Alpha Analytical, Inc. ID No.

:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 1 of 6

pH in Aqueous, Soil/Sediment, Solid and Waste Samples

References: USEPA “Method 9045D Soil and Waste pH,” in Test Methods for Evaluating Solid
Waste, SW846, Revision 4, November 2004.

USEPA “Method 9040C pH Electrometric Measurement” in Test Methods for

Evaluating Solid Waste, SW846, Revision 3, November 2004.

SM 4500H-B, Standard Methods for the Examination of Water and

Wastewater, APHA-AWWA-WPCF, 21st Edition, 2005.

1. Scope and Application

Matrices: Aqueous (at least 20% aqueous phase), Soil/Sediment, Solid and Waste
Definitions: Refer to Alpha Analytical Quality Manual.

The data report packages present the documentation of any method modification related to the
samples tested. Depending upon the nature of the modification and the extent of intended use, the
laboratory may be required to demonstrate that the modifications will produce equivalent results for
the matrix. Approval of all method modifications is by one or more of the following laboratory
personnel before performing the modification: Area Supervisor, Department Supervisor, Laboratory
Director, or Quality Assurance Officer.
This method is restricted to use by or under the supervision of analysts experienced in the
operation of the pH equipment and in the interpretation of data. Each analyst must demonstrate the
ability to generate acceptable results with this method by performing an initial demonstration of
capability, analyzing a proficiency test sample and completing the record of training.
After initial demonstration, ongoing demonstration is based on acceptable laboratory performance
of at least a quarterly laboratory control sample or acceptable performance from an annual
proficiency test sample. A major modification to this procedure requires demonstration of
performance. The identification of major method modification requiring performance demonstration
is directed by the Quality Assurance Officer and/or Laboratory Director on a case-by-case basis.

2. Summary of Method
An aliquot of a water/aqueous sample (analyzed “as is”); soil/sediment or waste sample; is mixed
with laboratory reagent water. The pH of the solution is measured electrometrically with a pH meter
using a combination electrode.

2.1 Method Modifications from Reference

None.

3. Reporting Limits
There is no reporting limit for this method.

4. Interferences
Samples with very low or very high pH may produce incorrect readings on the meter. For samples
with a true pH of > 10, the measured pH may be incorrectly low. This error can be minimized by

Printouts of this document may be out of date and should be considered uncontrolled. To accomplish work,
the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004
Alpha Analytical, Inc. ID No.:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 2 of 6

using a low-sodium-error electrode. Strong acid solutions, with a true pH of < 1, may give
incorrectly high pH measurements.
Temperature fluctuations may cause measurement errors. The use of an automatic temperature
compensation probe will minimize temperature errors. If this is not an option, the temperature and
pH shall be recorded at the time of the pH reading.
Measurement errors can occur when the electrodes become coated. If an electrode becomes
coated with sample material that will not rinse off, perform the following maintenance of the probe.
1) clean the electrode in an ultrasonic bath, or 2) wash the electrode with detergent, rinse several
times with reagent water, place in 1:10 HCl solution so that the lower third of the electrode is
submerged, and then thoroughly rinse with reagent water.
Solvents should be avoided as they may damage the probe operation.

5. Health and Safety

The toxicity or carcinogenicity of each reagent and standard used in this method is not fully
established; however, each chemical compound must be treated as a potential health hazard. From
this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by
whatever means available. A reference file of material data handling sheets is available to all
personnel involved in the chemical analysis. Additional references to laboratory safety are available
in the Chemical Hygiene Plan.
All personnel handling environmental samples known to contain or to have been in contact with
municipal waste must follow safety practices for handling known disease causative agents.

6. Sample Collection, Preservation, Shipping and Handling

6.1 Sample Collection
The sample should be collected in clean plastic or glass containers. Approximately 20g of
soil/sediment sample, and approximately 100mL if aqueous/water sample, is required to allow
for sample analysis and/or matrix QC.
6.2 Sample Preservation
None.
6.3 Sample Shipping
No special shipping requirements are necessary. Refer to Sample Receipt and Login SOP
(SOP/01-01).
6.4 Sample Handling
+ o
Maintain samples at 4°C 2 C from sample collection until analysis. Analyze soil/sediment or
waste pH samples as soon as possible, and within 24 hours of receipt.
Refer to Refer to Sample Receipt and Login SOP (SOP/01-01).

