
The mean response was calculated by dividing the mean TPH result for a triplicate set by the interferent concentration and multiplying by 100.

78
examined through analysis of PE samples containing volatile compound, may have been lost during PE sample
(1) weathered gasoline or diesel (control) and preparation, transport, storage, and handling, thus lowering
(2) weathered gasoline or diesel plus a given interferent at the MTBE concentrations to levels that would not have
two levels. Information on the selection of interferents is increased the TPH results beyond the reference method’s
provided in Chapter 4. precision (7 percent).

Triplicate sets of control samples and samples containing Effect of Tetrachloroethene

interferents were prepared for analysis using the OCMA-
350 and reference method. A parametric or nonparametric The effect of PCE was evaluated for soil PE samples
test was selected for statistical evaluation of the results containing weathered gasoline. Based on the liquid PE
using the approach presented in Figure 7-1. sample (neat material) analytical results, PCE was
expected to have no effect on the TPH results for the
TPH results for samples with and without interferents, OCMA-350; however, it was expected to bias the reference
statistical tests performed, and statistical test conclusions method results high.
for both the OCMA-350 and reference method are
presented in Table 7-10. The null hypothesis for the For the OCMA-350, PCE appeared to have biased the TPH
statistical tests was that mean TPH results for samples with results high. However, the bias decreased with an increase
and without interferents were equal. The statistical results in the PCE level. Specifically, the bias was 144 percent at
for each interferent are discussed below. the low level and 90 percent at the high level. For this
reason, no conclusion was drawn regarding the effect of
Effect of Methyl-Tert-Butyl Ether PCE on TPH measurement using the OCMA-350.

The effect of MTBE was evaluated for soil PE samples For the reference method, at the interferent levels used,
containing weathered gasoline. Based on the liquid PE PCE was expected to bias the TPH results high by
sample (neat material) analytical results, MTBE was 24 percent (low level) and 113 percent (high level). The
expected to bias both the OCMA-350 and reference expected bias would be lower (20 and 92 percent,
method results high. respectively) if PCE in soil samples was assumed to be
extracted as efficiently as weathered gasoline in soil
For the OCMA-350, at the interferent levels used, MTBE samples. The statistical tests showed that the probability
was expected to bias the TPH results high by 127 percent of the three means being equal was less than 5 percent.
(low level) and 196 percent (high level). The expected However, the tests also showed that at the high level, PCE
bias would be lower (37 and 58 percent, respectively) if biased the TPH results high, which appeared to be
MTBE in soil samples was assumed to be extracted as reasonable based on the conclusions drawn from the
efficiently as weathered gasoline in soil samples. analytical results for neat PCE. As to the reason for PCE
Table 7-10 shows that MTBE biased the OCMA-350 TPH at the low level having no effect on the TPH results,
results high at both low and high interferent levels, which volatilization during PE sample preparation, transport,
confirmed the conclusions drawn from the results of the storage, and handling may have lowered the PCE
neat MTBE analysis. Although the statistical tests concentrations to levels that would not have increased the
confirmed the observed bias, they indicated that the TPH results beyond the reference method’s precision
observed bias was statistically the same at both low and (7 percent).
high MTBE levels.
Effect of Stoddard Solvent
For the reference method, at the interferent levels used,
MTBE was expected to bias the TPH results high by The effect of Stoddard solvent was evaluated for
21 percent (low level) and 33 percent (high level). The weathered gasoline and diesel soil PE samples. Based on
expected bias would be lower (17 and 27 percent, the liquid PE sample (neat material) analytical results,
respectively) if MTBE in soil samples was assumed to be Stoddard solvent was expected to bias both the
extracted as efficiently as weathered gasoline in soil OCMA-350 and reference method results high.
samples. However, no effect on TPH measurement was
observed for soil PE samples analyzed during the For the OCMA-350, at the interferent levels used,
demonstration. A significant amount of MTBE, a highly Stoddard solvent was expected to bias the TPH results

79
 Table 7-10. Comparison of OCMA-350 and Reference Method Results for Soil Performance Evaluation Samples Containing Interferents

OCMA-350 Reference Method

Were Mean Probability of Were Mean Probability of
TPH Results Mean TPH TPH Results Mean TPH
for Samples Results for for Samples Results for
With and Samples With With and Samples With
Without and Without Without and Without
Mean TPH Interferents Interferents Being TPH Mean TPH Interferents Interferents
Sample Matrix and TPH Result Result the Same or the Same Result Result the Same or Being the Same
Interferenta (mg/kg) (mg/kg) Statistical Tests Different? (percent) (mg/kg) (mg/kg) Statistical Tests Different? (percent)
Soil Samples Without Interferents
Weathered gasoline 657 630 1,880 2,030
595 Not applicable 2,020 Not applicable
638 2,180
Diesel 992 982 2,480 2,720
995 Not applicable 2,890 Not applicable
958 2,800
Soil Samples With Interferents
Weathered MTBE 1,150 1,210 One-way Mean without 0.29 1,900 1,950 One-way analysis of Same 11.21
gasoline (1,100 mg/kg) analysis of interferent variance
882 variance was different 1,750 (parametric) and

80
(parametric) and from means Tukey (honest,
1,610 Tukey (honest, with 2,210 significant
significant interferent at difference) pairwise
MTBE 1,580 1,540 difference) low and high 2,150 2,340 comparison of
(1,700 mg/kg) pairwise levels means (parametric)
1,370 comparison of 2,320
means
1,680 2,560
(parametric)
PCE 1,590 1,540 Kruskal-Wallis Mean without 2.73 2,540 2,380 Mean with 0.00
(2,810 mg/kg) one-way interferent interferent at
1,530 analysis of was same as 2,160 high level
variance mean with was different
(nonparametric) interferent at from means
1,510 2,450
and Kruskal- high level; without
Wallis pairwise mean with interferent
PCE 1,290 1,200 comparison of interferent at 4,740 4,450 and with
(13,100 mg/kg) means low level was interferent at
1,390 (nonparametric) same as 4,570 low level
mean with
934 interferent at 4,040
high level
 Table 7-10. Comparison of OCMA-350 and Reference Method Results for Soil Performance Evaluation Samples Containing Interferents (Continued)

OCMA-350 Reference Method

Were Mean Probability of Were Mean Probability of
TPH Results Mean TPH TPH Results Mean TPH
for Samples Results for for Samples Results for
With and Samples With With and Samples With
Without and Without Without and Without
Mean TPH Interferents Interferents Being TPH Mean TPH Interferents Interferents
Sample Matrix and TPH Result Result the Same or the Same Result Result the Same or Being the Same
Interferenta (mg/kg) (mg/kg) Statistical Tests Different? (percent) (mg/kg) (mg/kg) Statistical Tests Different? (percent)
Soil Samples With Interferents (Continued)
Weathered Stoddard 1,930 1,910 One-way All three 0.00 4,350 4,410 One-way analysis of All three 0.00
gasoline solvent analysis of means (with variance means (with
(Continued) (2,900 mg/kg) 2,030 variance and without 4,760 (parametric) and and without
(parametric) and interferents) Tukey (honest, interferents)
Tukey (honest, were significant were
1,770 4,110
significant significantly difference) pairwise significantly
difference) different from comparison of different from
Stoddard 13,000 15,400 pairwise one another 10,300 11,900 means (parametric) one another
solvent comparison of
(15,400 mg/kg) 17,700 means 14,300
(parametric)
15,400 11,000

81
Diesel Stoddard 2,650 2,630 Kruskal-Wallis Mean without 2.73 4,390 4,520 All three 0.00
solvent one-way interferent means (with
(3,650 mg/kg) 3,400 analysis of was same as 4,640 and without
variance mean with interferents)
(nonparametric) interferent at were
1,840 4,520
and Kruskal- low level; significantly
Wallis pairwise mean with different from
Stoddard 13,400 14,700 comparison of interferent at 8,770 7,880 one another
solvent means low level was
(18,200 mg/kg) 13,800 (nonparametric) same as 6,580
mean with
16,900 interferent at 8,280
high level
Weathered Turpentine 1,870 1,820 One-way All three 0.00 4,410 4,240 All three 0.00
gasoline (2,730 mg/kg) analysis of means (with means (with
1,650 variance and without 3,870 and without
(parametric) and interferents) interferents)
1,930 Tukey (honest, were 4,440 were
significant significantly significantly
Turpentine 12,500 12,700 difference) different from 12,800 12,900 different from
(12,900 mg/kg) pairwise one another one another
12,200 comparison of 11,200
means
13,300 14,600
(parametric)
 Table 7-10. Comparison of OCMA-350 and Reference Method Results for Soil Performance Evaluation Samples Containing Interferents (Continued)

OCMA-350 Reference Method

Were Mean Probability of Were Mean Probability of
TPH Results Mean TPH TPH Results Mean TPH
for Samples Results for for Samples Results for
With and Samples With With and Samples With
Without and Without Without and Without
Mean TPH Interferents Interferents Being TPH Mean TPH Interferents Interferents
Sample Matrix and TPH Result Result the Same or the Same Result Result the Same or Being the Same
Interferenta (mg/kg) (mg/kg) Statistical Tests Different? (percent) (mg/kg) (mg/kg) Statistical Tests Different? (percent)
Soil Samples With Interferents (Continued)
Diesel Turpentine 2,380 2,690 One-way All three 0.00 5,860 5,760 Kruskal-Wallis one- Mean without 2.65
(3,850 mg/kg) analysis of means (with way analysis of interferent
2,710 variance and without 5,810 variance was same as
(parametric) and interferents) (nonparametric) and mean with
Tukey (honest, were Kruskal-Wallis interferent at
2,980 5,610
significant significantly pairwise low level;
difference) different from comparison of mean with
Turpentine 13,500 12,800 pairwise one another 15,000 13,900 means interferent at
(19,600 mg/kg) comparison of (nonparametric) low level was
13,100 means 13,300 same as
(parametric) mean with
11,900 13,300 interferent at
high level

