United States                    Office of Water              EPA-821-B-98-016
Environmental Protection              Washington, DC 20460               July 1998
Agency	


 SEPA     Analytical Methods for the Determination

            of Pollutants in Pharmaceutical

            Manufacturing Industry Wastewater

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                                  Acknowledgments

This methods compendium was prepared under the direction of William A. Telliard of the Engineering and
Analysis Division within EPA's Office of Water. This document was prepared under EPA Contract No.
68-C3-0337 by DynCorp Environmental with the assistance of Interface, Inc.
                                       Disclaimer

This methods compendium has been reviewed by the Engineering and Analysis Division, U.S.
Environmental Protection Agency, and approved for publication. Mention of trade names or commercial
products does not constitute and endorsement or recommendation for use.

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                                                             Table of Contents
Introduction
                                                                              IV
Method 1666
Volatile Organic Compounds Specific to the Pharmaceutical Manufacturing Industry by Isotope
Dilution GC/MS
Revision A, July 1998	1

Method 1667
Formaldehyde, Isobutyraldehyde, and Furfural by Derivatization Followed by High
Performance Liquid Chromatography
Revision A, July 1998	53

Method 1671
Volatile Organic Compounds Specific to the Pharmaceutical
Manufacturing Industry by GC/FID
Revision A, July 1998	75
                                                                         July 1998

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                                                                              Introduction

       The U.S. Environmental Protection Agency (EPA) has promulgated effluent limitations guidelines and
standards at 40  CFR part 439 for the Pharmaceutical Manufacturing Industry to control the discharge of
pollutants into surface waters of the United States. This compendium of test procedures (methods) supports
the final rule.  These  methods and methods promulgated at 40 CFR part  136 are used for filing permit
applications and for compliance  monitoring under the National Pollutant Discharge Elimination System
(NPDES) program.

       This compendium includes only those methods unique to the Pharmaceutical Manufacturing
Industry.  Other methods allowed under the proposed rule have been promulgated at 40 CFR part 136.

       Questions concerning the  methods in this compendium should be directed to:

               W.A.  Telliard
               U.S. EPA
               Engineering and Analysis Division
               Office of Science and Technology
               401 M Street, SW
               Washington, DC 20460
July 1998                                      iv

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                                  Method 1666

Volatile Organic Compounds Specific to the Pharmaceutica
        Manufacturing Industry by Isotope Dilution GC/MS
                                      Revision A, July 1998

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                          Method 1666, Revision A
 Volatile Organic Compounds Specific to the Pharmaceutical Manufacturing
                         Industry by Isotope Dilution GC/MS


1.0    Scope and Application


1.1     This method is for surveying and monitoring under the Clean Water Act. It is used to determine
       certain volatile organic pollutants specific to the pharmaceutical manufacturing industry (PMI) that
       are amenable to purge-and-trap gas chromatography/mass spectrometry (GC/MS) or direct
       aqueous injection GC/MS.

1.2     The PMI analytes listed in Tables 1 and 2 may be determined in waters, soils, and municipal
       sludges by this method or the method referenced at the end of that table.

1.3     The detection limits of the method are usually dependent on the level of interferences rather than
       instrumental limitations. The minimum levels (MLs) in Tables 3 and 4 are the level that can be
       attained with no interferences present.

1.4     The GC/MS portions of this method are for use only by analysts experienced with GC/MS or
       under the close supervision of such qualified persons.  Laboratories unfamiliar with analysis of
       environmental samples by GC/MS should run the performance tests in Reference 1 before
       beginning.

1.5     This method is performance-based. The analyst is permitted to modify the method to overcome
       interferences or to lower the cost of measurements, provided that all performance criteria in this
       method are met. The requirements for establishing method equivalency are given in Section 9.1.2.

2.0    Summary  of Method

2.1     Purge-and-trap GC/MS.

       Stable, isotopically labeled analogs of the compounds  of interest are added to the sample and the
       sample is purged with an inert gas at 45 °C in a chamber designed for soil or water samples, as
       appropriate. In the purging process, the volatile compounds are transferred from the aqueous
       phase into the vapor phase, where they are passed into a sorbent column and trapped. After
       purging is completed, the trap is backflushed and heated rapidly to desorb the compounds into a
       gas chromatograph (GC).  The compounds are separated by the GC and detected by a mass
       spectrometer (MS) (References 2 and 3).

2.2     Direct aqueous injection.

       Certain volatile, water-soluble organic compounds do not purge well from water and are analyzed
       by direct aqueous injection.
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Method 1666, Revision A
       2.2.1   The percent solids content of the sample is determined.  If the solids content is known or
               determined to be less than 1%, stable, isotopically labeled analogs of the compounds of
               interest are added to a 5-mL sample. If the solids content of the sample is greater than 1%,
               5 mL of reagent water and the labeled compounds are added to a 5-g aliquot of sample.
               The mixture is sonicated in a centrifuge vial with little or no headspace for 5 minutes.
               During this period the native analytes and labeled analogs will equilibrate between the
               solid and aqueous  phases.  In some cases, additional sonication will be necessary to
               establish equilibrium. The resulting suspension is centrifuged and the supernatant liquid
               analyzed.

       2.2.2   One (iL or more of the aqueous solution (or supernate) is injected into the GC/MS. The
               compounds are separated by the GC and detected by the MS (References 2 and 3).  The
               labeled compounds serve to correct the variability of the analytical technique.

2.3    Identification of a pollutant (qualitative analysis) is performed by calibrating the GC/MS with
       authentic standards and storing a mass spectrum and retention time for each compound in a
       user-created library. A compound is identified when its retention time and mass spectrum agree
       with the library retention time and spectrum.

2.4    Quantitative analysis is performed in one of two ways by using extracted-ion current profile
       (EICP) areas.  (1) For those compounds listed in Table 1 and Table 2, and for other compounds for
       which labeled analogs are available, the GC/MS system is calibrated and the compound
       concentration is determined using an isotope dilution technique.  (2) For those compounds listed in
       Table  1 and Table  2, and for other compounds for which authentic  standards but no labeled
       compounds are available, the GC/MS system is calibrated and the compound concentration is
       determined using an internal standard technique.

2.5    The quality of the analysis is assured through reproducible calibration of the GC/MS system.

3.0    Definitions

There are no definitions unique to this method.

4.0    Interferences

4.1    Impurities in the purge gas, organic compounds outgassing from the plumbing upstream of the
       trap, and solvent vapors in the laboratory account for the majority of contamination problems
       encountered with this method.  The analytical system is demonstrated to be free from interferences
       under conditions of the analysis by analyzing reagent water blanks initially and with each sample
       batch (samples analyzed on the same 12-hour shift), as described in Section 9.5.

4.2    Samples can be contaminated by diffusion of volatile organic compounds (particularly methylene
       chloride) through the bottle seal during shipment and storage. A field blank prepared from reagent
       water and carried through the sampling and handling protocol may  serve as a check on such
       contamination.

July 1998                                       4

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                                                                           Method 1666, Revision A
4.3    Contamination by carryover can occur when high-level and low-level samples are analyzed
       sequentially.  To reduce carryover, the purging device (Figure 1 for samples containing less than
       1% solids; Figure 2 for samples containing 1% solids or greater) in purge-and-trap analysis or the
       syringe in direct aqueous injection analysis is cleaned or replaced with a clean purging device or
       syringe after each sample is analyzed. When an unusually concentrated sample is encountered, it is
       followed by analysis of a reagent water blank to check for carryover. Purging devices and syringes
       are cleaned by washing with soap solution, rinsing with tap and distilled water, and drying in an
       oven at 100-125 °C. The trap and other parts of the system are also  subject to contamination;
       therefore, frequent bakeout and purging of the entire system may be  required.

4.4    Interferences resulting from samples will vary considerably from source to source, depending on
       the diversity of the site being sampled.

5.0    Safety

5.1    The toxicity or carcinogenicity of each compound or reagent used in this method has not been
       precisely determined; however, each chemical compound should be treated as a potential health
       hazard. Exposure to these compounds should be reduced to the lowest possible level.  The
       laboratory is responsible for maintaining a current awareness file of OSF£A regulations regarding
       the safe handling of the chemicals specified in this method.  A reference file of material safety data
       sheets  should also be made available to all personnel involved in these analyses.  Additional
       information on laboratory safety can be found in References 5 through 7.

6.0    Equipment and  Supplies

       Disclaimer: The mention of trade names or commercial products in this Method is for
       illustrative purposes only and does not constitute endorsement or recommendation for use by the
       Environmental Protection Agency.  Equivalent performance may be achievable using apparatus,
       materials, or cleaning procedures other than those suggested here.  The laboratory is
       responsible for demonstrating equivalent performance.

6.1    Sample bottles and septa.

       6.1.1   Bottle—25- to 40-mL with screw-cap (Pierce 13075, or equivalent). Detergent wash,
               rinse  with tap and distilled water,  and dry at > 105 °C for a minimum of 1 hour before use.

       6.1.2   Septum-Polytetrafluoroethylene (PTFE)-faced silicone (Pierce 12722, or equivalent),
               cleaned as above and baked at 100-200 °C for a minimum of 1 hour.

6.2    Purge-and-trap device-Consists of purging device, trap, and desorber.

       6.2.1   Purging devices for water and soil samples.

               6.2.1.1 Purging device for water samples-Designed to accept 5-mL samples with water
                      column at least 3 cm deep. The volume of the gaseous headspace between the

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Method 1666, Revision A
                      water and trap shall be less than 15 mL. The purge gas shall be introduced less
                      than 5 mm from the base of the water column and shall pass through the water as
                      bubbles with a diameter less than 3 mm. The purging device shown in Figure 1
                      meets these criteria.

               6.2.1.2 Purging device for solid samples-Designed to accept 5 g of solids plus 5 mL of
                      water. The volume of the gaseous head space between the water and trap shall be
                      less than 25 mL. The purge gas shall be introduced less than 5 mm from the base
                      of the sample and shall pass through the water as bubbles with a diameter less
                      than 3 mm.  The purging device shall be capable of being controlled at a
                      temperature of 45±2  °C while the sample is being purged. The purging device
                      shown in Figure 2 meets these criteria.

