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(continued)

7.2.1 Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding appropriate volumes of one or more stock standards to a volumetric flask. To each calibration standard or standard mixture, add a known constant amount of one or more internal standards, and dilute to volume with acetone. One of the calibration standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the GC/MS system.

7.2.2 Using injections of 2 to 5 µL, analyze each calibration standard according to Section 13 and tabulate the area of the primary characteristic m/z (Tables 4 and 5) against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.

Equation 1
where:

As=Area of the characteristic m/z for the parameter to be measured.

Ais=Area of the characteristic m/z for the internal standard.

Cis=Concentration of the internal standard (µg/L).

Cs=Concentration of the parameter to be measured (µg/L).

If the RF value over the working range is a constant (<35% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, As/Ais, vs. RF.

7.3 The working calibration curve or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±20%, the test must be repeated uning a fresh calibration standard. Alternatively, a new calibration curve must be prepared for that compound.

8. Quality Control

8.1 Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. 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. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.

8.1.1 The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.

8.1.2 In recognition of advances that are occuring in chromatography, the analyst is permitted certain options (detailed in Sections 10.6 and 13.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.

8.1.3 Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.

8.1.4 The laboratory must, on an ongoing basis, spike and analyze a minimum of 5% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.

8.1.5 The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 5% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.

8.1.6 The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.

8.2 To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.

8.2.1 A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 100 µg/mL in acetone. Multiple solutions may be required. PCBs and multicomponent pesticides may be omitted from this test. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.

8.2.2 Using a pipet, prepare QC check samples at a concentration of 100 µg/L by adding 1.00 mL of QC check sample concentrate to each of four 1–L aliquots of reagent water.

8.2.3 Analyze the well-mixed QC check samples according to the method beginning in Section 10 or 11.

8.2.4 Calculate the average recovery (X) in µg/L, and the standard deviation of the recovery (s) in µg/L, for each parameter using the four results.

8.2.5 For each parameter compare s and X with the corresponding acceptance criteria for precision and accuracy, respectively, found in Table 6. If s and X for all parameters of interest meet the acceptance criteria, the system performance is acceptable and analysis of actual samples can begin. If any individual s exceeds the precision limit or any individual X falls outside the range for accuracy, the system performance is unacceptable for that parameter.

Note: The large number of parameters in Table 6 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.

8.2.6 When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.

8.2.6.1 Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.

8.2.6.2 Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.2.

8.3 The laboratory must, on an ongoing basis, spike at least 5% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing 1 to 20 samples per month, at least one spiked sample per month is required.

8.3.1. The concentration of the spike in the sample should be determined as follows:

8.3.1 If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.

8.3.1.2 If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 100 µg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.

8.3.1.3 If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or 100 µg/L.

8.3.2 Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.

8.3.3 Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 6. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.7 If spiking was performed at a concentration lower than 100 µg/L, the analyst must use either the QC acceptance criteria in Table 6, or optional QC acceptance criteria calculated for the specific spike concentration. To calculate optional acceptance criteria for the recovery of a parameter: (1) Calculate accuracy (X') using the equation in Table 7, substituting the spike concentration (T) for C; (2) calculate overall precision (S') using the equation in Table 7, substituting X' for X ; (3) calculate the range for recovery at the spike concentration as (100 X'/T)±2.44(100 S'/T)%7

8.3.4 If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.

8.4 If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.

Note: The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of single-component parameters in Table 6 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spike sample.

8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.

8.4.2 Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (PS) as 100 (A/T)%, where T is the true value of the standard concentration.

8.4.3 Compare the percent recovery (Ps) for each parameter with the corresponding QC acceptance criteria found in Table 6. Only parameters that failed the test in Section 8.3 need to be compared with these criteria. If the recovery of any such parameter falls outside the designated range, the laboratory performance for that parameter is judged to be out of control, and the problem must be immediately identified and corrected. The analytical result for that parameter in the unspiked sample is suspect and may not be reported for regulatory compliance purposes.

8.5 As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P ) and the standard deviation of the percent recovery (sp). Express the accuracy assessment as a percent interval from P -2sp to P +2sp. If P =90% and sp=10%, for example, the accuracy interval is expressed as 70-110%. Update the accuracy assessment for each parameter on a regular basis (e.g. after each five to ten new accuracy measurements).