7. Equipment and Supplies

7.1 pH Meter: Orion Model 720A pH/mV/Temperature meter.
7.2 Combination pH electrode: Orion, gel-filled. Note: The combination electrode has both
measuring and reference functions; therefore, a separate reference electrode is not required.
7.3 Automatic Temperature Compensation Probe: Orion
7.4 Glass Beakers: 50mL volume
Printouts of this document may be out of date and should be considered uncontrolled. To accomplish work,
the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004
Alpha Analytical, Inc. ID No.:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 3 of 6

7.5 Magnetic stirrer

7.6 Teflon-coated stir bars
7.7 Analytical balance: Accurate to 0.1g.
7.8 Graduated cylinder: 10mL volume
7.9 Shaker Table: New Brunswick Scientific, Innova 2300

8. Reagents and Standards

8.1 Laboratory Reagent Water: ASTM Type II, deionized (DI) water
8.2 Buffer Solutions: Fisherbrand standard buffer solutions, certified at the following pH
concentrations: 4.00, 7.00, 10.00, ~2, ~13. Additionally, a second source of buffer 4.00, 7.00
and 10.00 is required for LCS/ICV and CCV analysis. Buffers are labeled upon receipt and
initial opening, and must be used prior to the manufacturer’s expiration date. Store buffers at
room temperature.

9. Quality Control
The laboratory must maintain records to document the quality of data that is generated. Ongoing
data quality checks are compared with established performance criteria to determine if the results
of analyses meet the performance characteristics of the method.
9.1 Blank(s)
Not applicable to this method.
9.2 Laboratory Control Sample (LCS)
A second source pH 7.00 buffer is analyzed immediately following pH meter calibration.
Criterion for acceptable recovery is + 0.05 pH units. Corrective action: If the LCS is outside the
acceptable range, re-calibrate the pH meter. Acceptable second source LCS recovery must be
obtained prior to the analysis of samples.
9.3 Initial Calibration Verification (ICV)
Refer to Section 9.2.
9.4 Continuing Calibration Verification (CCV)
A CCV is analyzed every 10 samples and at the end of an analytical batch to monitor the
accuracy of the calibration during analysis. The CCV is a second source buffer solution (4.00,
7.00, or 10.00) in the appropriate range of the samples. Criterion for acceptable recovery is +
0.05 pH units. Corrective action: If the CCV is outside of acceptable range, re-calibrate the pH
meter and re-analyze all samples since the last acceptable CCV.
9.5 Matrix Spike
Not applicable to this method.
9.6 Laboratory Duplicate
Samples are analyzed in duplicate at a frequency of 10% or 1 per batch of 10 samples or less,
whichever is more frequent. Relative percent difference (RPD) between sample duplicate

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the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004
 Alpha Analytical, Inc. ID No.:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 4 of 6

results must be < 15%. Corrective action: If RPD does not meet criteria, determine if the cause
is matrix related or lab related. If matrix related, include a narrative with the client report
explaining the matrix effect on the imprecision of the pH result. If error was lab related, repeat
the analysis.

RPD = (R1 - R2) X 100

(R1 + R2)
2
9.7 Method-specific Quality Control Samples
None.
9.8 Method Sequence
• pH Meter calibration
• LCS / ICV
• Samples 1-9
• Laboratory Duplicate
• CCV

10. Procedure
10.1 Equipment Set-up
Turn on pH meter and allow to warm up.

10.2 Initial Calibration

The pH meter/electrode system must be calibrated at a minimum of two points that bracket the
expected pH of the samples. Calibrate using pH buffer 7 and 4 for neutral or acidic samples.
Calibrate using pH buffer 7 and 10 for basic samples. For extremely acidic or basic samples use
the ~2 or ~13 buffers in place of the 4 or 10 buffers, respectively.
10.2.1 Immerse the clean probe in a fresh 25 - 50mL aliquot of pH buffer 7.00, add a magnetic
stir bar and place the beaker on a magnetic stirring plate. Using the front knob, adjust the
digital read-out to 7.00.
10.2.2 Rinse the probe and transfer to a fresh 25 - 50mL aliquot of 4.00 or 10.00 buffer solution,
as appropriate. Place the beaker on a magnetic stirring plate. While stirring, use the rear
knob to adjust the digital read-out to 4.00, or 10.00, as appropriate for the buffer solution
being used for calibration of the meter.
10.2.3 To verify that the calibration remains correct after the adjustment for the second buffer,
rinse the probe in reagent water and immerse in the second source pH buffer 7.00. If the
reading is 7.00 + 0.05 pH units, proceed with sample analysis. Corrective Action: If the
pH reading is not within the defined limits, repeat Sections 10.2.1 through 10.2.3.