82
1,2,4-Trichloro- 981 1,100 Mean with 0.00 3,220 3,510 One-way analysis of Mean with 0.01
benzene interferent at variance interferent at
(3,350 mg/kg) 1,220 high level 3,750 (parametric) and high level
was different Tukey (honest, was different
1,100 3,550
from means significant from means
1,2,4-Trichloro- 1,980 1,870 without 7,940 7,060 difference) pairwise without
benzene interferent comparison of interferent
(16,600 mg/kg) 1,810 and with 6,560 means (parametric) and with
interferent at interferent at
1,820 low level 6,690 low level
 Table 7-10. Comparison of OCMA-350 and Reference Method Results for Soil Performance Evaluation Samples Containing Interferents (Continued)

OCMA-350 Reference Method

Were Mean Probability of Were Mean Probability of
TPH Results Mean TPH TPH Results Mean TPH
for Samples Results for for Samples Results for
With and Samples With With and Samples With
Without and Without Without and Without
Mean TPH Interferents Interferents Being TPH Mean TPH Interferents Interferents
Sample Matrix and TPH Result Result the Same or the Same Result Result the Same or Being the Same
Interferenta (mg/kg) (mg/kg) Statistical Tests Different? (percent) (mg/kg) (mg/kg) Statistical Tests Different? (percent)
Soil Samples With Interferents (Continued)
Diesel Humic acid 612 529 One-way All three 0.00 2,150 2,200 One-way analysis of Mean without 3.87
(Continued) (3,940 mg/kg) analysis of means (with variance interferent
504 variance and without 2,080 (parametric) and was same as
(parametric) and interferents) Tukey (honest, mean with
Tukey (honest, were significant interferent at
470 2,360
significant significantly difference) pairwise high level;
difference) different from comparison of mean with
Humic acid 318 325 pairwise one another 2,660 2,450 means (parametric) interferent at
(19,500 mg/kg) comparison of low level was
292 means 2,420 same as
(parametric) mean with
364 2,270 interferent at
high level

83
Notes:

mg/kg = Milligram per kilogram

MTBE = Methyl-tert-butyl ether
PCE = Tetrachloroethene
a
All samples were prepared at a 9 percent moisture level.
high by 396 percent (low level) and 2,100 percent (high PE sample (neat material) analytical results, turpentine
level) for weathered gasoline soil PE samples and by was expected to bias both the OCMA-350 and reference
320 percent (low level) and 1,600 percent (high level) for method results high.
diesel soil PE samples. The expected bias would be lower
(116 and 618 percent, respectively, for weathered gasoline For the OCMA-350, at the interferent levels used,
soil PE samples and 92 and 458 percent, respectively, for turpentine was expected to bias the TPH results high by
diesel soil PE samples) if Stoddard solvent in soil samples 368 percent (low level) and 1,740 percent (high level) for
was assumed to be extracted as efficiently as weathered weathered gasoline soil PE samples and by 333 percent
gasoline and diesel in soil samples. The statistical tests (low level) and 1,700 percent (high level) for diesel soil PE
showed that the mean TPH results with and without the samples. The expected bias would be lower (108 and
interferent were different for weathered gasoline soil PE 512 percent, respectively, for weathered gasoline soil PE
samples, which confirmed the conclusions drawn from the samples and 96 and 488 percent, respectively, for diesel
analytical results for neat Stoddard solvent. However, for soil PE samples) if turpentine in soil samples was assumed
diesel soil PE samples, (1) the mean TPH result without to be extracted as efficiently as weathered gasoline and
the interferent and the mean TPH result with the diesel in soil samples. The statistical tests showed that the
interferent at the low level were equal and (2) the mean mean TPH results with and without the interferent were
TPH results with the interferent at the low and high levels different for both weathered gasoline and diesel soil PE
were equal, indicating that Stoddard solvent at the low samples, which confirmed the conclusions drawn from the
level did not affect the TPH results for the diesel soil PE analytical results for neat turpentine.
samples but that Stoddard solvent at the high level did
affect the TPH results. The conclusion reached for the For the reference method, at the interferent levels used,
interferent at the low level was unexpected and did not turpentine was expected to bias the TPH results high by
seem reasonable based on a simple comparison of means 69 percent (low level) and 327 percent (high level) for
that differed by a factor of three. The anomaly might have weathered gasoline soil PE samples and by 72 percent (low
been associated with the nonparametric test used to level) and 371 percent (high level) for diesel soil PE
evaluate the effect of Stoddard solvent on TPH results for samples. The expected bias would be lower (56 and
diesel soil PE samples, as nonparametric tests do not 266 percent, respectively, for weathered gasoline soil PE
account for the magnitude of the difference between TPH samples and 39 and 200 percent, respectively, for diesel
results. soil PE samples) if turpentine in soil samples was assumed
to be extracted as efficiently as weathered gasoline and
For the reference method, at the interferent levels used, diesel in soil samples. The statistical tests showed that the
Stoddard solvent was expected to bias the TPH results high mean TPH results with and without the interferent were
by 121 percent (low level) and 645 percent (high level) for different for weathered gasoline soil PE samples, which
weathered gasoline soil PE samples and by 114 percent confirmed the conclusions drawn from the analytical
(low level) and 569 percent (high level) for diesel soil PE results for neat turpentine. However, for diesel soil PE
samples. The expected bias would be lower (99 and samples, (1) the mean TPH result without the interferent
524 percent, respectively, for weathered gasoline soil PE and the mean TPH result with the interferent at the low
samples and 61 and 289 percent, respectively, for diesel level were equal and (2) the mean TPH results with the
soil PE samples) if Stoddard solvent in soil samples was interferent at the low and high levels were equal,
assumed to be extracted as efficiently as weathered indicating that turpentine at the low level did not affect the
gasoline and diesel in soil samples. The statistical tests TPH results for the diesel soil PE samples but that
showed that the mean TPH results with and without the turpentine at the high level did affect the TPH results. The
interferent were different for both weathered gasoline and conclusion reached for the interferent at the low level was
diesel soil PE samples, which confirmed the conclusions unexpected and did not seem reasonable based on a simple
drawn from the analytical results for neat Stoddard comparison of means that differed by a factor of three.
solvent. The anomaly might have been associated with the
nonparametric test used to evaluate the effect of turpentine
Effect of Turpentine on TPH results for diesel soil PE samples, as
nonparametric tests do not account for the magnitude of
The effect of turpentine was evaluated for weathered the difference between TPH results.
gasoline and diesel soil PE samples. Based on the liquid

84
Effect of 1,2,4-Trichlorobenzene For the OCMA-350, humic acid biased the TPH results
low; the bias was statistically significant at both the low
The effect of 1,2,4-trichlorobenzene was evaluated for and high interferent levels. This observation appeared to
diesel soil PE samples. Based on the liquid PE sample contradict the conclusions drawn from the analytical
(neat material) analytical results, 1,2,4-trichlorobenzene results for soil PE samples containing humic acid (quasi-
was expected to have no effect on the TPH results for the control samples); however, the apparent contradiction was
OCMA-350; however, it was expected to bias the reference attributable to the fact that the quasi-control sample
method results high. analyses could predict only a positive bias (a negative bias
is equivalent to a negative concentration).
For the OCMA-350, 1,2,4-trichlorobenzene appears to
have biased the TPH results high; the bias was statistically For the reference method, humic acid appeared to have
significant only at the high interferent level. The observed biased the TPH results low. However, the bias decreased
bias contradicted the conclusions drawn from the results of with an increase in the humic acid level. Specifically, the
the neat 1,2,4-trichlorobenzene analysis, which cannot be negative bias was 19 percent at the low level and
explained. 10 percent at the high level. For this reason, no conclusion
was drawn regarding the effect of humic acid on TPH
For the reference method, at the interferent levels used, measurement using the reference method.
1,2,4-trichlorobenzene was expected to bias the TPH
results high by 62 percent (low level) and 305 percent 7.1.4 Primary Objective P4: Effect of Soil
(high level). The expected bias would be lower (33 and Moisture Content
164 percent, respectively) if 1,2,4-trichlorobenzene in soil
samples was assumed to be extracted as efficiently as To measure the effect of soil moisture content on the
diesel in soil samples. The statistical tests showed that the ability of the OCMA-350 and reference method to
probability of three means being equal was less than accurately measure TPH, high-concentration-range soil PE
5 percent. However, the tests also showed that when the samples containing weathered gasoline or diesel at two
interferent was present at the high level, TPH results were moisture levels were analyzed. The OCMA-350 and
biased high. The effect observed at the high level reference method results were converted from a wet weight
confirmed the conclusions drawn from the analytical basis to a dry weight basis in order to evaluate the effect of
results for neat 1,2,4-trichlorobenzene. The statistical tests moisture content on the sample TPH results. The OCMA-
indicated that the mean TPH result with the interferent at 350 and reference method dry weight TPH results for
the low level was not different from the mean TPH result weathered gasoline samples and the reference method dry
without the interferent, indicating that the low level of weight TPH results for diesel samples were normally
1,2,4-trichlorobenzene did not affect TPH measurement. distributed; therefore, a two-tailed, two-sample Student’s
However, a simple comparison of the mean TPH results t-test was performed to determine whether the device and
revealed that the low level of 1,2,4-trichlorobenzene reference method results were impacted by soil moisture
increased the TPH result to nearly the result based on the content—that is, to determine whether an increase in soil
expected bias of 33 percent. Specifically, the mean TPH moisture content resulted in an increase or decrease in the
result with the interferent at the low level was 3,510 mg/kg TPH concentrations measured. Because the OCMA-350
rather than the expected value of 3,620 mg/kg. The dry weight TPH results for diesel samples were not
conclusions drawn from the statistical tests were justified normally distributed, a Kruskal-Wallis one-way analysis of
when the variabilities associated with the mean TPH variance (a nonparametric test) was performed. The null
results were taken into account. hypothesis for the t-test and the analysis of variance was
that the two means were equal or that the difference
Effect of Humic Acid between the means was equal to zero. Table 7-11 shows
the sample moisture levels, TPH results, mean TPH results
The effect of humic acid was evaluated for diesel soil PE for sets of triplicate samples, whether the mean TPH
samples. Based on the analytical results for soil PE results at different moisture levels were the same, and the
samples containing humic acid, this interferent was probability of the null hypothesis being true.
expected to have no effect on the TPH results for the
OCMA-350 and reference method.