8.6 As a quality control check, the laboratory must spike all samples with the surrogate standard spiking solution as described in Section 10.2, and calculate the percent recovery of each surrogate compound.

8.7 It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.

9. Sample Collection, Preservation, and Handling

9.1 Grab samples must be collected in glass containers. Conventional sampling practices8 should be followed, except that the bottle must not be prerinsed with sample before collection. Composite samples should be collected in refrigerated glass containers in accordance with the requirements of the program. Automatic sampling equipment must be as free as possible of Tygon tubing and other potential sources of contamination.

9.2 All sampling must be iced or refrigerated at 4 °C from the time of collection until extraction. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.9 Field test kits are available for this purpose.

9.3 All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.

10. Separatory Funnel Extraction

10.1 Samples are usually extracted using separatory funnel techniques. If emulsions will prevent achieving acceptable solvent recovery with separatory funnel extractions, continuous extraction (Section 11) may be used. The separatory funnel extraction scheme described below assumes a sample volume of 1 L. When sample volumes of 2 L are to be extracted, use 250, 100, and 100-mL volumes of methylene chloride for the serial extraction of the base/neutrals and 200, 100, and 100-mL volumes of methylene chloride for the acids.

10.2 Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2–L separatory funnel. Pipet 1.00 mL of the surrogate standard spiking solution into the separatory funnel and mix well. Check the pH of the sample with wide-range pH paper and adjust to pH>11 with sodium hydroxide solution.

10.3 Add 60 mL of methylene chloride to the sample bottle, seal, and shake for 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask. If the emulsion cannot be broken (recovery of less than 80% of the methylene chloride, corrected for the water solubility of methylene chloride), transfer the sample, solvent, and emulsion into the extraction chamber of a continuous extractor and proceed as described in Section 11.3.

10.4 Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner. Label the combined extract as the base/neutral fraction.

10.5 Adjust the pH of the aqueous phase to less than 2 using sulfuric acid. Serially extract the acidified aqueous phase three times with 60-mL aliquots of methylene chloride. Collect and combine the extracts in a 250-mL Erlenmeyer flask and label the combined extracts as the acid fraction.

10.6 For each fraction, assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.

10.7 For each fraction, pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.

10.8 Add one or two clean boiling chips and attach a three-ball Snyder column to the evaporative flask for each fraction. Prewet each Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus from the water bath and allow it to drain and cool for at least 10 min. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe is recommended for this operation.

10.9 Add another one or two clean boiling chips to the concentrator tube for each fraction and attach a two-ball micro-Snyder column. Prewet the Snyder column by adding about 0.5 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus from the water bath and allow it to drain and cool for at least 10 min. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with approximately 0.2 mL of acetone or methylene chloride. Adjust the final volume to 1.0 mL with the solvent. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extracts will be stored longer than two days, they should be transferred to Teflon-sealed screw-cap vials and labeled base/neutral or acid fraction as appropriate.

10.10 Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.

11. Continuous Extraction

11.1 When experience with a sample from a given source indicates that a serious emulsion problem will result or an emulsion is encountered using a separatory funnel in Section 10.3, a continuous extractor should be used.

11.2 Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Check the pH of the sample with wide-range pH paper and adjust to pH >11 with sodium hydroxide solution. Transfer the sample to the continuous extractor and using a pipet, add 1.00 mL of surrogate standard spiking solution and mix well. Add 60 mL of methylene chloride to the sample bottle, seal, and shake for 30 s to rinse the inner surface. Transfer the solvent to the extractor.

11.3 Repeat the sample bottle rinse with an additional 50 to 100-mL portion of methylene chloride and add the rinse to the extractor.

11.4 Add 200 to 500 mL of methylene chloride to the distilling flask, add sufficient reagent water to ensure proper operation, and extract for 24 h. Allow to cool, then detach the distilling flask. Dry, concentrate, and seal the extract as in Sections 10.6 through 10.9.