       6.2.2   Trap-25-30 cm long  x 2.5 mm i.d. minimum, containing the following:

               6.2.2.1 Methyl silicone packing-l±0.2 cm, 3% OV-1 on 60/80 mesh Chromosorb W, or
                      equivalent.

               6.2.2.2 Porous polymer-15± 1.0 cm, Tenax GC (2,6-diphenylene oxide polymer), 60/80
                      mesh, chromatographic grade, or equivalent.

               6.2.2.3 Silica gel-8± 1.0 cm, Davison Chemical, 35/60 mesh, grade 15, or equivalent. The
                      trap shown in Figure  3 meets these specifications.

       6.2.3   Desorber-Shall heat the trap to 175±5 °C in 45 seconds or less.  The polymer section of
               the trap shall not exceed a temperature of 180°C and the remaining sections shall not
               exceed 220 °C during desorb, and no portion of the trap shall exceed 225 °C during
               bakeout.  The desorber shown in Figure 3 meets these  specifications.

       6.2.4   The purge-and-trap device may be a separate unit or coupled to a GC, as shown in Figures
               4 and  5.

6.3    Gas chromatograph-Shall be linearly temperature programmable with initial and final holds,  and
       shall produce results that meet the calibration (Section 10), quality assurance (Section 9), and
       performance tests (Section 15) of this method.

       6.3.1   Column for purge-and-trap analyses-60 m long x 0.32 mm i.d., fused-silica microbore
               column coated with 1.5 (im of phenylmethyl polysiloxane (Restek RTX-Volatiles, or
               equivalent).

       6.3.2   Column for direct aqueous injection analyses-30 m long x 0.32 mm i.d. fused-silica
               microbore column coated with 1.5 (im of 95% dimethyl- 5%  diphenyl polysiloxane
               specially passivated for chromatography of amines (Restek RTX-5 Amine, or equivalent).

       6.3.3   GC operating conditions.

July 1998                                       6

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                                                                            Method 1666, Revision A
               6.3.3.1 Purge-and-trap-4 minutes at 0 ° C, 8 ° C per minute to 170 ° C. Helium carrier gas
                      at 1.5 mL per minute.

               6.3.3.2 Direct aqueous injection-4 minutes at 40 °C, 8 °C per minute to 100 °C, then 25 °C
                      to 220°C with a 3-minute hold at 220°C.  Helium carrier gas at 1.5 mL per
                      minute. A pre-column split may be used to achieve acceptable peak shape.

6.4    Mass spectrometer-70 electron volt (eV) electron-impact ionization;  shall repetitively scan from 20
       to 250 Dalton every 2 to 3 seconds, and produce a unit resolution (valleys between m/z 174 to 176
       less than 10% of the height of the m/z 175 peak), background-corrected mass spectrum from 50 ng
       4-bromofluorobenzene (BFB) injected into the GC.  The BFB spectrum shall meet the
       mass-intensity criteria in Table 5. All portions of the GC column, transfer lines, and separator that
       connect the GC column to the ion source shall remain at or above the column temperature during
       analysis to preclude condensation of less volatile compounds.

6.5    Data system-Shall collect and record MS data, store mass-intensity data in spectral libraries,
       process GC/MS data and generate reports, and calculate and record  response factors.

       6.5.1   Data acquisition-Mass spectra shall be collected continuously throughout the analysis and
               stored on a mass-storage device.

       6.5.2   Mass spectral libraries-User-created libraries containing mass spectra obtained from
               analysis of authentic standards shall be employed to reverse search GC/MS runs for the
               compounds of interest (Section 10.2).

       6.5.3   Data processing-The data system shall be used to search, locate, identify, and quantify the
               compounds of interest in each GC/MS analysis. Software routines shall be employed to
               compute retention times and EICP areas. Displays of spectra, mass chromatograms, and
               library comparisons are required to verify results.

       6.5.4   Response factors and multipoint calibrations-The data system shall be used to record and
               maintain lists of response factors (response ratios for isotope dilution) and generate
               multi-point calibration curves (Section 10.4).  Computations of relative standard deviation
               (coefficient of variation) are useful for testing calibration linearity.  Statistics on initial and
               ongoing performance shall be maintained (Sections 9 and 10).

6.6    Syringes-5-mL glass hypodermic, with Luer-lok tips.

6.7    Micro syringes-10-, 25-, and 100-(iL.

6.8    Syringe valves-2-way, with Luer ends (PTFE).

6.9    Syringe-5 -mL, gas-tight, with shut-off valve.

6.10   Bottles-15-mL, screw-cap with PTFE liner.

                                                7                                        July 1998

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Method 1666, Revision A
6.11   Balances.

       6.11.1  Analytical, capable of weighing 0.1 mg.

       6.11.2  Top-loading, capable of weighing 10 mg.

6.12   Equipment for determining percent moisture.

       6.12.1  Oven, capable of temperature control at 110±5 °C.

       6.12.2  Desiccator.

       6.12.3  Beakers-50-to 100-mL.

6.13   Centrifuge apparatus.

       6.13.1  Centrifuge capable of rotating 10-mL centrifuge tubes at 5000 rpm.

       6.13.2  Centrifuge tubes, 10-mL, with screw-caps to fit centrifuge.

6.14   Sonication apparatus capable of sonicating 10 mL centrifuge tubes and thoroughly agitating
       contents.

7.0   Reagents and Standards

7.1    Reagent water-Water in which the compounds of interest and interfering compounds are not
       detected by this method. It may be generated by any of the following methods.

       7.1.1    Activated carbon-Pass tap water through a carbon bed (Calgon Filtrasorb-300, or
               equivalent).

       7.1.2    Water purifier-Pass tap water through a purifier (Millipore Super Q, or equivalent).

       7.1.3    Boil and purge-Heat tap water to 90-100 °C and bubble contaminant-free inert gas
               through it for approximately 1 hour. While still hot, transfer the  water to screw-cap
               bottles and seal with a PTFE-lined cap.

 7.2   Sodium thiosulfate-ACS granular.

 7.3   Methanol-Pesticide-quality or equivalent.

 7.4   Standard solutions-Purchased as solutions or mixtures with certification to their purity,
       concentration, and authenticity, or prepared from materials of known purity and composition. If
       compound purity is 96% or greater, the weight may be used without correction to calculate the
       concentration of the standard.

July 1998                                       8

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                                                                            Method 1666, Revision A
 7.5    Preparation of stock solutions for purge-and-trap analysis.

       7.5.1   Place approximately 9.5 mL of methanol in a 10-mL ground-glass-stoppered volumetric
               flask. Allow the flask to stand unstoppered for approximately 10 minutes or until all
               methanol-wetted surfaces have dried.  In each case, weigh the stoppered flask, add the
               compound, restopper, then immediately reweigh to prevent evaporation losses from
               affecting the measurement.

       7.5.2   Using a 100-(iL syringe, permit two drops of liquid to fall into the methanol without
               contacting the neck of the flask.  Alternatively, inject a known volume of the compound
               into the methanol in the flask using a microsyringe.

       7.5.3   Fill the flask to volume, stopper, then mix by inverting several times.  Calculate the
               concentration in milligrams per milliliter (mg/mL; equivalent to micrograms per microliter
               [|ig/(iL]) from the weight gain.

       7.5.4   Transfer the stock solution to a PTFE-sealed screw-cap bottle.  Store, with minimal
               headspace, in the dark at -20 to -10 °C.

       7.5.5   Replace standards after one month, or sooner if comparison with check standards indicate
               a change in concentration.  Quality control check standards that can be used to determine
               the accuracy of calibration standards may  be available from the National Institute of
               Standards  and Technology, Gaithersburg,  Maryland.

7.6    Preparation of stock solutions for direct aqueous injection analysis.

       7.6.1   Place approximately 9.0 mL of reagent water in a 10-mL ground-glass-stoppered
               volumetric flask. Allow the flask to stand unstoppered for approximately 10 minutes or
               until all wetted surfaces have dried. In each case, weigh the stoppered flask, add the
               compound, restopper, then immediately reweigh to prevent evaporation losses from
               affecting the measurement.

       7.6.2   Using a microsyringe, add sufficient liquid (about 100 mg) so that the final  solution will
               have a concentration of about 10 mg/mL.

       7.6.3   Fill the flask to volume, stopper, then mix by inverting several times.  Calculate the
               concentration in milligrams per milliliter (mg/mL; equivalent to micrograms per microliter
               [|ig/(iL]) from the weight gain.

       7.6.4   Transfer the stock solution to a PTFE-sealed screw-cap bottle.  Store, with minimal
               headspace, in the dark at approximately 4°C. Do not freeze.

       7.6.5   Replace standards after one month, or sooner if comparison with check standards indicate
               a change in concentration.  Quality control check standards that can be used to determine
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Method 1666, Revision A
               the accuracy of calibration standards may be available from the National Institute of
               Standards and Technology, Gaithersburg, Maryland.

7.7    Labeled compound spiking solutions.

       7.7.1   Purge-and-trap analysis-From stock standard solutions (Section 7.5), or from mixtures,
               prepare the spiking solution to contain a concentration of labeled compound such that a 5-
               to 10-(iL spike into each 5-mL sample, blank, or aqueous standard analyzed will result in
               a concentration of 50 (ig/L of each compound with a minimum level (ML) of 20 (ig/L or
               less, a concentration of 500 (ig/L for each compound with an ML of 100 or 200 (ig/L, and
               a concentration of 1 mg/L for each compound with an ML of 500 (ig/L (see Table 3).
               Include the internal standards (Section 10.4.2) in this solution, if appropriate, so that a
               concentration of 50 (ig/L in each sample, blank, or aqueous  standard will be produced.

       7.7.2   For direct aqueous injection-From stock standard solutions (Section 7.6), or from
               mixtures, prepare the spiking solution to contain a concentration such that a 50- to
               100-(iL spike into each  sample, blank, or aqueous standard analyzed will result in a
               concentration of 1 mg/mL of each labeled compound. Include the internal standard in this
               solution so that a concentration of 1 mg/mL will be produced.

7.8    Secondary standards-Using stock solutions, prepare a secondary standard in methanol or water, as
       appropriate, to contain each pollutant at a concentration of 1 mg/mL, or 2.5  mg/mL for compounds
       with higher MLs.

       7.8.1   Aqueous calibration standards-Using a microsyringe, add sufficient secondary standard
               (Section 7.8) to five reagent water aliquots to produce concentrations in the range of
               interest.