85
 Table 7-11. Comparison of Results for Soil Performance Evaluation Samples at Different Moisture Levels

OCMA-350 Reference Method

TPH Result on Dry Mean TPH Were Mean TPH Probability of TPH Result on Mean TPH Were Mean TPH Probability of
Weight Basis Result Results at Different Null Hypothesis Dry Weight Basis Result Results at Different Null Hypothesis
(milligram per (milligram per Moisture Levels the Being Truec (milligram per (milligram per Moisture Levels the Being Truec
Sample Type and Moisture Level kilogram) kilogram) Same or Different?a,b (percent) kilogram) kilogram) Same or Different?a (percent)
Weathered gasoline at 9 percent 724 694 Different 3.64 2,070 2,230 Same 66.52
moisture level
655 2,220
703 2,400
Weathered gasoline at 16 percent 1,740 1,950 2,070 2,300
moisture level
2,060 2,390
2,050 2,440
Diesel at less than 1 percent 3,570 3,550 Different 4.63 2,740 3,000 Same 71.95
moisture level
3,600 3,180
3,490 3,070
Diesel at 9 percent moisture level 1,100 1,080 2,720 2,930
1,100 2,970
1,050 3,100

86
Notes:
a
A two-tailed, two-sample Student’s t-test (parametric) was used to evaluate the effect of soil moisture content on OCMA-350 and reference method TPH results for weathered gasoline samples
and on reference method TPH results for diesel samples.
b
A Kruskal-Wallis one-way analysis of variance (nonparametric) was used to evaluate the effect of moisture content on OCMA-350 TPH results for diesel samples.
c
The null hypothesis was that the two means were equal or that the difference between the two means was equal to zero.
Table 7-11 shows that OCMA-350 results for weathered Information regarding the time required for each
gasoline and diesel soil samples at different moisture levels measurement activity during the entire 6-day
were statistically different at a significance level of demonstration and for extraction and analysis of the first
5 percent; therefore, the OCMA-350 results were impacted and last batches of soil samples is provided below.
by soil moisture content. Based on a simple comparison of
the results, this conclusion appeared to be reasonable. The setup time for the OCMA-350 was measured at the
Specifically, on average at the higher moisture level, the beginning of each day during the 6-day demonstration
mean TPH result (1) for weathered gasoline soil samples period. Setup activities included OCMA-350 setup;
was higher by a factor of three and (2) for diesel soil analysis of QC check standards; and organization of
samples was lower by a factor of three. The opposite extraction, dilution, analysis, and decontamination
effect of soil moisture content on TPH results for supplies. OCMA-350 setup required a total of 1 hour,
weathered gasoline and diesel soil samples could not be 45 minutes, during the 6-day demonstration, or an average
explained. of 17.5 minutes per day. The setup times on the days when
the first and last soil sample batches were analyzed were
Table 7-11 also shows that reference method results for 25 and 10 minutes, respectively, or an average of
weathered gasoline soil samples and diesel soil samples at 17.5 minutes per day. The total setup time for the entire
different moisture levels were statistically the same at a demonstration and the setup time on the days when the
significance level of 5 percent; therefore, the reference first and last soil sample batches were analyzed suggested
method results were not impacted by soil moisture content. that the field technician gradually became more familiar
Based on a simple comparison of the results, this with the OCMA-350 setup procedure as the demonstration
conclusion appeared to be reasonable. progressed.

7.1.5 Primary Objective P5: Time Required for Extraction of all 163 soil samples required 25 hours,
TPH Measurement 45 minutes, resulting in an average extraction time of
9 minutes per sample. However, the field technician also
During the demonstration, the time required for TPH completed other activities associated with sample
measurement activities, including OCMA-350 setup, extraction during the demonstration, such as
sample extraction, sample analysis, OCMA-350 decontaminating metal spatulas and glass beakers. Thus,
disassembly, and data package preparation, was measured. the average sample extraction time of 9 minutes included
During the demonstration, one field technician performed the time required to complete these activities.
the TPH measurement activities using the OCMA-350.
Time measurement began at the start of each The time required for extraction of the first and last
demonstration day when the technician began to set up the batches of soil samples was also recorded. In general,
OCMA-350 and ended when he disassembled the OCMA- Horiba designated 24 samples for each analytical batch.
350. Time not measured included (1) the time spent by the The number of samples was based on the capacity of the
technician verifying that he had received all the test tube rack used during extraction. However, fewer than
demonstration samples indicated on chain-of-custody 24 samples comprised an analytical batch in some cases;
forms and (2) the times when he took breaks. In addition for example, the last batch of soil samples consisted of
to the total time required for TPH measurement, the time only 17 samples. The first batch of soil samples (which
required to extract and analyze the first and last analytical consisted of 24 samples) required 2 hours, 50 minutes, for
batches of soil samples was measured. The number and extraction, or an average of 7 minutes per sample. The last
type of samples in a batch were selected by Horiba. batch of soil samples (which consisted of 17 samples)
required 1 hour, 30 minutes, for extraction, or an average
The time required to complete TPH measurement activities of 5 minutes per sample. The decrease in the average
using the OCMA-350 is shown in Table 7-12. The time extraction time between the first and last batches of soil
required for each activity was rounded to the nearest samples suggested that the field technician became more
5 minutes. familiar with the OCMA-350 extraction procedure as the
demonstration progressed. The difference between the
Overall, Horiba required 46 hours, 15 minutes, for TPH 9-minute average extraction time for all the soil samples
measurement of 74 soil environmental samples, 89 soil PE and the average extraction time for the first and last
samples, 36 liquid PE samples, and 9 extract duplicates. batches of soil samples (6 minutes) may be attributable to

87
Table 7-12. Time Required to Complete TPH Measurement Activities Using the OCMA-350

Time Requireda
Measurement Activity First Soil Sample Batchb Last Soil Sample Batchb 6-Day Demonstration Period
c
OCMA-350 setup 25 minutes 10 minutes 1 hour, 45 minutes
Sample extraction 2 hours, 50 minutes 1 hour, 30 minutes 25 hours, 45 minutes
Sample analysis 2 hours 1 hour, 10 minutes 16 hours, 45 minutes
OCMA-350 disassemblyc 20 minutes 10 minutes 1 hour, 30 minutes
Data package preparation Not measured Not measured 30 minutes
Total 5 hours, 35 minutes 3 hours 46 hours, 15 minutes

Notes:
a
The time required for each activity was rounded to the nearest 5 minutes.
b
The first sample batch required 29 TPH analyses (24 sample extract analyses, 3 extract duplicate analyses, and 2 reanalyses). The last sample
batch required 22 TPH analyses (17 sample extract analyses and 5 reanalyses).
c
The OCMA-350 setup and disassembly times were measured at the beginning and end of each day, respectively. The times reported for the first
soil sample batch were the times recorded on the first day and the times reported for the last soil sample batch were the times recorded on the
fifth day of the 6-day demonstration period.

the additional extraction activities mentioned above that The disassembly time was measured at the end of each day
were conducted by the field technician. of the 6-day demonstration. Disassembly included packing
up the OCMA-350 and associated supplies required for
A total of 16 hours, 45 minutes, was required to obtain and TPH measurement. OCMA-350 disassembly required 10
report 208 TPH results using the OCMA-350, resulting in to 20 minutes each day, totaling 1 hour, 30 minutes, for the
an average analysis time of 5 minutes per sample. In 6-day demonstration. Thus, the average disassembly time
addition to performing the 208 analyses required to report was 15 minutes per day. The disassembly times on the
208 TPH results, the field technician performed extract days when the first and last soil sample batches were
dilutions and reanalyses for the high-concentration-range analyzed were 20 and 10 minutes, respectively, or an
samples. The average analysis time does not include the average of 15 minutes per day. The total disassembly time
time taken to perform these additional activities. for the entire demonstration and the setup times on the
days when the first and last soil sample batches were
The time required to analyze the first and last batches of analyzed suggested that the field technician gradually
soil samples was also recorded. A total of 2 hours was became more familiar with the OCMA-350 disassembly
required to analyze the first batch of samples, which procedure as the demonstration progressed.
required 29 TPH analyses (24 sample extract analyses,
3 extract duplicate analyses, and 2 reanalyses); therefore, Preparation of the OCMA-350 data package required
an average of 4 minutes was required to complete one 30 minutes in the field. Preparation of the data package
analysis. A total of 1 hour, 10 minutes, was required to submitted to the EPA at the end of the demonstration
analyze the last batch of soil samples, which required involved compiling printouts of TPH results and
22 TPH analyses (17 sample extract analyses and photocopying Horiba’s log sheets, which included sample
5 reanalyses); therefore, an average of 3 minutes was identification numbers, the mass of soil and volume of
required to complete one analysis. The decrease in the solvent used, and TPH results. Additional information was
average analysis time between the first and last batches of provided in cases when dilutions had been necessary.
soil samples suggested that the field technician became Although the data package preparation time was
more familiar with the OCMA-350 analysis procedure as 30 minutes in the field, during the weeks following the
the demonstration progressed. The difference between the demonstration, Horiba spent additional time revising the
5-minute average sample analysis time for the entire data package to address EPA comments. The revisions
demonstration and the average sample analysis time for the primarily consisted of identifying in the data package TPH
first and last batches (3.5 minutes) may be attributable to results below the reporting limit based on the revised
the additional analysis activities mentioned above that MDL. The amount of additional time that Horiba spent
were conducted by the field technician.