11.5 Charge a clean distilling flask with 500 mL of methylene chloride and attach it to the continuous extractor. Carefully, while stirring, adjust the pH of the aqueous phase to less than 2 using sulfuric acid. Extract for 24 h. Dry, concentrate, and seal the extract as in Sections 10.6 through 10.9.

12. Daily GC/MS Performance Tests

12.1 At the beginning of each day that analyses are to be performed, the GC/MS system must be checked to see if acceptable performance criteria are achieved for DFTPP.10 Each day that benzidine is to be determined, the tailing factor criterion described in Section 12.4 must be achieved. Each day that the acids are to be determined, the tailing factor criterion in Section 12.5 must be achieved.

12.2 These performance tests require the following instrumental parameters:

Electron Energy: 70 V (nominal)

Mass Range: 35 to 450 amu

Scan Time: To give at least 5 scans per peak but not to exceed 7 s per scan.

12.3 DFTPP performance test—At the beginning of each day, inject 2 µL (50 ng) of DFTPP standard solution. Obtain a background-corrected mass spectra of DFTPP and confirm that all the key m/z criteria in Table 9 are achieved. If all the criteria are not achieved, the analyst must retune the mass spectrometer and repeat the test until all criteria are achieved. The performance criteria must be achieved before any samples, blanks, or standards are analyzed. The taililg factor tests in Sections 12.4 and 12.5 may be performed simultaneously with the DFTPP test.

12.4 Column performance test for base/neutrals—At the beginning of each day that the base/neutral fraction is to be analyzed for benzidine, the benzidine tailing factor must be calculated. Inject 100 ng of benzidine either separately or as a part of a standard mixture that may contain DFTPP and calculate the tailing factor. The benzidine tailing factor must be less than 3.0. Calculation of the tailing factor is illustrated in Figure 13. 11 Replace the column packing if the tailing factor criterion cannot be achieved.

12.5 Column performance test for acids—At the beginning of each day that the acids are to be determined, inject 50 ng of pentachlorophenol either separately or as a part of a standard mix that may contain DFTPP. The tailing factor for pentachlorophenol must be less than 5. Calculation of the tailing factor is illustrated in Figure 13. 11 Replace the column packing if the tailing factor criterion cannot be achieved.

13. Gas Chromatography/Mass Spectrometry

13.1 Table 4 summarizes the recommended gas chromatographic operating conditions for the base/neutral fraction. Table 5 summarizes the recommended gas chromatographic operating conditions for the acid fraction. Included in these tables are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by these columns are shown in Figures 1 through 12. Other packed or capillary (open-tubular) columns or chromatographic conditions may be used if the requirements of Section 8.2 are met.

13.2 After conducting the GC/MS performance tests in Section 12, calibrate the system daily as described in Section 7.

13.3 The internal standard must be added to sample extract and mixed thoroughly immediately before it is injected into the instrument. This procedure minimizes losses due to adsorption, chemical reaction or evaporation.

13.4 Inject 2 to 5 µL of the sample extract or standard into the GC/MS system using the solvent-flush technique. 12 Smaller (1.0 µL) volumes may be injected if automatic devices are employed. Record the volume injected to the nearest 0.05 µL.

13.5 If the response for any m/z exceeds the working range of the GC/MS system, dilute the extract and reanalyze.

13.6 Perform all qualitative and quantitative measurements as described in Sections 14 and 15. When the extracts are not being used for analyses, store them refrigerated at 4°C, protected from light in screw-cap vials equipped with unpierced Teflon-lined septa.

14. Qualitative Identification

14.1 Obtain EICPs for the primary m/z and the two other masses listed in Tables 4 and 5. See Section 7.3 for masses to be used with internal and surrogate standards. The following criteria must be met to make a qualitative identification:

14.1.1 The characteristic masses of each parameter of interest must maximize in the same or within one scan of each other.

14.1.2 The retention time must fall within ±30 s of the retention time of the authentic compound.

14.1.3 The relative peak heights of the three characteristic masses in the EICPs must fall within ±20% of the relative intensities of these masses in a reference mass spectrum. The reference mass spectrum can be obtained from a standard analyzed in the GC/MS system or from a reference library.