       7.8.2   Aqueous performance standard-An aqueous standard containing all pollutants, internal
               standards, labeled compounds,  and BFB is prepared daily, and analyzed each shift to
               demonstrate performance (Section 15). This standard shall contain concentrations of
               pollutants, labeled compounds, BFB, and internal standards, as appropriate, within a
               factor of 1-5 times the MLs of the pollutants listed in Table  3 or 4.  It may be one of the
               aqueous calibration standards described in Section 7.8.1.

       7.8.3   A methanolic standard containing all pollutants specific to this method (Table 1) and
               internal standards is prepared to demonstrate recovery of these compounds when syringe
               injection and purge-and-trap analyses are compared.  This standard shall contain either
               100 (ig/mL or 500 (ig/mL of the PMI analytes, and 100  (ig/mL of the internal standards
               (consistent with the amounts in the aqueous performance standard in Section 7.8.2).

       7.8.4   Other standards that may be needed are those for test of BFB performance (Section  10.1)
               and for collection of mass spectra for storage in spectral libraries (Section 10.1.1).
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                                                                           Method 1666, Revision A
8.0    Sample Collection, Preservation, and Storage

8.1     Grab samples are collected in glass containers having a total volume greater than 20 mL. For
       aqueous samples that pour freely, fill sample bottles so that no air bubbles pass through the sample
       as the bottle is filled and seal each bottle so that no air bubbles are entrapped. Maintain the
       hermetic seal on the sample bottle until time of analysis.

8.2     Samples are maintained at 0-4°C from the time of collection until analysis. If an aqueous sample
       contains residual chlorine, add sodium thiosulfate preservative (10 mg/40 mL) to the empty sample
       bottles just prior to shipment to the sample site. EPA Methods 330.4 and 330.5 may be used for
       measurement of residual chlorine (Reference 8).  If preservative has been added, shake the bottle
       vigorously for  1 minute immediately after filling.

8.3     For aqueous samples, experimental evidence indicates that some PMI analytes are susceptible to
       rapid biological degradation under certain environmental conditions. Refrigeration alone may not
       be adequate to preserve these compounds in wastewaters for more than seven days. For this
       reason, a separate sample should be collected, acidified, and analyzed when compounds susceptible
       to rapid biological degradation are to be determined.  Collect about 500 mL of sample in a clean
       container.  Adjust the pH of the sample to about 2 by adding hydrochloric acid (1:1) while stirring.
       Check pH with narrow range (1.4-2.8) pH paper. Fill a sample bottle as described in Section 8.1.
       If residual chlorine is present, add sodium thiosulfate to a separate sample bottle and fill as in
       Section 8.1.

8.4     All samples shall be analyzed within 14 days of collection.

9.0    Quality Assurance/Quality Control

9.1     Each laboratory that uses this method  is required to operate a formal quality assurance program
       (Reference 9).  The minimum requirements of this program consist of an initial demonstration of
       laboratory capability, analysis of samples spiked with labeled compounds to evaluate and
       document data quality, and analysis of standards and blanks as tests of continued performance.
       Laboratory performance is compared to established performance criteria to determine if the results
       of analyses meet the performance characteristics of the method.

       9.1.1  The analyst shall make an initial demonstration of the ability to generate acceptable
              accuracy and precision with this method. This ability is established as described in
               Section 9.2.

       9.1.2  In recognition of advances that are occurring in analytical technology, and to allow the
              analyst to overcome sample matrix interferences, the analyst is permitted certain options to
              improve separations or lower the costs of measurements.  These options include alternative
              concentration and cleanup procedures, and changes in columns and detectors. Alternative
              techniques, such as the substitution of spectroscopy or immunoassay, and changes that
              degrade method performance, are not allowed.  If an analytical technique other than the
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Method 1666, Revision A
               techniques specified in this method is used, that technique must have a specificity equal to
               or better than the specificity of the techniques in this method for the analytes of interest.

               9.1.2.1  Each time a modification is made to this method, the analyst is required to repeat
                       the procedure in Section 9.2.  If the detection limit of the method will be affected
                       by the change, the laboratory is required to demonstrate that the MDL (40 CFR
                       part 136, Appendix B) is lower than one-third the regulatory compliance level. If
                       calibration will be affected by the change, the analyst must recalibrate the
                       instrument per Section 10.

               9.1.2.2  The laboratory is required to maintain records of modifications made to this
                       method. These records include the information below, at a minimum.

                       9.1.2.2.1        The names, titles, addresses, and telephone numbers of the
                                      analyst(s) who performed the analyses and modification, and of
                                      the quality control officer who witnessed and will verify the
                                      analyses and modification.

                       9.1.2.2.2        A listing of pollutant(s) measured, by name and CAS Registry
                                      Number.

                       9.1.2.2.3        A narrative stating the reason(s) for the modification.

                       9.1.2.2.4        Results from all quality control (QC) tests comparing the
                                      modified method to this method, including:

                                      (a)     Calibration (Section  10)
                                      (b)     Calibration verification (Section 15)
                                      (c)     Initial precision and accuracy (Section 9.2)
                                      (d)     Labeled compound recovery (Section 9.3)
                                      (e)     Analysis of blanks (Section 9.5)
                                      (f)     Accuracy assessment (Section 9.4)

                       9.1.2.3 Data that will allow an independent reviewer to validate each
                              determination by tracing the instrument output (peak height, area,  or other
                              signal) to the final result, including:

                                      (a)     Sample numbers and other identifiers
                                      (b)     Analysis dates and times
                                      (c)     Analysis sequence/run chronology
                                      (d)     Injection logs
                                      (e)     Sample  weight or volume
                                      (f)     Sample volume prior to each cleanup step, if applicable
                                      (g)     Sample volume after each cleanup step, if applicable
July 1998                                        12

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                                                                             Method 1666, Revision A
                                      (h)     Final sample volume prior to injection (Sections 11 and
                                             12)
                                      (i)     Injection volume (Sections 11 and 12)
                                      (j)     Dilution data, differentiating between dilution of a sample
                                             or an extract (Section 16.4)
                                      (k)     Instrument and operating conditions
                                      (1)     Column (dimensions, liquid phase, solid support, film
                                             thickness, etc.)
                                      (m)    Operating conditions (temperature, temperature program,
                                             flow rates, etc.)
                                      (n)     Detector (type, operating condition, etc.)
                                      (o)     Chromatograms, printer tapes, and other recording of raw
                                             data
                                      (p)     Quantitation reports, data system outputs, and other data
                                             necessary to link raw data to the results reported.

        9.1.3   Analyses of blanks are required to demonstrate freedom from  contamination and that the
               compounds of interest and interfering compounds have not been carried over from a
               previous analysis (Section 4.3). The procedures and criteria for analysis of a blank are
               given in Section 9.5.

        9.1.4   The laboratory shall spike all samples with labeled compounds to monitor method
               performance. This test is described in Section 9.3. When results of these spikes indicate
               atypical method performance for samples, the samples are diluted to bring method
               performance within acceptable limits (Section 16).

        9.1.5   The laboratory shall, on an ongoing basis, demonstrate through the analysis of the aqueous
               performance standard (Section 7.8.2) that the analysis system is in control. This
               procedure is described in Sections 15.1 and 15.5.

        9.1.6   The laboratory shall maintain records to define the quality of data that is generated.
               Development of accuracy statements is described in Sections 9.4 and 15.5.2.

9.2     Initial precision and accuracy—To establish the ability to generate acceptable precision and
        accuracy, the analyst shall perform the following operations for compounds to be calibrated:

        9.2.1   Analyze two sets of four 5-mL aliquots (eight aliquots total) of the aqueous performance
               standard (Section 7.8.2) containing Table 1 PMI analytes by purge-and-trap.  Or, for
               Table 2 PMI analytes, analyze two sets of four aliquots (eight aliquots total) by direct
               aqueous injection.

        9.2.2   Using results of the first set of four analyses in Section 9.2.1, compute the average
               recovery (X) in percent of spike level and the standard deviation of the recovery (s) in
               percent of spike level, for each compound, by isotope dilution for pollutants with a labeled
                                                13                                        July 1998

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Method 1666, Revision A
               analog, and by internal standard for labeled compounds and pollutants with no labeled
               analog.

       9.2.3   For each compound, compare s and X with the corresponding limits for initial precision
               and accuracy found in Table 6.  If s and X for all compounds meet the acceptance criteria,
               system performance is acceptable and analysis of blanks and samples may begin.  If,
               however, any individual s exceeds the precision limit or any individual X falls outside the
               range for accuracy, system performance is unacceptable for that compound

Note:  The large number of compounds in Table 6 presents a substantial probability that one or more
       will fail one of the acceptance criteria when all compounds are analyzed.  To determine if the
       analytical system is out of control, or if the failure can be attributed to probability, proceed as
	follows.	

       9.2.4   Using the results of the second set of four analyses, compute s and X for only those
               compounds that failed the test of the first set of four analyses (Section 9.2.3). If these
               compounds now pass, system performance is acceptable for all compounds, and analysis
               of blanks and samples may begin.  If, however, any of the same compounds fail again, the
               analysis system is not performing properly for the compound(s) in question. In this event,
               correct the problem and repeat the entire test (Section 9.2.1).

 9.3    The laboratory shall spike all samples with labeled compounds to assess method performance on
       the sample matrix.

       9.3.1   Spike and analyze each sample according to the appropriate method in Section 11 or 12.

       9.3.2   Compute the percent recovery (P) of the labeled compounds using the internal standard
               method (Section 10.4.2).

       9.3.3   Compare the percent recovery for each compound with the corresponding labeled
               compound recovery limit in Table 6. If the recovery of any compound falls outside its
               warning limit, method performance is unacceptable for that compound in that sample.
               Therefore, the sample matrix is complex and the sample is to be diluted and reanalyzed,
               per Section 16.