88
finalizing the data package could not be quantified and instructor’s travel and per diem for 1 day. Horiba does not
was not included as part of the time for TPH measurement. provide a training video for the OCMA-350.

For the reference method, time measurement began when With the OCMA-350, minimal effort is required to
the reference laboratory received all the investigative calculate a TPH concentration because the mass of soil and
samples and continued until the EPA received the first volume of solvent used during sample extraction can be
draft data package from the laboratory. The reference programmed into the device, and the concentration can be
laboratory took 30 days to deliver the first draft data read from the digital display in units of mg/kg TPH on a
package to the EPA. Additional time taken by the wet weight basis. For a diluted sample extract, the user
reference laboratory to address EPA comments on all the must multiply the digital display reading by an appropriate
draft laboratory data packages was not included as part of dilution factor. During the demonstration, Horiba
the time required for TPH measurement. connected the OCMA-350 to a printer that printed a hard
copy of the TPH concentrations. After the demonstration,
7.2 Secondary Objectives Horiba made minimal revisions to the TPH results reported
in the field. Specifically, of the 208 TPH results reported
This section discusses the performance results for the in the field at the end of the demonstration, fewer than
OCMA-350 in terms of the secondary objectives stated in 5 percent were corrected based on EPA review of the data
Section 4.1. The secondary objectives were addressed package. The corrections primarily involved use of
based on (1) observations of the performance of the inappropriate reporting limits.
OCMA-350 during the demonstration and (2) information
provided by Horiba. During the demonstration, Horiba used supplies and took
steps that significantly increased the time and effort
7.2.1 Skill and Training Requirements for associated with sample preparation and analysis activities.
Proper Device Operation For example, to calculate TPH concentrations, Horiba
used the built-in function of the OCMA-350 that specified
Based on observations made during the demonstration, the the standard mass of soil and volume of solvent used
OCMA-350 is easy to operate, requiring one field during sample extraction. As a result, Horiba had to
technician with basic wet chemistry skills acquired on the measure exactly 5.0 grams of each soil sample and
job or in a university. Because the amount of sample carefully place the measured amount in a narrow-mouthed,
drying agent (sodium sulfate) used and the sample 40-mL vial without losing any mass; this step took a
extraction time may need to be adjusted based on soil type significant amount of the field technician’s time (an
and moisture content, basic knowledge of soil types is also average of 5 minutes per sample). Taking full advantage
recommended so that the technician can differentiate of the device features that allow use of varying amounts of
among sand, silt, and clay soil types and modify the soil and solvent during sample extraction as well as using
sample drying and extraction steps accordingly. During vials with wider mouths would have made the extraction
the demonstration, Horiba chose to conduct sample process less time-consuming. In addition, Horiba used a
analyses using one technician. gravity filtration setup that required significant time,
space, and supplies–such as glass funnels, a funnel rack,
According to Horiba, normal training for using the Whatman No. 40 filter paper, and glass beakers–and that
OCMA-350 is limited to reading the instruction manual may have resulted in loss of some volatiles. Use of
and simplified operating instruction sheet that are included disposable filter syringes may have resulted in savings of
with the device. The sample analysis procedure for the time, space, and supplies. Horiba also used its Model SR-
OCMA-350 can be learned in the field with a few practice 300 solvent reclaimer to recycle spent solvent. Although
attempts. In addition, during regular business hours, the solvent reclaimer was easy to set up and use, it took a
Horiba provides technical support over the telephone at no significant amount of time to generate solvent. In
additional cost. Horiba also offers a 1-day training course summary, some of the TPH measurement steps described
at its facility or at a user-specified site for $960; for this above reduced the quantity of waste generated during the
cost, Horiba provides one OCMA-350 for training demonstration but made the TPH measurement procedures
purposes and one instructor to train up to 10 people. If the less simple and more time-consuming.
training is conducted at a user-specified site, the user
would have to pay an additional cost to cover the

89
7.2.2 Health and Safety Concerns Associated Other supplies that Horiba used during the demonstration
with Device Operation come in several boxes but not in carrying cases that would
facilitate transport of the supplies between sampling areas.
The chemical hazards associated with operating the As a result, significant effort would be required for the
OCMA-350 are considered to be insignificant. The two user to move these supplies between sampling areas in the
chemicals required for use of the OCMA-350 are field. For example, the Model SR-300 solvent reclaimer
anhydrous sodium sulfate drying agent and Horiba’s and 7-kg bottle of S-316 extraction solvent each come in
proprietary S-316 extraction solvent, both of which are a cardboard box and weigh 15 and 18 pounds,
nontoxic. respectively. Glassware and other laboratory supplies–
such as 40-mL vials, a test tube rack, funnels, a funnel
During the demonstration, the Horiba field technician rack, and beakers–also come in separate boxes. In
operated the OCMA-350 in modified Level D personal addition, the Model GE-50 ultrasonic mixer (6 pounds)
protective equipment (PPE) to prevent eye and skin contact and the Epson LQ-500 dot-matrix printer (10 pounds)
with chemicals. The PPE included safety glasses, work come in separate boxes and require an AC power source
boots, work clothes with long sleeves and long pants, and for operation; however, because a typical user does not
occasionally disposable gloves when soil samples were require these two items for TPH measurement using the
wet. Sample analyses were performed outdoors in a well- OCMA-350, they are considered to be optional. In
ventilated area; therefore, exposure to volatile chemicals summary, the portability of the OCMA-350 and other
through inhalation was not a concern. required supplies depends on the number of samples to be
analyzed, site characteristics (for example, the availability
During the demonstration, Horiba used the Model GE-50 of AC power), and the needs of the user (for example, a
ultrasonic mixer, which is no longer available from the printer is needed only if a printout of the TPH results is
developer. According to Horiba, the ultrasonic mixer that required).
is currently available (Model VC-50) is functionally the
same as Model GE-50. A potential physical hazard To operate the OCMA-350, a sample preparation and
observed during the demonstration involved use of the analysis area is required. The area must be large enough
ultrasonic mixer, which emitted a very high-frequency to accommodate the infrared spectrophotometer and its
sound; Horiba’s field technician wore ear plugs while accessories, the Model SR-300 solvent reclaimer, and
using the mixer to prevent ear damage. glassware and other laboratory supplies. The size of the
area depends on the number of samples to be analyzed and
In general, a user of the OCMA-350 should employ good is thus project-specific. During the demonstration, Horiba
laboratory practices during sample analysis to minimize performed sample preparation and analysis under one 8- by
exposure to potential chemical and physical hazards. 8-foot tent that housed two 8-foot-long, folding tables; two
Example guidelines for good laboratory practices are folding chairs; one 20-gallon laboratory pack for
described in ASTM’s “Standard Guide for Good flammable waste; and one 55-gallon drum for general
Laboratory Practices in Laboratories Engaged in Sampling refuse. Horiba used the AC power source available at the
and Analysis of Water” (ASTM 1998). demonstration site to operate the OCMA-350, ultrasonic
mixer, and printer.
7.2.3 Portability of the Device
7.2.4 Durability of the Device
The OCMA-350 infrared spectrophotometer and its
accessories come in an optional, hard-plastic carrying case Horiba used several reusable items during the
and weigh 36 pounds. The carrying case is 22 inches long, demonstration. Of the reusable items that Horiba provides,
16 inches wide, and 15 inches high. The OCMA-350 is the infrared spectrophotometer and Model GE-50
operated using a 110- or 220-volt AC power source or a ultrasonic mixer contain mechanical or electronic parts that
DC power source such as a 12-volt power outlet in an could potentially malfunction during sample analysis.
automobile along with a DC/AC power inverter. Because Based on observations made during the demonstration,
the OCMA-350 comes in an optional carrying case, and these reusable items are durable; neither of them
because an AC power source is not required to operate the malfunctioned or was damaged. These items are
device, it is easily transported between sampling areas in manufactured by Horiba and are distributed by Horiba and
the field. authorized distributors of Horiba products. The infrared