14.2 Structural isomers that have very similar mass spectra and less than 30 s difference in retention time, can be explicitly identified only if the resolution between authentic isomers in a standard mix is acceptable. Acceptable resolution is achieved if the baseline to valley height between the isomers is less than 25% of the sum of the two peak heights. Otherwise, structural isomers are identified as isomeric pairs.

15. Calculations

15.1 When a parameter has been identified, the quantitation of that parameter will be based on the integrated abundance from the EICP of the primary characteristic m/z in Tables 4 and 5. Use the base peak m/z for internal and surrogate standards. If the sample produces an interference for the primary m/z, use a secondary characteristic m/z to quantitate.

Calculate the concentration in the sample using the response factor (RF) determined in Section 7.2.2 and Equation 3.

Equation 3
where:

As=Area of the characteristic m/z for the parameter or surrogate standard to be measured.

Ais=Area of the characteristic m/z for the internal standard.

Is=Amount of internal standard added to each extract (µg).

Vo=Volume of water extracted (L).

15.2 Report results in µg/L without correction for recovery data. All QC data obtained should be reported with the sample results.

16. Method Performance

16.1 The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.1 The MDL concentrations listed in Tables 4 and 5 were obtained using reagent water.13 The MDL actually achieved in a given analysis will vary depending on instrument sensitivity and matrix effects.

16.2 This method was tested by 15 laboratories using reagent water, drinking water, surface water, and industrial wastewaters spiked at six concentrations over the range 5 to 1300 µg/L.14 Single operator precision, overall precision, and method accuracy were found to be directly related to the concentration of the parameter and essentially independent of the sample matrix. Linear equations to describe these relationships are presented in Table 7.

17. Screening Procedure for 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8–TCDD)

17.1 If the sample must be screened for the presence of 2,3,7,8–TCDD, it is recommended that the reference material not be handled in the laboratory unless extensive safety precautions are employed. It is sufficient to analyze the base/neutral extract by selected ion monitoring (SIM) GC/MS techniques, as follows:

17.1.1 Concentrate the base/neutral extract to a final volume of 0.2 ml.

17.1.2 Adjust the temperature of the base/neutral column (Section 5.6.2) to 220 °C.

17.1.3 Operate the mass spectrometer to acquire data in the SIM mode using the ions at m/z 257, 320 and 322 and a dwell time no greater than 333 milliseconds per mass.

17.1.4 Inject 5 to 7 µL of the base/neutral extract. Collect SIM data for a total of 10 min.

17.1.5 The possible presence of 2,3,7,8–TCDD is indicated if all three masses exhibit simultaneous peaks at any point in the selected ion current profiles.

17.1.6 For each occurrence where the possible presence of 2,3,7,8–TCDD is indicated, calculate and retain the relative abundances of each of the three masses.

17.2 False positives to this test may be caused by the presence of single or coeluting combinations of compounds whose mass spectra contain all of these masses.

17.3 Conclusive results of the presence and concentration level of 2,3,7,8–TCDD can be obtained only from a properly equipped laboratory through the use of EPA Method 613 or other approved alternate test procedures.

References

1. 40 CFR part 136, appendix B.

2. “Sampling and Analysis Procedures for Screening of Industrial Effluents for Priority Pollutants,” U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1977, Revised April 1977. Available from Effluent Guidelines Division, Washington, DC 20460.

3. ASTM Annual Book of Standards, Part 31, D3694–78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.

4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77–206, August 1977.

5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).

6. “Safety in Academic Chemistry Laboratories,”American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.

7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,” American Laboratory, 15, 58–63 (1983). (The value 2.44 used in the equation in Section 8.3.3 is two times the value 1.22 derived in this report.)

8. ASTM Annual Book of Standards, Part 31, D3370–76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.

9. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA–600/4–79–020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.

10. Eichelberger, J.W., Harris, L.E., and Budde, W.L. “Reference Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectometry,” Analytical Chemistry, 47, 995 (1975).

11. McNair, N.M. and Bonelli, E.J. “Basic Chromatography,” Consolidated Printing, Berkeley, California, p. 52, 1969.

12. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,” Journal of the Association of Official Analytical Chemists, 48, 1037 (1965).