 9.4    As part of the QA program for the laboratory, it is  suggested but not required that method
       accuracy for wastewater samples be assessed and records maintained. After the analysis of five
       wastewater samples for which the labeled compounds pass the tests in Section 9.3.3, compute the
       average percent recovery (P) and the standard deviation of the percent recovery (sp) for the labeled
       compounds only.  Express the accuracy assessment as a percent recovery interval from P - 2sp to P
       + 2sp. For example, if P = 90% and sp = 10%, the accuracy interval is expressed as 70-110%.
       Update the accuracy assessment for each compound on a regular basis (e.g., after each five to ten
       new accuracy measurements).
July 1998                                       14

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                                                                            Method 1666, Revision A
 9.5    Blanks-Reagent water blanks are analyzed to demonstrate freedom from carryover and
       contamination (Section 4).

       9.5.1   The level at which the purge-and-trap system will carry greater than the ML of a pollutant
               of interest (Table 1) into a succeeding blank shall be determined by analyzing successively
               larger concentrations of these compounds. When a sample contains this concentration or
               more, a blank shall be analyzed immediately following this sample to demonstrate no
               carryover at the ML.

       9.5.2   With each sample batch (samples analyzed on the same 12-hour shift), a blank shall be
               analyzed immediately after analysis of the aqueous performance standard (Section 15.1) to
               demonstrate freedom from contamination. If any of the compounds of interest (Table 1 or
               2) or any potentially interfering compound is found in a blank at greater than the ML
               (assuming a response factor of 1 relative to the nearest-eluted internal standard for
               compounds not listed in Tables 1 and 2), analysis of samples is halted until the source of
               contamination is eliminated and a blank shows no evidence of contamination at this level.
               All results must be associated with an uncontaminated method blank.

9.6    The specifications contained in this method can be met if the apparatus used is calibrated properly,
       then maintained in a calibrated state.  The standards used for calibration (Section 7), calibration
       verification (Section 15.5), and initial (Section 9.2) and ongoing (Section 15.5) precision and
       accuracy should be identical, so that the most precise results will be obtained. The GC/MS
       instrument in particular will provide the most reproducible results if dedicated to the settings and
       conditions required for the analyses of volatiles by this method.

9.7    Depending on specific program requirements, field replicates may be collected to determine the
       precision of the sampling technique, and spiked samples may be required to determine the accuracy
       of the analysis when the internal-standard method is used.

10.0  Calibration and Standardization

Calibration of the  GC/MS system is performed by direct aqueous injection (Section 10.3) or purging the
compounds of interest and their labeled analogs from reagent water at the temperature to be used for
analysis of samples (Section 10.2).

10.1   Assemble the GC/MS apparatus and establish the operating conditions to be used for sample
       analysis (Section 6.3.3.1 or Section 6.3.3.2).  By injecting standards into the GC, demonstrate that
       the analytical system meets the minimum levels in Tables 3  or 4 for the compounds for which
       calibration is to be performed, and the mass-intensity criteria in Table 5 for 50 ng BFB.

        10.1.1  Mass-spectral libraries-Detection and identification of the compounds of interest are
               dependent upon the spectra stored in user-created libraries.

               10.1.1.1        For the compounds in Tables 1 and 2, and other compounds for which the
                              GC/MS is to be calibrated, obtain a mass spectrum of each pollutant and

                                                15                                       July 1998

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Method 1666, Revision A
                              labeled compound and each internal standard by analyzing an authentic
                              standard either singly or as part of a mixture in which there is no
                              interference between closely eluted components. Examine the spectrum to
                              determine that only a single compound is present.  Fragments not
                              attributable to the compound under study indicate the presence of an
                              interfering compound. Adjust the analytical conditions and scan rate (for
                              this test only) to produce an undistorted spectrum at the GC peak
                              maximum.  An undistorted spectrum will usually be obtained if five
                              complete spectra are collected across the upper half of the GC peak.
                              Software algorithms designed to "enhance" the spectrum may eliminate
                              distortion, but may also eliminate authentic m/z's or introduce other
                              distortion.

               10.1.1.2        The authentic reference spectrum is obtained under BFB tuning conditions
                              (Section 10.1 and Table 5) to normalize it to spectra from other
                              instruments.

               10.1.1.3        The spectrum is edited by saving the five most intense mass-spectral
                              peaks and all other mass-spectral peaks greater than 10%  of the base
                              peak. The spectrum may be further edited to remove common interfering
                              masses. If five mass-spectral peaks cannot be obtained under the scan
                              conditions  given in Section 6.4, the mass spectrometer may be scanned to
                              an m/z  lower than 20 to gain additional spectral information.  The
                              spectrum obtained is stored for reverse search and for compound
                              confirmation.

        10.2    Assemble the GC/MS apparatus and establish operating conditions given in Section
               6.3.3.1.  By injecting standards into the GC, demonstrate that the analytical system meets
               the minimum levels in Table 3 for the compounds for which calibration is to be performed,
               and the mass-intensity criteria in Table 5 for 50 ng BFB.

               10.2.1  Assemble the purge-and-trap device.  Pack the trap as shown in Figure 3 and
                      condition overnight at 170-180°C by backflushing with  an inert gas at a flow rate
                      of 20-30 mL/min.  Condition traps daily for a minimum  of 10 minutes prior to
                      use.

                       10.2.1.1       Analyze the  aqueous performance standard (Section 7.8.2)
                                     according to the purge-and-trap procedure in Section 11.
                                     Compute the area at the primary m/z (Table 7) for each
                                     compound. Compare these areas to those obtained by injecting 1
                                     (iL of the methanolic standard (Section  7.5.1) to determine
                                     compound recovery.  The recovery shall be greater than 50% for
                                     the PMI analytes.  Maximum allowable recovery  for the PMI
                                     analytes found in Table 1 are shown in Table 8.  This recovery is
                                     demonstrated initially for each purge-and-trap GC/MS system.

July 1998                                       16

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                                                                            Method 1666, Revision A
                                     The test is repeated only if the purge-and-trap or GC/MS systems
                                     are modified in any way that might result in a change in recovery.

                      10.2.1.2       Demonstrate that a reliable calibration point can be established at
                                     the ML for each compound (Table 2). If the MLs cannot be met,
                                     adjust the analytical system until this performance is achieved.

10.3   Assemble the GC/MS system for direct aqueous injection and establish the operating conditions to
       be used for sample analysis (Section 6.3.3.2). By injecting standards into the GC, demonstrate that
       the analytical system meets the minimum levels in Table 4 for the compounds for which calibration
       is to be performed, and the mass-intensity criteria in Table 5 for 50 ng BFB.

       Demonstrate that 100 ng o-xylene (or o-xylene-d10) produces an area at m/z  106 (or 116)
       approximately one-tenth that required to exceed the  linear range of the system. The exact value
       must be determined by experience for each instrument. It is used to match the calibration range of
       the instrument to the analytical range and detection limits required.

10.4   The following calibration steps are to be performed for both the purge-and-trap PMI analytes
       found in Table 1 and the direct aqueous injection PMI analytes found in Table 2, as appropriate.

       10.4.1  Calibration by isotope dilution-The isotope  dilution approach is used for the PMI analytes
               when appropriate labeled compounds are available and when interferences do not preclude
               the analysis. If labeled compounds are not available, or interferences are present, the
               internal standard method (Section 10.4.2) is used.  A calibration curve encompassing the
               concentration range of interest is prepared for each compound determined. The relative
               response (RR) vs. concentration in micrograms per liter is plotted or computed using a
               linear regression.  An example of a calibration curve for o-xylene using o-xylene-d10 is
               given in Figure  6. Also shown are the ±10% error limits (dotted lines). Relative response
               is determined according to the  procedures described below. A minimum of five data points
               are required for calibration.

               10.4.1.1        The relative response (RR) of pollutant to labeled compound is determined
                              from isotope ratio values calculated from acquired data.  Three isotope
                              ratios are used in this process:

                              Rx =   The isotope ratio measured in the pure pollutant (Figure  7A)

                              Ry =   The isotope ratio of pure labeled compound (Figure IB)

                              Rm =   The isotope ratio measured in the analytical mixture  of the
                                     pollutant and labeled compounds (Figure  7C)

                              The correct way to calculate RR is:
                                                17                                        July 1998

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Method 1666, Revision A
                                       RR =
                              If Rm is not between 2Ry and 0.5RX, the method does not apply and the
                              sample is analyzed by the internal standard method (Section 10.4.2).

               10.4.1.2       In most cases, the retention times of the pollutant and labeled compound
                              are similar, and isotope ratios (R's) can be calculated from the EICP
                              areas, where:
                                              (area at mj ^)
                                         R =
                              If either of the areas is zero, it is assigned a value of 1 in the calculations;
                              that is, if area of m/z = 50721, and area of m2/z = 0, then R = 50721/1 =
                              50720.

                              The data from these analyses are reported to three significant figures (see
                              Section 14.6). In order to prevent rounding errors from affecting the
                              values to be reported, all calculations performed prior to the final
                              determination of concentrations should be carried out using at least four
                              significant figures.  Therefore, the calculation of R above is rounded to
                              four significant figures.

                              The m/z's are always selected such that Rx > Ry. When there is a
                              difference in retention times (RT) between the pollutant and labeled
                              compounds, special precautions are required to determine the isotope
                              ratios.

                              Rx, Ry, and Rm are defined as follows:

                                           [area  mj ^ (at
                                     R  =
                                     R  =
                                           [area mj ^ (at RTJ]
               10.4.1.3       An example of the above calculations can be taken from the data plotted
                              in Figure 7 for o-xylene and o-xylene-d10. For these data:

July 1998                                        18

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                                                                     Method 1666, Revision A
                            R  =         =  16890Q
                             R  = —— =  0.00001640
                              J    60960

                            R  = 96868 =
                                  82508
       10.4.1.4       The RR for the above data is then calculated using the equation given in
                      Section 10.4.1.1.  For the example, rounded to four significant figures,
                      RR = 1.174. Not all labeled compounds elute before their pollutant
                      analogs.

                      To calibrate the analytical system by isotope dilution, analyze an aliquot
                      of each of the aqueous calibration standards (Section 7.8.1) spiked with
                      an appropriate constant amount of the labeled compound spiking solution
                      (Section 7.7), using the appropriate procedure in Section 10. Compute
                      the RR at each concentration.

       10.4.1.5       Linearity-If the ratio of relative response to concentration for any
                      compound is constant (less than 20% coefficient of variation) over the
                      five-point calibration range, an averaged relative response/concentration
                      ratio may be used for that compound; otherwise, the complete calibration
                      curve for that compound shall be used over the five-point calibration
                      range.