90
spectrophotometer is housed in an optional, hard-plastic printer cable can be replaced with other brands of cable
carrying case to prevent damage during transport, and the that are compatible with the OCMA-350 and are available
Model GE-50 ultrasonic mixer comes in a padded, in computer hardware stores. According to Horiba,
cardboard box. replacement parts for the other items can be obtained from
Horiba or an authorized distributor of Horiba products
The Mettler-Toledo digital balance (Model BD202) and within 2 days, depending on the shipping procedures and
the Epson LQ-500 dot-matrix printer are reusable supplies site location. Except for an extra 3.15-ampere fuse for the
that were used during the demonstration but that Horiba infrared spectrophotometer, spare parts for reusable items
does not provide. These supplies also proved to be durable are not provided with the OCMA-350. Horiba
and did not malfunction or become damaged. recommends that the infrared spectrophotometer, Model
SR-300 solvent reclaimer, and Model GE-50 ultrasonic
Based on observations made during the demonstration, the mixer be returned to Horiba or an authorized distributor of
operation of the OCMA-350 was unaffected by the varying Horiba products for service if they malfunction. Because
temperature and humidity conditions encountered between Horiba provides a 1-year warranty for these items, they
8:00 a.m. and 5:00 p.m. on any given day. During the will be repaired at no additional cost during the warranty
daytime, the temperature ranged from about 17 to 24 °C, period. According to Horiba, repairs are generally
and the relative humidity ranged from 53 to 88 percent. completed in 1 week or less, depending on the repairs
During sample analysis, wind speeds up to 20 miles per needed.
hour did not affect the operation of the reusable items.
All reusable items not provided by Horiba can be obtained
7.2.5 Availability of the Device and Spare Parts from a scientific equipment or computer hardware supplier,
as appropriate.
During the demonstration, none of the reusable items
provided by Horiba–specifically, the infrared Of the expendable items used during the demonstration,
spectrophotometer, Model SR-300 solvent reclaimer, the S-316 extraction solvent can be obtained from Horiba
Model GE-50 ultrasonic mixer, and Centronics printer or an authorized distributor of Horiba products.
cable–required repair or replacement. Except for the Expendable items not provided by Horiba can be obtained
Centronics printer cable, replacement parts for these items from a scientific equipment supplier.
would not have been available in stores. The Centronics

91
 Chapter 8
Economic Analysis

As discussed throughout this ITVR, the OCMA-350 was cost categories were included in the economic analysis for
demonstrated by using it to analyze soil environmental the demonstration: capital equipment, supplies, support
samples, soil PE samples, and liquid PE samples. The equipment, labor, and IDW disposal. The issues and
environmental samples were collected from three assumptions associated with these categories and the costs
contaminated sites, and the PE samples were obtained from not included in the analysis are briefly discussed below.
a commercial provider, ERA. Collectively, the Because the reference method costs were based on a fixed
environmental and PE samples provided the different cost per analysis, the issues and assumptions discussed
matrix types and the different levels and types of PHC below apply only to the OCMA-350 unless otherwise
contamination needed to perform a comprehensive stated.
economic analysis for the OCMA-350.
8.1.1 Capital Equipment Cost
During the demonstration, the OCMA-350 and the off-site
laboratory reference method were each used to perform The capital equipment cost was the cost associated with the
more than 200 TPH analyses. The purpose of the purchase of the OCMA-350 used during the
economic analysis was to estimate the total cost of TPH demonstration. This cost was obtained from a standard
measurement for the OCMA-350 and then compare this price list provided by Horiba. Because the device must be
cost to that for the reference method. The cost per analysis purchased, no salvage value was included in the capital
was not estimated for the OCMA-350 because the cost per equipment cost.
analysis would increase as the number of samples analyzed
decreased. This increase would be primarily the result of 8.1.2 Cost of Supplies
the distribution of the initial capital equipment cost across
a smaller number of samples. Thus, this increase in the The cost of supplies was estimated based on the supplies
cost per analysis cannot be fairly compared to the reference required to analyze all demonstration samples using the
laboratory’s fixed cost per analysis. OCMA-350 that were not included in the capital
equipment cost category. The supplies that Horiba used
This chapter provides information on the issues and during the demonstration fall into two general categories:
assumptions involved in the economic analysis expendable and reusable. Examples of expendable
(Section 8.1), discusses the costs associated with using the supplies include anhydrous sodium sulfate and solvent as
OCMA-350 (Section 8.2), discusses the costs associated well as disposable gloves and pipettes; however, Horiba
with using the reference method (Section 8.3), and presents promotes solvent recovery and reuse by providing an
a comparison of the economic analysis results for the optional accessory, the Model SR-300 solvent reclaimer.
OCMA-350 and the reference method (Section 8.4). Examples of reusable supplies include beakers and a
digital balance. During the demonstration, the types and
8.1 Issues and Assumptions quantities of all supplies used by Horiba were noted each
day.
Several factors affect TPH measurement costs. Wherever
possible in this chapter, these factors are identified in such For supplies provided by Horiba during the demonstration,
a way that decision-makers can independently complete a Horiba’s costs were used to estimate the cost of supplies.
project-specific economic analysis. The following five The costs for supplies not provided by Horiba were

92
estimated based on price quotes from independent sources. technician (R.S. Means Company [Means] 2000), and a
Because a user cannot typically return unused supplies, no multiplication factor of 2.5 was applied to labor costs in
salvage value for supplies that were not used during the order to account for overhead costs. Based on this hourly
demonstration was included in the cost of supplies. rate and multiplication factor, a daily rate of $332.60 was
used for the economic analysis.
8.1.3 Support Equipment Cost
8.1.5 Investigation-Derived Waste Disposal Cost
During the demonstration, the OCMA-350, the Model
GE-50 ultrasonic mixer, and the Epson LQ-500 dot-matrix During the demonstration, Horiba was provided with two
printer were operated using an AC power source. The 20-gallon laboratory packs for collecting hazardous wastes
costs associated with providing the power supply and the generated (one for flammable wastes and one for corrosive
electrical energy consumed were not included in the wastes) and was charged for each laboratory pack used.
economic analysis; the demonstration site provided AC Unused samples and sample extracts, used EnCores, and
power at no cost. Of the three items mentioned above, the unused chemicals that could not be returned to Horiba or
OCMA-350 can also be operated using a DC power source an independent vendor were disposed of in a laboratory
such as an automobile cigarette lighter. A typical user pack. Items such as used PPE and disposable glassware
does not require the other two items for TPH measurement were disposed of with municipal garbage in accordance
using the OCMA-350, so these items are considered to be with demonstration site waste disposal guidelines. Horiba
optional. was required to provide any containers necessary to
containerize individual wastes prior to their placement in
Because of the large number of samples analyzed during a laboratory pack. The cost for these containers was not
the demonstration, the EPA provided support equipment, included in the IDW disposal cost estimate.
including a tent, tables, and chairs, for the field
technician’s comfort during sample extraction and 8.1.6 Costs Not Included
analysis. For the economic analysis, the support
equipment costs were estimated based on price quotes Items whose costs were not included in the economic
from independent sources. analysis are identified below along with a rationale for the
exclusion of each.
8.1.4 Labor Cost
Oversight of Sample Analysis Activities. A typical user
The labor cost was estimated based on the time required of the OCMA-350 would not be required to pay for
for OCMA-350 setup, sample preparation, sample analysis, customer oversight of sample analysis. EPA
and summary data package preparation. The data package representatives audited all activities associated with sample
included, at a minimum, a result summary table, a run log, analysis during the demonstration, but costs for EPA
and any supplementary information submitted by Horiba. oversight were not included in the economic analysis
The measurement of the time required for Horiba to because these activities were project-specific. For the
complete all analyses and submit the data package to the same reason, costs for EPA oversight of the reference
EPA was rounded to the nearest half-hour. For the laboratory were also not included in the analysis.
economic analysis, it was assumed that a field technician
who had worked for a fraction of a day would be paid for Travel and Per Diem for Field Technicians. Field
an entire 8-hour day. Based on this assumption, a daily technicians may be available locally. Because the
rate for a field technician was used in the analysis. availability of field technicians is primarily a function of
the location of the project site, travel and per diem costs
During the demonstration, EPA representatives evaluated for field technicians were not included in the economic
the skill level required for the field technician to complete analysis.
analyses and calculate TPH concentrations. Based on the
field observations, a field technician with basic wet Sample Collection and Management. Costs for sample
chemistry skills acquired on the job or in a university and collection and management activities, including sample
a few hours of device-specific training was considered to homogenization and labeling, were not included in the
be qualified to operate the OCMA-350. For the economic economic analysis because these activities were project-
analysis, an hourly rate of $16.63 was used for a field

93
specific and were not device- or reference method- Model GE-50 ultrasonic mixer was used to disperse soil
dependent. samples in the extraction solvent, and the Model SR-300
solvent reclaimer was used to recycle spent solvent; the use
Shipping. Costs for shipping (1) the OCMA-350 and of the other reusable supplies is self-explanatory.
necessary supplies to the demonstration site and (2) sample
coolers to the reference laboratory were not included in the Cost information for all the supplies used during the
economic analysis because such costs vary depending on demonstration is presented in Table 8-1. The total cost of
the shipping distance and the service used (for example, a the supplies used by Horiba during the demonstration was
courier or overnight shipping versus economy shipping). $6,715 (the cost of each item was rounded to the nearest
$1). Of these supplies, the S-316 extraction solvent,
Items Costing Less Than $10. The cost of inexpensive Model GE-50 ultrasonic mixer, Model SR-300 solvent
items such as ice used for sample preservation in the field reclaimer, and Centronics printer cable are available from
was not included in the economic analysis because the Horiba. The other supplies have to be purchased from a
estimated cost was less than $10. retail vendor of laboratory supplies. The Centronics
printer cable can be replaced with other brands that are
8.2 OCMA-350 Costs compatible with the OCMA-350 and are available in
computer hardware stores.
This section presents information on the individual costs of
capital equipment, supplies, support equipment, labor, and During the demonstration, Horiba also used the following
IDW disposal for the OCMA-350 as well as a summary of supplies that cost less than $10 each: (1) a 280-count box
these costs. Additionally, Table 8-1 summarizes the of Kimwipes® ($3.60) for wiping the quartz cuvette and (2)
OCMA-350 costs. a 50-pound bag of concrete sand ($1.89) used as blank
material for QC checks (only about 50 grams of sand was
8.2.1 Capital Equipment Cost used during the demonstration).