13. Olynyk, P., Budde, W.L., and Eichelberger, J.W. “Method Detection Limit for Methods 624 and 625,” Unpublished report, May 14, 1980.

14. “EPA Method Study 30, Method 625, Base/Neutrals, Acids, and Pesticides,” EPA 600/4–84–053, National Technical Information Service, PB84–206572, Springfield, Virginia 22161, June 1984.


Table 1_Base/Neutral Extractables
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
Acenaphthene..................................... 34205 83-32-9
Acenaphthylene................................... 34200 208-96-8
Anthracene....................................... 34220 120-12-7
Aldrin........................................... 39330 309-00-2
Benzo(a)anthracene............................... 34526 56-55-3
Benzo(b)fluoranthene............................. 34230 205-99-2
Benzo(k)fluoranthene............................. 34242 207-08-9
Benzo(a)pyrene................................... 34247 50-32-8
Benzo(ghi)perylene............................... 34521 191-24-2
Benzyl butyl phthalate........................... 34292 85-68-7
ß-BHC....................................... 39338 319-85-7
d-BHC...................................... 34259 319-86-8
Bis(2-chloroethyl) ether......................... 34273 111-44-4
Bis(2-chloroethoxy)methane....................... 34278 111-91-1
Bis(2-ethylhexyl) phthalate...................... 39100 117-81-7
Bis(2-chloroisopropyl) ether a................... 34283 108-60-1
4-Bromophenyl phenyl ether a..................... 34636 101-55-3
Chlordane........................................ 39350 57-74-9
2-Chloronaphthalele.............................. 34581 91-58-7
4-Chlorophenyl phenyl ether...................... 34641 7005-72-3
Chrysene......................................... 34320 218-01-9
4,4[prime]-DDD................................... 39310 72-54-8
4,4[prime]-DDE................................... 39320 72-55-9
4,4[prime]-DDT................................... 39300 50-29-3
Dibenzo(a,h)anthracene........................... 34556 53-70-3
Di-n-butylphthalate.............................. 39110 84-74-2
1,3-Dichlorobenzene.............................. 34566 541-73-1
1,2-Dichlorobenzene.............................. 34536 95-50-1
1,4-Dichlorobenzene.............................. 34571 106-46-7
3,3[prime]-Dichlorobenzidine..................... 34631 91-94-1
Dieldrin......................................... 39380 60-57-1
Diethyl phthalate................................ 34336 84-66-2
Dimethyl phthalate............................... 34341 131-11-3
2,4-Dinitrotoluene............................... 34611 121-14-2
2,6-Dinitrotoluene............................... 34626 606-20-2
Di-n-octylphthalate.............................. 34596 117-84-0
Endosulfan sulfate............................... 34351 1031-07-8
Endrin aldehyde.................................. 34366 7421-93-4
Fluoranthene..................................... 34376 206-44-0
Fluorene......................................... 34381 86-73-7
Heptachlor....................................... 39410 76-44-8
Heptchlor epoxide................................ 39420 1024-57-3
Hexachlorobenzene................................ 39700 118-74-1
Hexachlorobutadiene.............................. 34391 87-68-3
Hexachloroethane................................. 34396 67-72-1
Indeno(1,2,3-cd)pyrene........................... 34403 193-39-5
Isophorone....................................... 34408 78-59-1
Naphthalene...................................... 34696 91-20-3
Nitrobenzene..................................... 34447 98-95-3
N-Nitrosodi-n-propylamine........................ 34428 621-64-7
PCB-1016......................................... 34671 12674-11-2
PCB-1221......................................... 39488 11104-28-2
PCB-1232......................................... 39492 11141-16-5
PCB-1242......................................... 39496 53469-21-9
PCB-1248......................................... 39500 12672-29-6
PCB-1254......................................... 39504 11097-69-1
PCB-1260......................................... 39508 11096-82-5
Phenanthrene..................................... 34461 85-01-8
Pyrene........................................... 34469 129-00-0
Toxaphene........................................ 39400 8001-35-2
1,2,4-Trichlorobenzene........................... 34551 120-82-1
------------------------------------------------------------------------
a The proper chemical name is 2,2[prime]-oxybis(1-chloropropane).