10.4.2  Calibration by internal standard-Used when criteria for isotope dilution (Section 10.4.1)
       cannot be met.  The method is applied to pollutants having no labeled analog and to the
       labeled compounds. The internal standards used for volatiles analyses are
       bromochloromethane, 1,4-difluorobenzene, chlorobenzene-d5, and tetrahydrofuran-d8.
       Concentrations of the labeled compounds and pollutants without labeled analogs are
       computed relative to the nearest eluting internal standard, as shown in Tables 3 and 4.

       10.4.2.1       Response factors-Calibration requires the determination  of response
                      factors (RF) which are defined by the following equation:
                                        (A  x C.)
                                 RF = -^	?-
                                        (A x Q

                      Where:

                      As      =      The EICP area at the characteristic m/zfor the
                                     compound in the daily standard

                                        19                                        July 1998

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Method 1666, Revision A
                              Ais     =      The EICP area at the characteristic m/zfor the internal
                                             standard
                              Cis     =      The concentration (pg/L) of the internal standard
                              Cs     =      The concentration of the pollutant in the daily standard

               10.4.2.2        The RF is determined at 10, 20, 50, 100, and 200 (ig/L for the pollutants
                              (optionally at 5 times or more these concentrations for highly
                              water-soluble pollutants; see Section 7.8), in a way analogous to that for
                              calibration by isotope dilution (Section 10.4.1).  To produce a calibration
                              curve, AS*C1S/A1S is plotted against concentration (Cs) for each compound.

               10.4.2.3        Linearity-If the relative standard deviation of the RFs for any compound
                              is constant (less than 35%) over the five-point calibration range, an
                              averaged RF may be used for that compound; otherwise, the complete
                              calibration curve for that compound shall be used over the five-point
                              range.

        10.4.3  Combined calibration-By  adding the  isotopically labeled compounds and internal standards
               (Section 7.7) to the aqueous calibration standards (Section 7.8.1), a single set of analyses
               can be used to produce calibration curves for the isotope-dilution and internal-standard
               methods. These curves are verified each shift (Section 15.5) by analyzing the aqueous
               performance standard (Section 7.8.2). Recalibration is required only if calibration and
               ongoing performance (Section 15.5) criteria cannot be met.

11.0   Purge, Trap, and  GC/MS Analysis

Samples containing less than 1% solids are analyzed directly as aqueous samples (Section 11.4). Samples
containing 1% solids or greater are analyzed as solid samples utilizing one of two methods, depending on
the levels of pollutants in the sample. Samples containing 1% solids or greater and low to  moderate levels
of pollutants are analyzed by purging a known weight of sample added to 5 mL of reagent water (Section
11.5).  Samples containing 1% solids or greater and high levels of pollutants are extracted with methanol,
and an aliquot of the methanol extract is added to reagent water and purged (Section 11.6).

11.1    Determination of percent solids.

        11.1.1  Weigh 5 to 10 g of sample into a tared beaker.

        11.1.2  Dry overnight (12 hours minimum) at 110°C (±5°C), and cool in a desiccator.

        11.1.3  Determine percent solids as follows:

                                ,,    ,.,   might  of sample dry   . _ _
                                % solids = —2	+	£	^x 100
                                          might  of sample wet

11.2    Remove standards and samples from cold storage and bring to 20-25 °C.

July 1998                                       20

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                                                                           Method 1666, Revision A
11.3    Adjust the purge gas flow rate to 40 mL/min (±4 mL/min).

11.4    Samples containing less than 1% solids.

       11.4.1  Mix the sample by shaking vigorously.  Remove the plunger from a 5-mL syringe and
               attach a closed syringe valve. Open the sample bottle and carefully pour the sample into
               the syringe barrel until it overflows.  Replace the plunger and compress the sample. Open
               the syringe valve and vent any residual air while adjusting the sample volume to 5±0.1 mL.
               Because this process of taking an aliquot destroys the validity of the sample for future
               analysis, fill a second syringe at this time to protect against possible loss of data.

       11.4.2  Add an appropriate amount of the labeled compound spiking solution (Section 7.7.1)
               through the valve bore, then close the valve.

       11.4.3  Attach the syringe valve assembly to the syringe valve on the purging device. Open both
               syringe valves and inject the sample into the purging chamber. Purge the sample per
               Section 11.7.

11.5    Samples containing 1% solids or greater and low to moderate levels of pollutants.

       11.5.1  Mix the sample thoroughly using a clean spatula and remove rocks, twigs, sticks, and
               other foreign matter.

       11.5.2  Weigh 5±1 g of sample into a purging vessel (Figure 2). Record the weight to three
               significant figures.

       11.5.3  Add 5±0.1 mL of reagent water to the vessel.

       11.5.4  Using a metal spatula, break up any lumps of sample to disperse the sample in the water.

       11.5.5  Add an appropriate amount of the labeled compound spiking solution (Section 7.7.1) to the
               sample in the purge vessel. Place a cap on the purging vessel and shake vigorously to
               further disperse the sample. Attach the purge vessel to the purging device, and purge the
               sample per Section 11.7.

11.6    Samples containing 1% solids or greater and high levels of pollutants, or samples requiring dilution
       by a factor of more than 100 (see Section 16).

       11.6.1  Mix the sample thoroughly using a clean spatula and remove rocks, sticks, twigs, and
               other foreign matter.

       11.6.2  Weigh 5±1 g of sample into a calibrated 15- to 25-mL centrifuge tube.  Record the weight
               of the sample to three significant figures.
                                               21                                       July 1998

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Method 1666, Revision A
        11.6.3  Add 10 mL of methanol to the centrifuge tube. Cap the tube and shake it vigorously for
               15 to 20 seconds to disperse the sample in the methanol. Allow the sample to settle in the
               tube. If necessary, centrifuge the sample to settle suspended particles.

        11.6.4  Remove approximately 0.1% of the volume of the supernatant methanol using a 15- to
               25-(iL syringe. This volume will be in the range of 10-15 (iL.

        11.6.5  Add this volume of the methanol extract to 5 mL reagent water in a 5-mL syringe, and
               analyze per Section 10.4.1.

        11.6.6  For further dilutions, dilute 1 mL of the supernatant methanol (Section 10.6.4) to 10 mL,
               100 mL, 1000 mL, etc., in reagent water. Remove a volume of this methanol
               extract/reagent water mixture equivalent to the volume in Section 10.6.4, add it to 5 mL
               reagent water in a 5-mL syringe, and analyze per Section 11.4.

11.7    Purge the sample for  11±0.1 minute at 45±2°C.

11.8    After the 11-minute purge time, attach the trap to the chromatograph and set the purge-and-trap
        apparatus to the desorb mode (Figure 5). Desorb the trapped compounds into the GC column by
        heating the trap to 170-180°C  while backflushing with carrier gas at 20-60 mL/min for 4 minutes.
        Start MS data acquisition upon start of the desorb cycle, and start the GC column temperature
        program 3 minutes later. Section 6.3.3.1 provides the recommended operating conditions for the
        gas chromatograph. Table 3 provides the retention times and minimum levels that can be achieved
        under these conditions.  An example of the separations achieved by the column listed is shown in
        Figure 8.  Other columns may  be used provided the requirements in  Section 9 are met.

11.9    After desorbing the sample for 4 minutes, recondition the trap by purging with purge gas while
        maintaining the trap temperature at 170-180°C.  After approximately 7 minutes, turn off the trap
        heater and stop the gas flow through the trap.  When cool, the trap is ready for the next sample.

11.10   While analysis of the  desorbed compounds proceeds, remove and clean the purge device.  Rinse
        with tap water, clean  with detergent and water, rinse with tap and distilled water, and dry for a
        minimum of 1 hour in an oven at a temperature greater than 15 0 ° C.

12.0   Direct Aqueous Injection and GC/MS Analysis

Samples containing less than  1% solids are analyzed directly as aqueous samples (Section 12.3).  Samples
containing 1% solids or greater are analyzed after equilibration with reagent  water containing labeled PMI
analytes and internal standards (Section 12.4).

12.1    Determine percent solids as in  Section 11.1.

12.2    Remove standards and samples from cold storage and bring to 20-25 °C.

12.3    Samples containing less than 1% solids.

July 1998                                       22

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                                                                           Method 1666, Revision A
        12.3.1  Allow solids to settle and remove 5 mL of sample.

        12.3.2  Add an appropriate amount of the labeled compound spiking solution (Section 7.7.2).

        12.3.3  Inject 1 mL or more directly into the GC injection port. The temperature of the injection
               block should be great enough to immediately vaporize the entire sample. An example of
               the separations achieved by the column listed is shown in Figure 9.

12.4    Samples containing 1% solids or greater.

        12.4.1  Mix the sample thoroughly using a clean spatula and remove rocks, twigs, sticks and other
               foreign matter.

        12.4.2  Add 5±1 g of sample to a 10-mL centrifuge tube. Using a clean metal spatula, break up
               any lumps of sample. Record the  sample weight to three significant figures.

        12.4.3  Add an appropriate amount of the labeled compound spiking solution (Section 7.7.2) to the
               sample in the centrifuge tube.

        12 A A  Add a measured quantity, Y, (to the nearest 0.1 mL) of reagent water to the tube so as to
               minimize headspace.

        12.4.5  Place a cap on the centrifuge tube  leaving little or no headspace. Place the tube in the
               sonicator for a minimum of 5 minutes, turning occasionally.  For most samples this should
               be sufficient time to distribute labeled and native analytes between the solid and aqueous
               phases and to establish equilibrium.  Some  sample matrices may require more sonication.

        12.4.6  On completion of sonication, centrifuge the sample and inject \\\L or more of supernate
               directly into the GC injection port.  The temperature of the injection block should be great
               enough to immediately vaporize the entire sample.

12.5    Liquid samples containing high solids concentrations, such as sludges or mud, may be weighed into
        a 10-mL centrifuge tube, have labeled compound spiking solution (Section 7.7.2) added, and be
        sonicated as in Section 12.4.5.  Centrifugation and injection are to be performed as in Section
        12.4.6.

13.0   Qualitative Determination

Identification is accomplished by comparison of data from analysis of a sample or blank with data stored in
the mass-spectral libraries.  For compounds for which the relative retention times and mass spectra are
known, identification is confirmed per Sections 13.1 and 13.2.