The capital equipment cost was the cost associated with the Other supplies that can be purchased from Horiba if
purchase of the OCMA-350. Horiba does not rent the additional quantities are needed include the proprietary,
OCMA-350. As discussed in Chapter 2, the OCMA-350 10-mm, quartz cuvette ($535) with the Teflon® cap ($60);
consists of the infrared spectrophotometer and its the 25-µL microsyringe ($210); 10-mL syringe ($34);
accessories, including (1) a proprietary, 10-mm, quartz 10 mL of B-heavy oil for calibration ($11); a 3.15-ampere
cuvette with a Teflon® cap; (2) a 25-µL microsyringe; (3) fuse ($3); a power supply cable ($17); and the instruction
a 10-mL syringe; (4) 10 mL of B-heavy oil for calibration; manual ($25). Horiba provides an electronic copy of the
(5) three 40-mL, VOA vials; (6) three 11-cm-diameter, simplified operating instruction sheet at no cost to the user.
No. 40 Whatman filter papers; and (7) two 10-mL, During the demonstration, Horiba did not require
disposable, glass pipettes. The OCMA-350 also contains additional quantities of these supplies; therefore, the costs
an instruction manual and a simplified operating of these items are not listed in Table 8-1.
instruction sheet. The OCMA-350 can be purchased from
Horiba for $6,500. 8.2.3 Support Equipment Cost

8.2.2 Cost of Supplies Horiba was provided with one 8- by 8-foot tent for
protection from inclement weather during the
The supplies that Horiba used during the demonstration demonstration as well as two tables and two chairs for use
fall into two general categories: expendable and reusable. during sample preparation and analysis activities. The
Table 8-1 lists all the expendable and reusable supplies that purchase cost for the tent ($159) and the rental cost for two
Horiba used during the demonstration. Of the expendable tables and two chairs for 1 week ($39) totaled $198.
supplies, Horiba’s proprietary S-316 extraction solvent
was used for extracting PHCs from soil and for cleaning 8.2.4 Labor Cost
glassware, anhydrous sodium sulfate was used for drying
wet soil samples, and the VOA vials were used for soil One field technician was required for 6 days during the
sample extraction; the use of the other expendable supplies demonstration to complete all sample analyses and prepare
is self-explanatory. Of the reusable supplies, the the summary data package. Based on a labor rate of

94
Table 8-1. OCMA-350 Cost Summary

Item Quantity Unit Cost ($) Itemized Costa ($)

Capital equipment
Purchase of infrared spectrophotometer and its accessories 1 unit 6,500 6,500
Supplies
Expendable
S-316 extraction solvent (7-kilogram bottle) 1 unit 1,040 1,040
Anhydrous sodium sulfate, 10-60 mesh (500-gram bottle) 2 units 19.75 40
40-mL, VOA vials (72 per box) 3 units 62.50 188
11-cm-diameter, No. 40 Whatman filter papers (100 per box) 2 units 26 52
10-mL, disposable, glass pipettes (12 per case) 1 unit 75.60 76
Disposable, latex gloves (100 per box) 1 unit 20.50 21
Reusable
Model GE-50 ultrasonic mixer 1 unit 2,080 2,080
Model SR-300 solvent reclaimer 1 unit 1,650 1,650
Epson LQ-500 dot-matrix printer 1 unit 275 275
Centronics printer cable 1 unit 40 40
Mettler-Toledo digital balance (Model BD202) 1 unit 715 715
Stainless-steel spatulas (three per pack) 1 unit 20.30 20
Filter forceps 1 unit 20 20
Glass funnel 4 units 17.67 71
50-mL, glass beakers (12 per pack) 1 unit 38.80 39
Pipette bulb 1 unit 19.50 20
10-microliter microsyringe 1 unit 19.80 20
VWR Model 511 bottle-top dispenser 1 unit 234.90 235
Test tube rack (24 holes) 1 unit 22.50 23
Funnel rack and stand (holds four small funnels) 1 unit 90 90
Support equipment
Tent 1 unit 159 159
Tables and chairs (two each) 1 set for 1 week 39 39
Labor
Field technician 6 person-days 332.60 1,996
Investigation-derived waste disposal 1 20-gallon container 345 345
Total Costb 15,750

Notes:

cm = Centimeter
mL = Milliliter
VOA = Volatile organic analysis
a
Itemized costs were rounded to the nearest $1.
b
The total dollar amount was rounded to the nearest $10.

95
$332.60 per day, the total labor cost for the OCMA-350 purchase cost for virgin solvent, and potential
was $1,996 (rounded to the nearest $1). environmental concerns associated with hazardous waste
disposal.
8.2.5 Investigation-Derived Waste Disposal Cost
8.3 Reference Method Costs
Horiba used one laboratory pack to collect flammable
hazardous waste, including unused soil and liquid samples This section presents the costs associated with the
that contained PHCs and used EnCores and ampules, reference method used to analyze the demonstration
generated during the demonstration. Horiba collected all samples for TPH. Depending on the nature of a given
the proprietary S-316 extraction solvent, including unused sample, the reference laboratory analyzed the sample for
solvent; reclaimed solvent; and to-be-reclaimed, used GRO, EDRO, or both and calculated the TPH
solvent, in different bottles. At the end of the concentration by adding the GRO and EDRO
demonstration, Horiba took all the solvent to its laboratory concentrations, as appropriate. The reference method costs
for reuse. As a result, the IDW disposal cost included only were calculated using unit cost information from the
the purchase cost of the laboratory pack ($38) and the cost reference laboratory invoices. To allow an accurate
associated with hazardous waste disposal in a landfill comparison of the OCMA-350 and reference method costs,
($307) (Means 2000). The total IDW disposal cost was the reference method costs were estimated for the same
$345. number of samples as was analyzed by Horiba. For
example, although the reference laboratory analyzed
8.2.6 Summary of OCMA-350 Costs MS/MSD samples for TPH and all soil samples for percent
moisture, the associated sample analytical costs were not
The total cost for performing more than 200 TPH analyses included in the reference method costs because Horiba did
using the OCMA-350 and for preparing a summary data not analyze MS/MSD samples for TPH or soil samples for
package was $15,750 (rounded to the nearest $10). The percent moisture during the demonstration.
TPH analyses were performed for 74 soil environmental
samples, 89 soil PE samples, and 36 liquid PE samples. In Table 8-2 summarizes the reference method costs, which
addition to these 199 samples, 9 extract duplicates were totaled $42,050. This cost covered preparation of
analyzed for specified soil environmental samples. When demonstration samples and their analysis for TPH. In
Horiba performed multiple extractions, dilutions, or addition, at no additional cost, the reference laboratory
reanalyses for a sample, these were not included in the provided (1) analytical results for internal QC check
number of samples analyzed. During the demonstration, samples such as method blanks and LCS/LCSDs and (2) an
the multiple extractions, dilutions, and reanalyses electronic data deliverable and two paper copies of full,
collectively required only about 6 percent more supplies EPA Contract Laboratory Program-style data packages
than would otherwise have been needed. The total cost within 30 calendar days of the receipt of the last
included $6,500 for capital equipment; $6,715 for supplies; demonstration sample by the reference laboratory.
$198 for support equipment; $1,996 for labor; and $345
for IDW disposal. Of these five costs, the two largest were 8.4 Comparison of Economic Analysis Results
the capital cost (41 percent of the total cost) and the cost of
supplies (43 percent of the total cost). The total costs for the OCMA-350 ($15,750) and the
reference method ($42,050) are listed in Tables 8-1 and
A significant portion of the cost of supplies was associated 8-2, respectively. The total TPH measurement cost for the
with the Model GE-50 ultrasonic mixer (31 percent) and OCMA-350 was 62 percent less than that for the reference
Model SR-300 solvent reclaimer (25 percent). Although method. Although the OCMA-350 analytical results did
these two items were useful during the demonstration, they not have the same level of detail (for example, carbon
are considered to be optional, and their purchase is ranges) as the reference method analytical results or
justified only when a large number of samples will be comparable QA/QC data, the OCMA-350 provided TPH
analyzed. When a small number of samples will be analytical results on site at significant cost savings. In
analyzed, the ultrasonic mixer can be replaced with a addition, use of the OCMA-350 in the field will likely
cheaper means of agitation to disperse samples in solvent. produce additional cost savings because the results will be
Purchase of the solvent reclaimer should be considered available within a few hours of sample collection;
only after evaluation of the disposal cost for spent solvent, therefore, critical decisions regarding sampling and

96
Table 8-2. Reference Method Cost Summary

Item Number of Samples Analyzed Cost per Analysis ($) Itemized Costa ($)
Soil environmental samples
GRO 56 111 6,216
Extract duplicates 7 55.50 388
EDRO 74 142 10,508
Extract duplicates 9 71 639
Soil performance evaluation samples
GRO 55 111 6,105
EDRO 89 142 12,638
Liquid performance evaluation samples
GRO 27 111 2,997
EDRO 24 106.50 2,556
Total Costb 42,050

Notes:
a
Itemized costs were rounded to the nearest $1.
b
The total dollar amount was rounded to the nearest $10.

analysis can be made in the field, resulting in a more accurately estimated and thus were not included in the
complete data set. However, these savings cannot be economic analysis.