Table 2_Acid Extractables
------------------------------------------------------------------------
STORET
Parameter No. CAS No.
------------------------------------------------------------------------
4-Chloro-3-methylphenol.......................... 34452 59-50-7
2-Chlorophenol................................... 34586 95-57-8
2,4-Dichlorophenol............................... 34601 120-83-2
2,4-Dimethylphenol............................... 34606 105-67-9
2,4-Dinitrophenol................................ 34616 51-28-5
2-Methyl-4,6-dinitrophenol....................... 34657 534-52-1
2-Nitrophenol.................................... 34591 88-75-5
4-Nitrophenol.................................... 34646 100-02-7
Pentachlorophenol................................ 39032 87-86-5
Phenol........................................... 34694 108-95-2
2,4,6-Trichlorophenol............................ 34621 88-06-2
------------------------------------------------------------------------




Table 3_Additional Extractable Parameters a
------------------------------------------------------------------------
STORET
Parameter No. CAS No. Method
------------------------------------------------------------------------
Benzidine................................ 39120 92-87-5 605
ß-BHC............................... 39337 319-84-6 608
d-BHC.............................. 39340 58-89-8 608
Endosulfan I............................. 34361 959-98-8 608
Endosulfan II............................ 34356 33213-65-9 608
Endrin................................... 39390 72-20-8 608
Hexachlorocylopentadiene................. 34386 77-47-4 612
N-Nitrosodimethylamine................... 34438 62-75-9 607
N-Nitrosodiphenylamine................... 34433 86-30-6 607
------------------------------------------------------------------------
a See Section 1.2.