13.1    A labeled compound or pollutant having no labeled analog (Tables 1 and 2).
                                               23                                       July 1998

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Method 1666, Revision A
        13.1.1  The signals for all characteristic m/z's stored in the spectral library (Section 10.1.1) shall
               be present and shall maximize within the same two consecutive scans.

        13.1.2  Either (1) the background corrected EICP areas or (2) the corrected relative intensities of
               the mass-spectral peaks at the GC peak maximum shall agree within a factor of 2 (0.5-2
               times) for all m/z's stored in the library.

        13.1.3  The relative  retention time (RRT) shall be within ±10% of the RRT in the system
               performance standard (Section 15.1)

13.2    Pollutants having a labeled analog (Tables 1 and 2).

        13.2.1  The signals for all characteristic m/z's stored in the spectral library (Section 10.1.1) shall
               be present and shall maximize within the same two consecutive scans.

        13.2.2  Either (1) the background corrected EICP areas or (2) the corrected relative intensities of
               the mass-spectral peaks at the GC peak maximum shall agree within a factor of 2 for all
               m/z's stored  in the spectral library.

        13.2.3  The RRT for the pollutant relative to its labeled analog shall be within -2% to +1% of the
               RRT in the system performance standard (Section 15.1).

13.3    The m/z's present in the sample mass spectrum that are not present in the reference mass spectrum
        shall be accounted for by contaminant or background ions.  If the sample mass spectrum is
        contaminated, or if identification is ambiguous, an experienced spectrometrist (Section 1.4) is to
        determine the presence or absence of the compound.

14.0   Quantitative Determination

14.1    Isotope dilution-Because the pollutant and its labeled analog exhibit the same effects upon purging
        and desorption, or equilibration combined with gas chromatography, correction for recovery of the
        pollutant can be made by adding a known amount of a labeled compound to every sample prior to
        purging or equilibration. Relative response (RR) values for sample mixtures  are used in
        conjunction with the  calibration curves described in Section 10.4.1 to determine concentrations
        directly, so long as labeled compound spiking levels are constant. For the o-xylene example given
        in Figure 7 (Section  10.4.1.3), RR would be equal to 1.174. For this RR value, the o-xylene
        calibration curve given in Figure 6 indicates a concentration of 31.8 (ig/L.

14.2    Internal standard-For the compounds for which the system was calibrated (Table 1 and Table 2)
        according to Section 10.4.2, use the response factor determined during the calibration to calculate
        the concentration from the equation below, where the terms are as defined in  Section  10.4.2.1.
July 1998                                       24

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                                                                              Method 1666, Revision A
                                                    (As
                                    Concentration  = 	—
14.3   Samples containing >1% solids—The concentration of the pollutant in the solid phase of the
       sample is computed using the concentration of the pollutant detected in the aqueous solution, as
       follows:

       14.3.1  Samples containing low to moderate levels of pollutants (Section 11.5)

               r          .     ,-i
               Concentration in  solid
                                            sample weight  (kg)  x percent solids (g) x DF

               where:

               "percent solids" is from Section 11.1.3 or Section 12.1
               Y = volume of water in liters (L) from Section 12.4.4
               DF = dilution factor (as a decimal number), where necessary

        14.3.2  Methanol extracts (Section 11.6)

                                                Y (L) x  p  x  aqueous cone (Mg/-L)
               Concentration in  solid (^gl kg)  = 	:	:	
                                            sample weight  (kg)  x percent solids (g) x DF

               where:

               Y = volume of methanol in liters (L) from Section 11.6.3
               Fm is the fraction of supernatant removed from the centrifuge tube (e.g., 0.001, Section
               11.6.4), and the other terms are as defined in Section 14.3.1

        14.3.3  Where the aqueous concentration is in mg/L, the result will be in mg/kg.

14.4    Sample dilution-If the EICP area at the quantitation m/z exceeds the calibration range of the
        system, the sample  is diluted by  successive factors of 10 until the area is within the calibration
        range. If dilution of high-solids samples by greater than a factor of 100 is required for
        purge-and-trap analysis, then extract the sample with methanol, as described in Section 11.6.

14.5    Dilution of samples containing high concentrations of compounds not in Table 1 or Table 2-When
        any peak in the mass spectrum is saturated, dilute the sample per Section 14.4.

14.6    Report results for all pollutants and labeled compounds found in all standards, blanks, and samples
        to three significant figures.  For samples containing less than 1% solids, the units are micrograms
        or milligrams per liter (ng/L or mg/L); and for undiluted samples containing 1% solids or greater,
        units are micrograms or milligrams per kilogram ((ig/kg or mg/kg).
                                                25                                         July 1998

-------
Method 1666, Revision A
        14.6.1  Results for samples that have been diluted are reported at the least dilute level at which the
               area at the quantitation m/z is within the calibration range (Section 14.4), or at which no
               m/z in the spectrum is saturated (Section 14.5). For compounds having a labeled analog,
               results are reported at the least dilute level at which the area at the quantitation m/z is
               within the calibration range (Section 14.4) and the labeled compound recovery is within the
               normal range for the method (Section 16.2).

15.0   System Performance

15.1    At the beginning of each 12-hour shift during which analyses are performed, system calibration
        and performance shall be verified for the pollutants and labeled compounds (Table  1 or Table 2).
        For these tests, analysis of the aqueous performance standard (Section 7.8.2) shall be used to
        verify all performance criteria. Adjustment and/or recalibration (per Section 10) shall be
        performed until all performance criteria are met. Only after all performance criteria are met may
        blanks and samples be analyzed.

15.2    BFB spectrum validity-The criteria in Table 5 shall be met.

15.3    Retention times.

        15.3.1  Purge-and-trap analysis-The absolute retention times of the internal standards shall fall
               within ±30 seconds of the following-bromochloromethane, 954 seconds;
               1,4-difluorobenzene, 1052 seconds; chlorobenzene-d5, 1359 seconds.  The relative
               retention times of all pollutants and labeled compounds shall fall within 5% of the value
               given in Table 3.

        15.3.2  Direct aqueous injection analysis-The absolute retention time of tetrahydrofuran-ds shall be
               263±30 seconds. The relative retention times of all  pollutants and labeled compounds
               shall fall within 10% of the value given in Table 4.

15.4    GC resolution-The valley height between o-xylene and o-xylene-d10 (at m/z 106 and 116 plotted on
        the same graph) shall be less than 10% of the taller of the two peaks.

15.5    Calibration verification and ongoing precision and accuracy-Compute the concentration of each
        pollutant (Table 1 or Table 2) by isotope dilution (Section 10.4.1) for those compounds that have
        labeled analogs.  Compute the concentration of each pollutant that has no labeled analog by the
        internal standard method (Section 10.4.2). Compute the concentrations of the labeled compounds
        by the internal standard method. These concentrations are computed based on the calibration data
        determined in Section 10.

        15.5.1  For each pollutant and labeled compound, compare  the concentration with the
               corresponding limit for ongoing accuracy in Table 6. If all compounds meet the
               acceptance criteria, system performance is acceptable and analysis of blanks and samples
               may continue.  If any individual value falls outside the range given, system  performance is
               unacceptable for that compound.

July 1998                                       26

-------
                                                                           Method 1666, Revision A
Note:  The large number of compounds in Table 6 present a substantial probability that one or more
       will fail the acceptance criteria when all compounds are analyzed.  To determine if the analytical
       system is out of control, or if the failure may be attributed to probability, proceed as follows.

               15.5.1.1        Analyze a second aliquot of the aqueous performance standard (Section
                              7.8.2).

               15.5.1.2        Compute the concentration for only those compounds that failed the first
                              test (Section 15.5.1). If these compounds now pass, system performance
                              is acceptable for all compounds, and analyses of blanks and samples may
                              proceed. If, however, any of the compounds fail again, the measurement
                              system is not performing properly for these compounds. In this event,
                              locate and correct the problem or recalibrate the system (Section  10), and
                              repeat the entire test (Section 15.1) for all compounds.

       15.5.2  It is suggested but not required that results that pass the specification in Section 15.5.1.2
               be added to initial (Section 9.2) and previous ongoing data, that QC charts be updated to
               form a graphic representation of laboratory performance (Figure 8), and that a statement
               of accuracy be developed for each pollutant and labeled compound by calculating the
               average percent recovery (R) and the standard deviation of percent recovery (sr).  Express
               the accuracy as a recovery interval from R - 2sr to  R + 2sr.  For example, if R = 95% and
               sr = 5%, the accuracy is 85-105%.

16.0  Analysis of Complex Samples

16.1   Some samples may contain high levels (>1000 (ig/kg) of the compounds  of interest and of
       interfering compounds.  Some samples will foam excessively when purged. Others will overload
       the trap or the GC column.

16.2   When the recovery of any labeled compound is outside the range given in Table 6, dilute samples
       by a factor of 10 with reagent water and analyze this diluted sample. If the recovery remains
       outside of the range for this diluted sample, the aqueous performance standard shall be analyzed
       (Section 15.1) and calibration verified (Section 15.5).  If the recovery for the labeled compound in
       the aqueous performance standard is outside the range given in Table 6, the analytical system is
       out of control. In this case, the instrument shall be repaired, the performance specifications in
       Section 15 shall be met, and the analysis of the undiluted sample shall be repeated. If the recovery
       for the aqueous performance standard is within the range given in Table 6, then the method does
       not apply to the sample being analyzed, and the result may not be reported for regulatory
       compliance purposes.

16.3   When a high level of the pollutant is present, reverse-search computer programs may misinterpret
       the spectrum of chromatographically unresolved pollutant and labeled compound pairs with
       overlapping spectra. Examine each chromatogram for peaks greater than the height of the internal
       standard peaks. These peaks can obscure the compounds of interest.