10.3 Equipment Operation and Sample Processing

Standardize the meter and electrode system as outlined above. Meter must be set to “PH”
during all sample analyses.

Printouts of this document may be out of date and should be considered uncontrolled. To accomplish work,
the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004
 Alpha Analytical, Inc. ID No.:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 5 of 6

Weigh 20g of soil/sediment or waste in a 50mL beaker. Add 20mL reagent water and
continuously stir the soil/water slurry on a magnetic stir plate for 5 minutes. NOTE: The analyst
may use 10g soil and 10mL reagent water, dependent upon the sample, provided the soil/water
ratio is 1:1. For sediments with high organic content: Weigh 10g to 20g in 125mL plastic bottle
with a 1/1 ratio of DI water. Shake sample for 30 minutes on a Shaker Table. Allow to settle
and then shake again for 5 minutes and let settle again.

Let a soil/water slurry suspension stand for about 1 hour to allow most of the suspended
particles to settle out. Let a waste/water slurry suspension stand for about 15 minutes to settle
particles.

Place the pH electrode in the beaker and adjust the level of the electrode such that it is just
below the suspension.

Allow probe to stabilize before recording the pH reading.

For water/aqueous samples, use 25-50mL of the sample provided. Analyze “as is” and DO
NOT MIX with any additional DI water. Transfer the sample aliquot to a 50mL beaker, and read
the pH as above for soil/sediment/waste samples.
Rinse electrode thoroughly between samples.

10.4 Continuing Calibration

To verify that the calibration remains accurate throughout the batch sequence, after every 10
samples or less and at the end of the batch sequence rinse the probe in reagent water and
immerse in the second source pH buffer 7.00. The pH reading must be 7.00 + 0.05 pH units.
Corrective Action: If the pH reading is not within the defined limits, repeat Sections 10.2.1
through 10.2.4 and reanalyze any samples since the last acceptable CCV.

10.5 Preventive Maintenance

The electrode is rinsed with DI and gently dried with a KimWipe between sample readings.

11. Data Evaluation, Calculations and Reporting

The pH meter reads directly in pH units. Report pH of the soil/sediment sample, as measured in
water, to the nearest 0.1 pH unit. Report “pH as soil/waste pH measured in water at [room
temperature]°C”, where the temperature of the measurement is reported as room temperature,
25°C. Results are reported as pH units between 1 and 12.
Very acid (low) pH samples are reported as <1 pH units, and very basic (high) pH samples are
reported as >12 pH units.

12. Contingencies for Handling Out-of-Control Data or Unacceptable

Data
Section 9 includes Corrective Actions for data that is out of tolerance.

Printouts of this document may be out of date and should be considered uncontrolled. To accomplish work,
the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004
 Alpha Analytical, Inc. ID No.:2178
Facility: Mansfield Revision 3
Department:Wet Chemistry Published Date:6/27/2012 6:22:14 AM
Title: pH in Aqueous and Soil Samples Page 6 of 6

13. Method Performance

13.1 Method Detection Limit Study (MDL) / Limit of Detection Study (LOD) /
Limit of Quantitation (LOQ)
The laboratory follows the procedure to determine the MDL, LOD, and/or LOQ as outlined in
Alpha SOP/08-05. These studies performed by the laboratory are maintained on file for review.
13.2 Demonstration of Capability Studies
13.2.1 Initial (IDC)
The analyst must make an initial, one-time, demonstration of the ability to generate
acceptable accuracy and precision with this method, prior to the processing of any
samples.
13.2.2 Continuing (DOC)
The analyst must make a continuing, annual, demonstration of the ability to generate
acceptable accuracy and precision with this method.

14. Pollution Prevention and Waste Management

Refer to Alpha’s Chemical Hygiene Plan the Hazardous Waste and Disposal SOP (G-006) for
further pollution prevention and waste management information.

15. Referenced Documents

Chemical Hygiene Plan
SOP/08-05 MDL Generation
SOP/08-12 IDC Generation
Hazardous Waste and Disposal SOP (G-006)
Sample Receipt and Login SOP (SOP/01-01)

16. Attachments
None.

Printouts of this document may be out of date and should be considered uncontrolled. To accomplish work,
the published version of the document should be viewed online.
Document Type: SOP-Technical Pre-Qualtrax Document ID: W-003 and W-004