97
 Chapter 9
Summary of Demonstration Results

As discussed throughout this ITVR, the OCMA-350 was This chapter compares the performance and cost results for
demonstrated by using it to analyze 74 soil environmental the OCMA-350 with those for the reference method, as
samples, 89 soil PE samples, and 36 liquid PE samples. In appropriate. The performance and cost results are
addition to these 199 samples, 9 extract duplicates discussed in detail in Chapters 7 and 8, respectively.
prepared using the environmental samples were analyzed. Tables 9-1 and 9-2 summarize the results for the primary
The environmental samples were collected from five and secondary objectives, respectively. As shown in these
individual areas at three contaminated sites, and the PE tables, during the demonstration, the OCMA-350 exhibited
samples were obtained from a commercial provider, ERA. the following desirable characteristics of a field TPH
Collectively, the environmental and PE samples provided measurement device: (1) good precision, (2) sensitivity to
the different matrix types and the different levels and types interferents that are PHCs (MTBE and Stoddard solvent),
of PHC contamination needed to perform a comprehensive and (3) high sample throughput. In addition, the
evaluation of the OCMA-350. OCMA-350 exhibited moderate measurement costs.

The OCMA-350 performance and cost data were compared In general, the OCMA-350 TPH results for the PE samples
to those for an off-site laboratory reference method, did not compare well with the reference method results. In
SW-846 8015B (modified). As discussed in Chapter 6, the addition, turpentine biased the OCMA-350 TPH results
reference method results were considered to be of adequate high, whereas humic acid biased the results low. These
quality for the following reasons: (1) the reference method findings indicated that the accuracy of TPH measurement
was implemented with acceptable accuracy (± 30 percent) using the device will likely be impacted by naturally
for all the samples except low- and medium-concentration- occurring oil and grease and organic matter present in soil
range soil samples containing diesel, which made up only samples. PCE and 1,2,4-trichlorobenzene did not impact
13 percent of the total number of samples analyzed during the OCMA-350 results in a consistent manner when the
the demonstration, and (2) the reference method was effect of these interferents was tested using neat materials
implemented with good precision for all samples. The and spiked soil samples. Finally, the device results were
reference method results generally exhibited a negative significantly impacted by soil moisture content: a
bias. However, the bias was considered to be significant 7 percentage point increase in soil moisture content
primarily for low- and medium-range soil samples resulted in (1) a three-fold increase in TPH results for
containing diesel. The reference method recoveries weathered gasoline soil PE samples and (2) a three-fold
observed during the demonstration were typical of the decrease in TPH results for diesel soil PE samples.
recoveries obtained by most organic analytical methods for Collectively, the demonstration findings indicated that the
environmental samples. OCMA-350 may be considered for TPH screening
purposes; however, the user should exercise caution when
considering the device for a field TPH measurement
application requiring definitive results.

98
 Table 9-1. Summary of OCMA-350 Results for the Primary Objectives

Performance Results

Primary Objective Evaluation Basisa OCMA-350 Reference Method

P1 Determine the method Method detection limit based on TPH analysis of 15.2 mg/kg 4.79 mg/kg
detection limit seven low-concentration-range diesel soil PE samples
P2 Evaluate the accuracy Comparison of project-specific action level Of the 108 OCMA-350 results, 1 result was inconclusive. Of the 107 remaining OCMA-350 conclusions,
and precision of TPH conclusions of the OCMA-350 with those of the 78 (73 percent) agreed with those of the reference method; 6 OCMA-350 conclusions were false
measurement reference method for 74 soil environmental and 34 positives, and 23 were false negatives.
soil PE samples
Comparison of OCMA-350 TPH results with those of 36 of 102 OCMA-350 results (35 percent) were within 30 percent of the reference method results; 16
the reference method for 74 soil environmental and 28 OCMA-350 results were biased high, and 20 were biased low.
soil PE samples
16 of 102 OCMA-350 results (16 percent) were within 30 to 50 percent of the reference method results; 5
OCMA-350 results were biased high, and 11 were biased low.

50 of 102 OCMA-350 results (49 percent) were not within 50 percent of the reference method results;
17 OCMA-350 results were biased high, and 33 were biased low.
Pairwise comparison of OCMA-350 and reference For soil environmental samples, the OCMA-350 results were statistically (1) the same as the reference
method TPH results for (1) soil environmental method results for four of the five sampling areas and (2) different from the reference method results for
samples collected from five areas; (2) soil PE one sampling area.
samples, including blank, weathered gasoline, and
diesel soil samples; and (3) liquid PE samples For soil PE samples, the OCMA-350 results were statistically (1) the same as the reference method

99
consisting of neat weathered gasoline and diesel results for blank samples and (2) different from the reference method results for medium- and high-
concentration-range weathered gasoline samples and low-, medium-, and high-concentration-range
diesel samples.

For liquid PE samples, the OCMA-350 results were statistically (1) the same as the reference method
results for weathered gasoline samples and (2) different from the reference method results for diesel
samples.
Correlation (as determined by linear regression The OCMA-350 results correlated highly with the reference method results for three of the five sampling
analysis) between OCMA-350 and reference method areas (R2 values were greater than or equal to 0.90, and F-test probability values were less than 5
TPH results for (1) soil environmental samples percent).
collected from five areas and (2) soil PE samples,
including weathered gasoline and diesel soil samples The OCMA-350 results correlated moderately with the reference method results for diesel soil PE
samples (the R2 value was 0.68, and the F-test probability value was less than 5 percent).

The OCMA-350 results correlated weakly with the reference method results for two sampling areas and
for weathered gasoline soil PE samples (R2 values ranged from 0.19 to 0.53, and F-test probability
values ranged from 22.58 to 62.68 percent).
 Table 9-1. Summary of OCMA-350 Results for the Primary Objectives (Continued)

Performance Results
a
Primary Objective Evaluation Basis OCMA-350 Reference Method
P2 Evaluate the accuracy Overall precision (RSD) for soil environmental, soil Soil environmental samples (11 triplicates) Soil environmental samples (12 triplicates)
and precision of TPH PE, and liquid PE sample replicates RSD range: 0 to 49 percent RSD range: 4 to 39 percent
measurement Median RSD: 20 percent Median RSD: 18 percent
(continued)
Soil PE samples (7 replicates) Soil PE samples (7 replicates)
RSD range: 2 to 17 percent RSD range: 2 to 10 percent
Median RSD: 5 percent Median RSD: 7 percent
Liquid PE samples (2 triplicates) Liquid PE samples (2 triplicates)
RSDs: 1 and 2 percent RSDs: 5 and 6 percent
Median RSD: 1.5 percent Median RSD: 5.5 percent
Analytical precision (RPD) for extract duplicates for RPD range: 0 to 3 RPD range: 0 to 11
soil environmental samples (9 for the OCMA-350 and Median RPD: 1 Median RPD: 4
13 for the reference method)
P3 Evaluate the effect of Mean responses for neat materials, including MTBE; MTBE: 72.5 percent MTBE: 39 percent
interferents on TPH PCE; Stoddard solvent; turpentine; and 1,2,4- PCE: 0 percent PCE: 17.5 percent
measurement trichlorobenzene, and for soil spiked with humic acid Stoddard solvent: 86 percent Stoddard solvent: 85 percent
(two triplicate sets each) Turpentine: 85 percent Turpentine: 52 percent
1,2,4-Trichlorobenzene: 0 percent 1,2,4-Trichlorobenzene: 50 percent
Humic acid: 0 percent Humic acid: 0 percent

100
Comparison of TPH results (one-way analysis of MTBE, a petroleum hydrocarbon, caused MTBE, a petroleum hydrocarbon, did not cause
variance) for weathered gasoline and diesel soil PE statistically significant interference at both statistically significant interference at either of the two
samples without and with interferents at two levels levels. levels.

Interferents for weathered gasoline soil PE samples: PCE results were inconclusive. PCE caused statistically significant interference only at
MTBE, PCE, Stoddard solvent, and turpentine the high level.
Stoddard solvent, a petroleum hydrocarbon, Stoddard solvent, a petroleum hydrocarbon, caused
Interferents for diesel soil PE samples: Stoddard caused statistically significant interference statistically significant interference at both levels for
solvent; turpentine; 1,2,4-trichlorobenzene; and humic (1) at both levels for weathered gasoline weathered gasoline and diesel samples.
acid samples and (2) only at the high level for
diesel samples.
Turpentine caused statistically significant Turpentine caused statistically significant interference
interference at both levels for weathered (1) at both levels for weathered gasoline samples and
gasoline and diesel samples. (2) only at the high level for diesel samples.
1,2,4-Trichlorobenzene caused statistically 1,2,4-Trichlorobenzene caused statistically significant
significant interference only at the high level. interference only at the high level.
Humic acid caused statistically significant Humic acid results were inconclusive.
interference at both levels.
P4 Evaluate the effect of Comparison of TPH results (two-sample Student’s Soil moisture content had a statistically Soil moisture content did not have a statistically
soil moisture content t-test) for weathered gasoline and diesel soil PE significant impact on both weathered significant impact.
on TPH measurement samples at two moisture levels: 9 and 16 percent for gasoline sample and diesel sample results.
weathered gasoline samples and less than 1 and
9 percent for diesel samples
 Table 9-1. Summary of OCMA-350 Results for the Primary Objectives (Continued)

Performance Results
a
Primary Objective Evaluation Basis OCMA-350 Reference Method
P5 Measure the time Total time from sample receipt through preparation of 46 hours, 15 minutes, for TPH measurement 30 days for TPH measurement of 74 soil environmental
required for TPH the draft data package of 74 soil environmental samples, 89 soil PE samples, 89 soil PE samples, 36 liquid PE samples, and
measurement (sample samples, 36 liquid PE samples, and 9 extract 13 extract duplicates
throughput) duplicates
P6 Estimate TPH Total cost (costs of capital equipment, supplies, $15,750 (including the capital equipment $42,050
measurement costs support equipment, labor, and IDW disposal) for TPH purchase cost of $6,500 for the OCMA-350)
measurement of 74 soil environmental samples, 89
soil PE samples, 36 liquid PE samples, and 9 extract
duplicates

Notes:

IDW = Investigation-derived waste PE = Performance evaluation

mg/kg = Milligram per kilogram R2 = Square of the correlation coefficient
MTBE = Methyl-tert-butyl ether RPD = Relative percent difference
PCE = Tetrachloroethene RSD = Relative standard deviation
a
All statistical comparisons were made at a significance level of 5 percent.