                                               27                                       July 1998

-------
Method 1666, Revision A
17.0  Method  Performance

17.1   This method was developed and validated in a single laboratory.

17.2   Chromatograms of the aqueous performance standards (Sections 7.8.2 and 15.1) are shown in
       Figures 8 and 9.

18.0  Pollution Prevention

18.1   Pollution prevention encompasses any technique that reduces or eliminates the quantity or toxicity
       of waste at the point of generation. Many opportunities for pollution prevention exist in laboratory
       operation. EPA has established a preferred hierarchy of environmental management techniques
       that places pollution prevention as the management option of first choice.  Whenever feasible,
       laboratory personnel should use pollution prevention techniques to address their waste  generation.
       When wastes cannot be reduced feasibly at the source, the Agency recommends recycling as the
       next best option.  The acids used in this Method should be reused as practicable by purifying by
       electrochemical techniques. The only other chemicals used in this Method are the neat materials
       used in preparing standards. These standards are used in extremely small amounts and pose little
       threat to the environment when managed properly.  Standards should be prepared in volumes
       consistent with laboratory use to minimize the disposal of excess volumes of expired standards.

18.2   For information about pollution prevention that may be applied to laboratories and research
       institutions, consult Less is Better: Laboratory Chemical Management for Waste Reduction,
       available from the American Chemical Society's Department of Governmental Relations and
       Science Policy, 1155 16th Street NW, Washington DC 20036, 202/872-4477.

19.0  Waste Management

19.1   It is the laboratory's responsibility to comply with all Federal, State, and local regulations
       governing waste management, particularly the hazardous waste identification rules and
       land-disposal restrictions. In addition it is the laboratory's responsibility to protect air, water, and
       land resources  by minimizing and  controlling all releases from fume hoods and bench operations.
       Also, compliance is required with  any sewage discharge permits and regulations.

19.2   Samples containing acids at a pH of less than 2 are hazardous and must be neutralized before
       being poured down a drain or must be handled as hazardous waste.

19.3   For further information on waste management, consult The Waste Management Manual for
       Laboratory Personnel and Less is Better: Laboratory Chemical Management for Waste
       Reduction, both available from the American Chemical Society's Department of Government
       Relations and Science Policy,  1155 16th Street NW, Washington, DC 20036.
July 1998                                      28

-------
                                                                        Method 1666, Revision A
20.0  References

1.      "Performance Tests for the Evaluation of Computerized Gas Chromatography/Mass Spectrometry
       Equipment and Laboratories," U.S. EPA, NERL Cincinnati, OH 45268, EPA-600/4-80-025 (April
       1980).

2.      Bellar, T. A. and Lichtenberg, J. J., "Journal American Water Works Association," 66, 739
       (1974).

3.      Bellar, T. A. and Lichtenberg, J. J., "Semi-Automated Headspace Analysis of Drinking Waters and
       Industrial Waters for Purgeable Volatile Organic Compounds," in Measurement of Organic
       Pollutants in Water and Wastewater, C.E. VanHall, ed., American Society for Testing Materials,
       Philadelphia, PA, Special Technical Publication 686 (1978).

4.      National Standard Reference Data System, "Mass Spectral Tape Format," U.S. National Bureau
       of Standards (1979 and later attachments).

5.      "Working with Carcinogens," DREW, PHS, NIOSH, Publication 77-206 (1977).

6.      "OSHA Safety and Health Standards, General Industry," 29 CFR 1910, OSHA 2206 (1976).

7.      "Safety in Academic Chemistry Laboratories," American Chemical Society Publication, Committee
       on Chemical Safety (1979).

8.      "Methods 330.4 and 330.5 for Total Residual Chlorine," USEPA, EMSL Cincinnati, OH 45268,
       EPA-4-79-020  (March 1979)"Handbook of Analytical Quality Control in Water and Wastewater
       Laboratories," U.S. EPA, EMSL Cincinnati, OH 45268, EPA-4-79-019 (March 1979).

9.      "Handbook for Analytical Quality Control in Water and Wastewater Laboratories," U.S. EPA,
       EMSL Cincinnati, OH 45268, EPA-600/4-79-019 (March 1979).
                                             29                                     July 1998

-------
Method 1666, Revision A
21.0 Tables



Table 1. Volatile PMI Analytes Amenable to Purge and Trap and Determined by GC/MS Using
Isotope Dilution and Internal Standard Techniques
Pollutant Labeled Compound
PMI Analyte
n-Amyl acetate
n-Amyl alcohol
n-Butyl acetate
n-Butyl alcohol
Tert-butyl alcohol
Cyclohexane
Ethyl acetate
Furfural2
n-Heptane
n-Hexane
Isobutyraldehyde2
Isopropanol
Isopropyl acetate
Isopropylether
Methyl formate
Methylisobutyl ketone
N-pentane3
Tetrahydrofuran
Trichlorofluoromethane
m+p-Xylene
CASRN1
628-63-7
71-41-0
123-86-4
71-36-3
75-65-0
110-82-7
141-78-6
98-01-1
142-82-5
110-54-3
78-84-2
67-63-0
108-21-4
108-20-3
107-31-3
108-10-1
109-66-0
109-99-9
75-69-4
136777-
61-2
EPA- Analog CAS
EGD
977
978
979
1036
.RN1 EPA-
EGD




1343 d10 53001-22-2 1243
1333 d12 1735-17-7 1233
1736 13C 84508-45-2 1636
981

1334 d16 33838-52-7 1234
1335 d14 21666-38-6 1235
982
1044
983
960
991
1341
984







1345 ds 1693-74-9 1245
552

1332 d10 41051-88-1 1232
     o-Xylene
95-47-6
1331
                                                               •Mo
56004-61-6     1231
July 1998
              30

-------
                                                                       Method 1666, Revision A
1 Chemical Abstracts Service Registry Number.
2 These aldehydes may also be analyzed by Method 1667.
3 n-Pentane is not explicitly a PMI analyte.  However, the sum of the concentrations of n-pentane,
 n-hexane, and n-heptane are to be used to estimate the concentration of petroleum naphtha in
 PMI wastewaters.
                                          31                                       July 1998

-------
Method 1666, Revision A
Table 2. Volatile PMI Analytes Determined by Direct Aqueous Injection GCMS Using Isotope
Dilution and Internal Standard Techniques
Pollutant Labeled Compound
CASRN1
PMI Analyte
Acetonitrile 75-05-8
Diethylamine 109-89-7
Dimethylamine 124-40-3
Dimethyl sulfoxide 67-68-5
Ethanol 64-17-5
Ethylene glycol 107-21-1
Formamide 75-12-7
Methanol 67-56-1
Methylamine 74-89-5
Methyl Cellosolve® 109-86-4
n-Propanol 71-23-8
Triethylamine 121-44-8
EPA-EGD Analog CAS
RN1 EPA-
EGD
972 d3 2206-26-0 1272
986
987


1037 d6 2206-27-1 1237
1734 d6 1516-08-1 1634
1038
988


1735 d3 1849-29-2 1635
989
1040


755 1-dj not avail. 1255
990

1 Chemical Abstracts Service Registry Number.
July 1998
32

-------
                                                                         Method 1666, Revision A
  Table 3. Gas Chromatographic Retention Times and Minimum Levels for Volatile PMI
           Analytes Determined by Purge and Trap GC/MS
      EGD

      No.1
       991
       552
       984
      1344
      1243
      1343
      1235
       982
      1335
       960
      1636
      1736
       181
      1245
      1345
      1233
      1333
      1234
      1336
      1334
       985
       983
      1341
       978
       979
       981
       207
      1232
      1332
      1231
       977
      1331
                                     Retention Time
                                                                 ML2
PMI Analyte
Methyl formate
Trichlorofluoromethane
n-Pentane
Isopropanol
Tert-butyl alcohol-d10
Tert-butyl alcohol
n-Hexane-d14
Isobutyraldehyde
n-Hexane
Isopropylether
Ethyl acetate-13C
Ethyl acetate
Bromochloromethane(I.S.)
Tetrahydrofuran-d8
Tetrahydrofuran
Cyclohexane-d12
Cyclohexane
n-Heptane-d16
n-Butanol
n-Heptane
1,4-Difluorobenzene(I. S.)
Isopropyl acetate
Methylisobutyl ketone
n-Amyl alcohol
n-Butyl acetate
Furfural
Chlorobenzene-d5 (I.S.)
p-Xylene-d10
m,p-Xylene
o-Xylene-d10
n-Amyl acetate
o-Xylene
Mean (sec)
526
613
622
687
730
741
820
823
839
865
925
925
954
956
964
981
996
1013
1015
1033
1052
1128
1157
1202
1268
1354
1359
1368
1379
1413
1417
1424
EGD
181
181
181
181
181
1243
181
181
1235
181
181
1636
181
181
181
181
1233
985
985
1234
985
985
985
985
207
207
207
207
1232
207
207
1231
Relative
0.551
0.642
0.652
0.720
0.765
1.016
0.860
0.863
1.023
0.907
0.970
.000
.000
.002
.012
.028
.015
0.963
0.964
.020
.000
.072
.100
.143
0.933
0.996
.000
.007
.008
.040
.043
.008
(^g/L
100
10
10
200

100

10
10
5

10


20

5

500
10

10
10
500
5
500


10

5
5
1 Three digit EGD numbers beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal
standard method; EGD numbers beginning with 2 or 6 indicated a labeled compound quantified by the
internal standard method; EGD numbers beginning with 3 or 7 indicate a pollutant quantified by isotope
dilution. The initial "1" in four digit EGD numbers is to be ignored in applying these rules.
                                              33
                                                                        July 1998

-------
Method 1666, Revision A
2 This is a minimum level at which the entire analytical system shall give recognizable mass spectra
(background corrected) and acceptable calibration points, taking into account method-specific sample and
injection volumes. The concentration in the aqueous or solid phase is determined using the equations in
Section 14.
July 1998                                        34

-------
                                                                           Method 1666, Revision A
Table 4.   Gas Chromatographic Retention Times and Minimum Levels for Volatile PMI Analytes by
           Direct Aqueous Injection GC/MS
     EGD
      No-1    PMI Analyte
      989    Methylamine
      1635    Methyl alcohol-d3
      1735    Methyl alcohol
      987    Diethylamine
      1634    Ethyl alcohol-d5
      1734    Ethyl alcohol
      1272    Acetonitrile-d3
      972    Acetonitrile
      1255    n-Propanol-l-d]
      755    n-Propanol
      986    Diethylamine
      1245    Tetrahydrofuran-d8 (I.S.)
      1040    Methyl Cellosolve®
              (2-Methoxyethanol)
      990    Triethylamine
      1038    Ethylene glycol
      988    Formamide
      1237    Dimethyl sulfoxide-d6
      1037    Dimethyl sulfoxide
Mean (sec)
81
85
85.5
93
103
104
119
121
170
170.5
188
263
290
EGD Ref
1245
1245
1635
1245
1245
1634
1245
1272
1245
1255
1245
1245
1245
Relative
0.308
0.323
1.006
0.354
0.394
1.010
0.452
1.017
0.464
1.003
0.717
1.000
1.103
1VXAJ
(mg/L)
200

50
200

20

5

20
200

50
372
398
400
639
643
1245
1245
1245
1245
1237
1.414
1.513
1.521
2.431
1.006
200
200
1000

100
     1 Three digit EGD numbers beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal
     standard method; EGD numbers beginning with 2 or 6 indicated a labeled compound quantified by the
     internal standard method; EGD numbers beginning with 3 or 7 indicate a pollutant quantified by isotope
     dilution. The initial "1" in four digit EGD numbers is to be ignored in applying these rules.