Table 4_Chromatographic Conditions, Method Detection Limits, and Characteristic Masses for Base/Neutral Extractables
--------------------------------------------------------------------------------------------------------------------------------------------------------
Method Characteristic masses
Retention detection -------------------------------------------------------------
Parameter time limit Electron impact Chemical ionization
(min) (µg/ -------------------------------------------------------------
L) Primary Secondary Secondary Methane Methane Methane
--------------------------------------------------------------------------------------------------------------------------------------------------------
1,3-Dichlorobenzene................................................ 7.4 1.9 146 148 113 146 148 150
1,4-Dichlorobenzene................................................ 7.8 4.4 146 148 113 146 148 150
Hexachloroethane................................................... 8.4 1.6 117 201 199 199 201 203
Bis(2-chloroethyl) ether a......................................... 8.4 5.7 93 63 95 63 107 109
1,2-Dichlorobenzene................................................ 8.4 1.9 146 148 113 146 148 150
Bis(2-chloroisopropyl) ether a..................................... 9.3 5.7 45 77 79 77 135 137
N-Nitrosodi-n-propylamine.......................................... ......... .......... 130 42 101 ........ ........ ........
Nitrobenzene....................................................... 11.1 1.9 77 123 65 124 152 164
Hexachlorobutadiene................................................ 11.4 0.9 225 223 227 223 225 227
1,2,4-Trichlorobenzene............................................. 11.6 1.9 180 182 145 181 183 209
Isophorone......................................................... 11.9 2.2 82 95 138 139 167 178
Naphthalene........................................................ 12.1 1.6 128 129 127 129 157 169
Bis(2-chloroethoxy) methane........................................ 12.2 5.3 93 95 123 65 107 137
Hexachlorocyclopentadiene a........................................ 13.9 .......... 237 235 272 235 237 239
2-Chloronaphthalene................................................ 15.9 1.9 162 164 127 163 191 203
Acenaphthylene..................................................... 17.4 3.5 152 151 153 152 153 181
Acenaphthene....................................................... 17.8 1.9 154 153 152 154 155 183
Dimethyl phthalate................................................. 18.3 1.6 163 194 164 151 163 164
2,6-Dinitrotoluene................................................. 18.7 1.9 165 89 121 183 211 223
Fluorene........................................................... 19.5 1.9 166 165 167 166 167 195
4-Chlorophenyl phenyl ether........................................ 19.5 4.2 204 206 141 ........ ........ ........
2,4-Dinitrotoluene................................................. 19.8 5.7 165 63 182 183 211 223
Diethyl phthalate.................................................. 20.1 1.9 149 177 150 177 223 251
N-Nitrosodiphenylamine b........................................... 20.5 1.9 169 168 167 169 170 198
Hexachlorobenzene.................................................. 21.0 1.9 284 142 249 284 286 288
ß-BHC b....................................................... 21.1 .......... 183 181 109 ........ ........ ........
4-Bromophenyl phenyl ether......................................... 21.2 1.9 248 250 141 249 251 277
d-BHC b...................................................... 22.4 .......... 183 181 109 ........ ........ ........
Phenanthrene....................................................... 22.8 5.4 178 179 176 178 179 207
Anthracene......................................................... 22.8 1.9 178 179 176 178 179 207
ß-BHC......................................................... 23.4 4.2 181 183 109 ........ ........ ........
Heptachlor......................................................... 23.4 1.9 100 272 274 ........ ........ ........
d-BHC........................................................ 23.7 3.1 183 109 181 ........ ........ ........
Aldrin............................................................. 24.0 1.9 66 263 220 ........ ........ ........
Dibutyl phthalate.................................................. 24.7 2.5 149 150 104 149 205 279
Heptachlor epoxide................................................. 25.6 2.2 353 355 351 ........ ........ ........
Endosulfan I b..................................................... 26.4 .......... 237 339 341 ........ ........ ........
Fluoranthene....................................................... 26.5 2.2 202 101 100 203 231 243
Dieldrin........................................................... 27.2 2.5 79 263 279 ........ ........ ........
4,4[prime]-DDE..................................................... 27.2 5.6 246 248 176 ........ ........ ........
Pyrene............................................................. 27.3 1.9 202 101 100 203 231 243
Endrin b........................................................... 27.9 .......... 81 263 82 ........ ........ ........
Endosulfan II b.................................................... 28.6 .......... 237 339 341 ........ ........ ........
4,4[prime]-DDD..................................................... 28.6 2.8 235 237 165 ........ ........ ........
Benzidine b........................................................ 28.8 44 184 92 185 185 213 225
4,4[prime]-DDT..................................................... 29.3 4.7 235 237 165 ........ ........ ........
Endosulfan sulfate................................................. 29.8 5.6 272 387 422 ........ ........ ........
Endrin aldehyde.................................................... ......... .......... 67 345 250 ........ ........ ........
Butyl benzyl phthalate............................................. 29.9 2.5 149 91 206 149 299 327
Bis(2-ethylhexyl) phthalate........................................ 30.6 2.5 149 167 279 149 ........ ........
Chrysene........................................................... 31.5 2.5 228 226 229 228 229 257
Benzo(a)anthracene................................................. 31.5 7.8 228 229 226 228 229 257
3,3[prime]-Dichlorobenzidine....................................... 32.2 16.5 252 254 126 ........ ........
Di-n-octyl phthalate............................................... 32.5 2.5 149
Benzo(b)fluoranthene............................................... 34.9 4.8 252 253 125 252 253 281
Benzo(k)fluoranthene............................................... 34.9 2.5 252 253 125 252 253 281
Benzo(a)pyrene..................................................... 36.4 2.5 252 253 125 252 253 281
Indeno(1,2,3-cd) pyrene............................................ 42.7 3.7 276 138 277 276 277 305
Dibenzo(a,h)anthracene............................................. 43.2 2.5 278 139 279 278 279 307
Benzo(ghi)perylene................................................. 45.1 4.1 276 138 277 276 277 305
N-Nitrosodimethylamine b........................................... ......... .......... 42 74 44 ........ ........ ........
Chlordane c........................................................ 19-30 .......... 373 375 377 ........ ........ ........
Toxaphene c........................................................ 25-34 .......... 159 231 233 ........ ........ ........
PCB 1016 c......................................................... 18-30 .......... 224 260 294 ........ ........ ........
PCB 1221 c......................................................... 15-30 30 190 224 260 ........ ........ ........
PCB 1232 c......................................................... 15-32 .......... 190 224 260 ........ ........ ........
PCB 1242 c......................................................... 15-32 .......... 224 260 294 ........ ........ ........ (continued)