101
Table 9-2. Summary of OCMA-350 Results for the Secondary Objectives

Secondary Objective Performance Results

S1 Skill and training The device can be operated by one person with basic wet chemistry skills.
requirements for proper
device operation The device’s instruction manual and simplified operating instruction sheet are considered to be adequate
training materials for proper device operation. The sample analysis procedure for the device can be learned
in the field with a few practice attempts.

The device’s digital display provides a sample’s TPH concentration in milligrams per kilogram TPH on a wet
weight basis; minimal effort is required to calculate a TPH concentration. At the end of the demonstration,
Horiba reported 208 TPH results. Of these, fewer than 5 percent required corrections, which primarily
involved use of inappropriate reporting limits.

Some of the device’s items, including the narrow-mouth vials used for weighing and extracting soil samples
and the gravity filtration setup, made the TPH measurement procedure less simple and more time-
consuming.
S2 Health and safety concerns No significant health and safety concerns were noted; when the device is used in a well-ventilated area,
associated with device basic eye and skin protection (safety glasses, disposable gloves, work boots, and work clothes with long
operation sleeves and long pants) should be adequate for safe device operation.
S3 Portability of the device The device can be easily moved between sampling areas in the field, if necessary.

The device can be operated using a 110-volt alternating current power source or a direct current power
source such as a 12-volt power outlet in an automobile.
S4 Durability of the device The primary component of the device, the infrared analyzer, is provided in an optional, hard-plastic carrying
case to prevent damage to the analyzer. During the demonstration, none of the device’s reusable items
malfunctioned or was damaged. The moderate temperatures (17 to 24 °C) and high relative humidities (53
to 88 percent) encountered during the demonstration did not affect device operation.
S5 Availability of device and During a 1-year warranty period, Horiba will repair any malfunctioning items of the device at no cost.
spare parts
Horiba does not supply some items necessary for TPH measurement using the device, including a test tube
rack, a funnel rack and stand, a digital balance, and miscellaneous glassware and laboratory supplies; the
availability of replacement or spare parts not supplied by Horiba depends on their manufacturer or distributor.

102
 Chapter 10
References

AEHS. 1999. “State Soil Standards Survey.” Soil & EPA. 2000. “Field Measurement Technologies for Total
Groundwater. December 1999/January 2000. Petroleum Hydrocarbons in Soil—Demonstration
Plan.” ORD. Washington, DC. EPA/600/R-01/060.
API. 1994. “Interlaboratory Study of Three Methods for June.
Analyzing Petroleum Hydrocarbons in Soils.”
Publication Number 4599. March. Ewing, Galen W. 1969. Instrumental Methods of
Chemical Analysis. Third Edition. McGraw-Hill
API. 1996. “Compilation of Field Analytical Methods for Book Company. New York.
Assessing Petroleum Product Releases.” Publication
Number 4635. December. Florida Department of Environmental Protection. 1996.
“FL-PRO Laboratory Memorandum.” Bureau of
API. 1998. “Selecting Field Analytical Methods: A Waste Cleanup. Accessed on April 21. On-Line
Decision-Tree Approach.” Publication Number 4670. Address: www.dep.state.fl.us/labs/docs/flpro.htm
August.
Fritz, James S., and George H. Schenk. 1987.
ASTM. 1998. “Standard Guide for Good Laboratory Quantitative Analytical Chemistry. Allyn and Bacon,
Practices in Laboratories Engaged in Sampling and Inc. Boston, Massachusetts. Fifth Edition.
Analysis of Water.” Designation: D 3856-95. Annual
Book of ASTM Standards. Volume 11.01. Gary, J.H., and G.E. Handwerk. 1993. Petroleum
Refining: Technology and Economics. Marcel Dekker,
California Environmental Protection Agency. 1999. Inc. New York, New York.
Memorandum Regarding Guidance for Petroleum
Hydrocarbon Analysis. From Bart Simmons, Chief, Massachusetts Department of Environmental Protection.
Hazardous Materials Laboratory. To Interested 2000. “VPH/EPH Documents.” Bureau of Waste Site
Parties. October 21. Cleanup. Accessed on April 13. On-Line Address:
www.state.ma.us/dep/bwsc/vp_eph.htm
Dryoff, George V. Editor. 1993. “Manual of Significance
of Tests for Petroleum Products.” ASTM Manual Means. 2000. Environmental Remediation Cost
Series: MNL 1. 6th Edition. Data-Unit Price. Kingston, Massachusetts.

EPA. 1983. “Methods for Chemical Analysis of Water Provost, Lloyd P., and Robert S. Elder. 1983.
and Waste.” Revision. Environmental Monitoring “Interpretation of Percent Recovery Data.” American
and Support Laboratory. Cincinnati, Ohio. EPA Laboratory. December. Pages 57 through 63.
600-4-79-020. March.
Simard, R.G., Ichiro Hasegawa, William Bandaruk, and C.
EPA. 1996. “Test Methods for Evaluating Solid Waste.” E. Headington. 1951. “Infrared Spectrophotometric
Volumes 1A through 1C. SW-846. Third Edition. Determination of Oil and Phenols in Water.”
Update III. OSWER. Washington, DC. December. Analytical Chemistry. Volume 23, No. 10. October.
Pages 1384 to 1387.

103
Speight, J.G. 1991. The Chemistry and Technology of Zilis, Kimberly, Maureen McDevitt, and Jerry Parr. 1988.
Petroleum. Marcel Dekker, Inc. New York, New “A Reliable Technique for Measuring Petroleum
York. Hydrocarbons in the Environment.” Paper Presented
at the Conference on Petroleum Hydrocarbons and
Texas Natural Resource Conservation Commission. 2000. Organic Chemicals in Groundwater. National Water
“Waste Updates.” Accessed on April 13. On-Line Well Association (Now Known as National Ground
Address: www.tnrcc.state.tx.us/permitting/ Water Association). Houston, Texas.
wastenews.htm#additional

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 Appendix
Supplemental Information Provided by the Developer

This appendix contains supplemental information provided Efficient Use of Resources

by Horiba. Specifically, updates and improvements to the
OCMA-350 resulting from the SITE demonstration are The Horiba Model SR-300 Solvent Reclaimer was used
summarized below. during the SITE demonstration and reduced the cost of
solvent used by reclaiming spent solvent. However, during
Sampling Technique the demonstration, only a small portion of the spent solvent
was regenerated because of time constraints. Greater
During the SITE demonstration, the weight of each sample efficiency and cost-effectiveness would be achieved by
was measured and adjusted to 5.0 ±0.04 grams to take collecting larger volumes of spent solvent and regenerating
advantage of the preset value in the OCMA-350. larger batches of spent solvent using the Model SR-300
Significant time was used to adjust the sample weight to solvent reclaimer.
exactly 5 grams. It was noted that much time could be
saved by quickly weighing the sample to obtain a nominal Consistency in Sample Preparation
value of 5 grams (say ±0.5 gram) but measuring its weight
to the nearest 0.1 gram. It is a simple matter to reset the The GE-50 ultrasonic disruptor was used to facilitate
sample weight in the microprocessor of the OCMA-350. extraction of PHCs in soil. The sonication time varied
from 30 seconds to 1 minute. After reviewing the
The balance used during the SITE demonstration measured extraction process, Horiba believes that 1 minute should
sample weight to within ±0.01 gram. The precision of the have been a fixed value for the sonication time for all
balance measurement and the balance’s sensitivity to gusty samples to be consistent.
winds encountered during the demonstration suggest that
the OCMA-350 instruction manual is correct in Safety Issue
recommending use of a balance with a resolution of
±0.1 gram. While using the GE-50 ultrasonic disruptor during the
SITE demonstration, Horiba made no provision for
During the SITE demonstration, a given soil sample was donning ear protection. Horiba now believes that ear
extracted using Horiba’s proprietary S-316 extraction protection is necessary during use of the GE-50 ultrasonic
solvent. The extract was then filtered through a Whatman disruptor.
No. 40 filter by gravity. It has been noted that use of a
syringe filter could reduce the filtering time by more than
50 percent.

This appendix was written solely by Horiba. The statements presented in this appendix represent the developer’s point of view and summarize
the claims made by the developer regarding the OCMA-350. Publication of this material does not represent the EPA’s approval or
endorsement of the statements made in this appendix; performance assessment and economic analysis results for the OCMA-350 are discussed
in the body of this ITVR.

105
Efficient Use of Time 350’s printer port allowed Horiba to get an estimated value
for subsequent dilution purposes. However, it was learned
During the SITE demonstration, the sample concentration that the time used to get the printout for the off-scale
was initially measured by allowing the microprocessor of reading would have been better spent by simply estimating
the OCMA-350 to achieve a stable reading even if it was a dilution factor and not waiting for the printout.
off the scale. The reasoning was that the OCMA

This appendix was written solely by Horiba. The statements presented in this appendix represent the developer’s point of view and summarize
the claims made by the developer regarding the OCMA-350. Publication of this material does not represent the EPA’s approval or
endorsement of the statements made in this appendix; performance assessment and economic analysis results for the OCMA-350 are discussed
in the body of this ITVR.

106