Subject

Environmental Management
L1-B-WASTE WATER SAMPLING
Muhammad Zaman Ul Haq

Wastewater Analysis
Sample labeling:
Identify each sample accurately and completely. Use labels or tags to identify the
samples that are moisture resistant and able to withstand field conditions. Use a
waterproof pen to complete the labels or tags. A numbered label or tag associated with
a field sample data sheet containing detailed information on the sample is preferable to
using only a label or tag for information1.
The information for each sample should include the following:
 Facility name/location
 Sample site location
 Sample number
 Name of sample collector
 Date and time of collection
 Indication of grab or composite sample with appropriate time and volume
information
 Identification of parameter to be analyzed
 Preservative used.
Wastewater Sample Preservation and Holding Time:
most cases, wastewater samples contain one or more unstable pollutants that require
immediate (e.g., within 15 minutes) preservation and/or analysis. Provide appropriate
chemical preservation before transferring samples to the laboratory. Procedures used to
preserve samples include cooling, pH adjustment, and chemical treatment. For some
parameters such as cyanide and phenols, add preservatives to sample bottles prior to
or immediately following sample collection. For many samples, if preservatives are not
appropriately used, bacteria can quickly degrade certain constituents (such as phenols
and phosphorus). Other constituents may volatilize (such as volatile organics and
sulfides) or may react to form different chemical species (hexavalent chromium, for
example). Proper preservation and holding times are essential to ensure sample
integrity. Analysis of samples within one day ensures against error from sample
deterioration. However, such prompt analysis is not feasible for composite samples in
which portions may be stored for as long as 24 hours. Where possible, provide sample
preservation during compositing, usually by refrigeration to 4°C (or icing). If using an
automatic sampler with ice, replace the ice as necessary to maintain low temperatures.
This is a particular limitation of automatic samplers used during the summer when ice
must be frequently replaced. The times listed at the table are the maximum holding
times between sample collection and analysis that are allowed for the sample to be
considered valid. Typically, the holding time limitations begin upon combination of the
last aliquot in a sample. When use of an automatic sampler makes it impossible to
preserve each aliquot, the preservation (chemical) should be done immediately
following the composite.

Transfer of Custody and Shipment of Samples:

To ensure the validity of the permit compliance sampling data in court, written records
must accurately trace the custody of each sample through all phases of the monitoring
program. The primary objective of this chain of-custody is to create an accurate written
record that can be used to trace the possession and handling of the sample from the
moment of its collection through its analysis and introduction as evidence.
 Use sample seals to protect the sample's integrity from the time of collection to
the time it is opened in the laboratory. The seal should indicate the collector's
name, the date and time of sample collection, and sample identification number.
 Pack samples properly to prevent breakage. Seal or lock the shipping container
to readily detect any evidence of tampering can be readily detected. Use of
tamper proof evidence tape is recommended.
 Place samples on ice or synthetic ice substitute that will maintain sample
temperature at 4°C throughout shipment.
 Accompany every sample with a sample tag and a chain-of-custody record that
has been completed, signed, and dated. The chain-of-custody record should
 include the names of sample collectors, sample identification numbers, date and
time of sample collection, location of sample collection, and names and
signatures of all persons handling the sample in the field and in the laboratory.
 The responsibility for proper packaging, labeling, and transferring of possession
of the sample lies with the inspector.
 Accompany all sample shipments with the chain-of-custody record and other
pertinent forms. The originator retains a copy of these forms. Also, the originator
must retain all receipts associated with the shipment.
 When transferring possession of samples, the transferee must sign and record
the date and time on the chain of-custody record (use the currently approved
record). In general, make custody transfers for each sample, although samples
may be transferred as a group, if desired. Each person who takes custody must
fill in the appropriate section of the chain-of-custody record.
Quality Control:
Conduct control checks during the actual sample collection to determine the
performance of sample collection techniques. In general, the most common monitoring
errors usually are improper sampling methodology, improper preservation, inadequate
mixing during compositing and splitting, and excessive sample holding time. In addition,
collect and analyze the following samples to check sample collection techniques:

1. Trip Blank. This is a sample vial(s) filled at the laboratory with deionized water. The
blank(s) follows the same handling and transport procedures as the samples collected
during the event. The blank(s) functions as a check on sample contamination originating
from sample transport, shipping and from site conditions. Note: Expose the trip blank
vial(s), to the same environmental conditions (i.e., light, temperature, etc.) of the sample
vial(s) but do not open until it is time for analysis.
2. Field Blank/Field Reagent Blank. These are similar to the trip blanks except they are
prepared in the field with deionized water exactly as the sample(s) that are collected.
Field blanks are used to check for analytical artifacts and/or background introduced by
sampling and analytical procedures.
3. Equipment/Rinsate Blank. Collect a blank when using an automatic sampler or other
non-dedicated equipment during the sampling process. The blank is a check of the
equipment cleanliness. For automatic samplers, prepare blanks prior to collecting
samples, by pumping deionized organic free water through the sampler and collecting
the discharge purge water in a sample container for analysis for the constituents of
concern.
Field Duplicate. Collect this sample simultaneously from the same source at selected
stations on a random time frame by grab samples or from two sets of field equipment
installed at the site. Duplicate samples check analytical precision as well as evaluate
the “representativeness” of the sample aliquot.
Split Samples. These are samples that have been divided into two containers for
analysis by separate laboratories. These samples provide an excellent means of
identifying discrepancies in the permittee’s analytical techniques and procedures. When
filling split samples from a single composite jug, shake the composited sample well and
half fill the EPA sample container, then shake the composite again and fill half of the
permittee’s container. Repeat the procedure for each parameter collected. The
laboratories performing the sample analyses should also use the following control
measures:
Prepare/Reagent Blank. A sample consisting of reagent(s), without the target analyte or
sample matrix, introduced into the analytical procedure at the appropriate point and
carried through all subsequent steps to determine the contribution of the reagents and
of the involved analytical steps to error in the observed value.
Quality Control Sample. This is an uncontaminated sample matrix spiked with known
amounts of analytes from a source independent from the calibration standards. Use this
sample to establish intra laboratory or analyst specific precision and bias or to assess
the performance of all or a portion of the measurements’ system.
Matrix Spike/Matrix Spike Duplicate (MS/MSD). This sample is three times the normal
volume required for a specific chemical analysis to which a known quantity of analyte
has been added prior to all sample preparation. The laboratory utilizes the MS/MSD
samples as part of their Quality Assurance/Quality Control Program.
. Use a matrix spike to verify accuracy of the analytical procedures.
. A matrix spike duplicate is a duplicate of a matrix spike sample. It measures the
precision of the analysis in terms of relative percent difference.

Data Handling and Reporting:

Verified analytical results are normally entered into a laboratory data management
system of some type. The system should contain the sampling data, including:
1. Time and exact location,
2. Analysis dates and times,
3. Names of analysts,
4. Analytical methods/techniques used, and
5. Analytical results.
Data are then reported to the project officer for inclusion into the compliance report.