     2 This is a minimum level at which the entire analytical system shall give recognizable mass spectra
     (background corrected) and acceptable calibration points, taking into account method-specific sample
     and injection volumes. The concentration in the aqueous or solid phase is determined using the
     equations in Section 14.
                                               35
                               July 1998

-------
Method 1666, Revision A
Table 5. BFB Mass-Intensity Specifications
                     m/z         Intensity Required



                     50          15-40% of m/z 95



                     75          30-60% of m/z 95



                     95          base peak, 100%



                     96          5-9% of m/z 95



                     173         less than 2% of m/z 174



                     174         greater than 50% of m/z 95



                     175         5-9% of m/z 174



                     176         95-101% of m/z 174



                     177         5-9% of m/z 176
July 1998                                     36

-------
                             Method 1666, Revision A
Table 6. Quality Control

EGD
No. PMI Analyte
972 Acetonitrile
977 Amyl acetate
978 Amyl alcohol
979 n-Butyl acetate
1036 n-Butyl alcohol
1343 tert-Butyl alcohol
1333 Cyclohexane
986 Diethylamine
987 Diethylamine
1037 Dimethyl sulfoxide
1734 Ethanol
1736 Ethyl acetate
1038 Ethylene glycol
988 Formamide
981 Furfural
1334 n-Heptane
1335 n-Hexane
982 Isobutyraldehyde
1044 Isopropanol
Acceptance Criteria for PMI Analytes
Acceptance Criteria for Performance Tests (% of Spike
Level)


Spike
Level
50mg/L
10 Mg/L
200 (ig/L
10 Mg/L
200 (ig/L
50 ng/L
10 ng/L
250 mg/L
250 mg/L
250 mg/L
50 mg/L
10 Mg/L
250 mg/L
500 mg/L
100 (ig/L
10 Mg/L
10 ng/L
10 Mg/L
100 (ig/L
Labeled and Native
PMI Analyte
Initial Precision
and Recovery
s
20
20
75
20
108
121
26
31
38
20
15
48
195
113
186
37
34
54
284
Labele
Ana
X Recov


Labeled and
dPMI Native PMI Analyte
ilyte On-going Recovery
ery (P) (R)
70-130 70-130 70-130
70-130
16-166
70-130
d-190
d-202
70-130
10-172
70-130
d-199
d-212
70-134 8-156 70-136
70-132
61-136
68-134
58-139
70-130 59-122 70-130
66-130 70-130 65-130
60-157 58-159 57-160
d-310
60-286
d-282
d-326
51-296
d-297
70-161 14-128 70-164
70-154 5-157 70-157
67-176
d-418
63-180
d-441
37
July 1998

-------
Method 1666, Revision A
  983  Isopropyl acetate           10 (ig/L      32     70-147                      70-150



  960  Isopropyl ether             10 jig/L      21     70-127                      70-129



  1735 Methanol                  50 mg/L     26     57-109      70-130          55-111



  989  Methylamine              250 mg/L     36     61-133                      59-136



  1040 Methyl cello solve         250 mg/L     20     70-130                      70-130



  991  Methyl formate             50 ng/L      73     20-165                      14-171



  1341 Methylisobutyl ketone       10 jig/L      42     70-162                      70-165



  984  n-Pentane                  10 (ig/L      52     51-155                      47-159



  755  n-Propanol                50 mg/L      25     42-130      54-149          40-130



  975  Tetrahydrofuran            10 jig/L      89     35-214      42-178          28-221



  552  Trichlorofluoromethane     20 (ig/L      20     70-130                      70-130



  990  Triethylamine             250 mg/L     31     70-133                      69-135



  1332 m,p-Xylene                20 ng/L      20     70-130      70-130          70-130



  1331 o-Xylene                  10 jig/L      20     70-130      70-130          70-130
Ju/y 7998                                     38

-------
                                                                          Method 1666, Revision A
Table 7. Characteristic
PMI Analyte
Acetonitrile
n-Amyl acetate
n-Amyl alcohol
n-Butyl acetate
n-Butyl alcohol
Tert-butyl alcohol
Cyclohexane
Diethylamine
Diethylamine
Dimethyl sulfoxide
Ethanol
Ethyl acetate
Ethylene glycol
Formamide
Furfural
n-Heptane
n-Hexane
Isobutyraldehyde
Isopropanol
Isopropyl acetate
Isopropyl ether
Methanol
Methylamine
Methyl Cellosolve® (2-
m/z's for Volatile PMI Analytes
Spike Level
I Labeled
(jig/L) (mg/L) Analog
50 d3
10
100
10
200
50 d10
10 d12
250
250
250 d6
50 d5
10 13C
250
500
100
10 d16
10 d14
10
100
10
10
50 d3
250
250

Primary m/z
(Native/Labeled)
41/44
43
70
43
56
59/66
56/96
58
44
47/50
31/33
43/44
31
45
96
71/82
57/66
72
45
43
45
31/33
30
45

Reference
Compound
1272
207
985
207
985
1234
1233
1245
1245
1237
1634
1636
1245
1245
207
1234
1235
181
181
985
181
1635
1245
1245
Methoxyethanol)
                                              39
July 1998

-------
Method 1666, Revision A
Methyl formate
Methylisobutyl ketone
n-Pentane
n-Propanol
Tetrahydrofuran
Trichlorofluoromethane
Triethylamine
m,p-Xylene
o-Xylene
50
10
10
50 1-dj
10 ds
20
250
20 d10
10 d10
60
43
43
31/32
72/80
101
86
106/116
106/16
181

181
1255
1245
181
1245
1232
1231
July 1998
40

-------
                                                                       Method 1666, Revision A
Table 8.   Maximum Recoveries for PMI Analytes by Purge-and-Trap GC/MS


                             PMI Analyte        Maximum Recovery
                                                       (%)
                       n-Amyl acetate                    130
                       n-Amyl alcohol                    300
                       n-Butyl acetate                    130
                       n-Butyl alcohol                    440
                       tert-Butyl alcohol                  130
                       Cyclohexane                      130
                       Ethyl acetate                      130
                       Furfural                          170
                       n-Heptane                        140
                       n-Hexane                         140
                       Isobutyraldehyde                  150
                       Isopropanol                       250
                       Isopropyl acetate                  130
                       Isopropyl ether                    130
                       Methyl formate                    130
                       Methylisobutyl ketone              130
                       n-Pentane                         130
                       Tetrahydrofuran                   150
                       Trichlorofluoromethane             130
                       m,p-Xylene                       130
                       o-Xylene                         130
                                            41                                      July 1998

-------
Method 1666, Revision A
    Optional
    Foam Trap
 ExU1/4ln.O.D.
  10 mmOass Fril,
  Medum Borosi ^
                               EN 11/4 in. O.D.
                               UrrmO.D.
Sanrple He I

2-WavS)*inge Valve

17
-------
                                                           Method 1666, Revision A
       Puge hlelRKng
      SampteGulelfiUing
3 in. Long x 6 rrm O.D. Gass Tubfrig
                  «-rr!Mal
                                           nrnn
                                                                Cap
           Figuie2.    Purging Devbe for Soils or Waters
                                   43
Ju/y 7998

-------
Method 1666, Revision A
    Paefctig Detail
             Consluciori De&i
          iz~  5 mmQassWool
         7.7emSiIea<3el
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July 1998
44

-------
                                                                        Method 1666, Revision A
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                                                         and GG should be heated
                                                         to 80^0.
      Fig ure 4.     Sc he mate of Pu ige-a nd -Trap Devbe—Pu rge Mode
                                            45
                                                                                     July 1998

-------
Method 1666, Revision A
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                 Figures.  SchernafcofP urge-and -Tra p Devbe—Deso rb iDbde
July 1998
                                46

-------
                                                                        Method 1666, Revision A
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        Figu IB 6.     Rela trye Response Cal ibratbn C uive b r o-Xybne
                                            47
                               July 1998

-------
Method 1666, Revision A
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                 (P) a flllkture of o-Xybne and o-Xybne-d10
July 1998
48

-------
                                                                  Method 1666, Revision A
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                             Standard of Arah/bs from Tabte 1
                                         49
                                                               July 1998

-------
Method 1666, Revision A
   100 H
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                                 Standard of Analytes from Table 2
July 1998
                            50

-------
                                                               Method 1666, Revision A


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                                    51
July 1998

-------

-------
                           Method  1667

  Formaldehyde, Isobutyraldehyde, and Furfural by
Derivatization Followed by High Performance Liquid
                             Chromatography

                               Revision A, July 1998

-------

-------
                           Method  1667, Revision A
 Formaldehyde, Isobutyraldehyde, and  Furfural  by Derivatization Followed by
                     High Performance Liquid Chromatography


1.0    Scope and Application

1.1     This method is for surveying and monitoring under the Clean Water Act.  It is used to determine
       certain organic pollutants specific to the pharmaceutical manufacturing industry (PMI) that can be
       derivatized and analyzed by high-performance liquid chromatography (HPLC).

1.2     The chemical compounds listed in Table 1 may be determined in waters, soils, and municipal sludges
       by this method.

1.3     The detection limits of the method are usually dependent on the level of interferences rather than
       instrumental limitations. The limits in Table 2 are the minimum levels that can be reliably quantified
       by this method with no interferences present.

       Furfural (2-furaldehyde) forms two relatively stable geometric isomers upon derivatization with
       2,4-dinitrophenylhydrazine (DNPH). The first isomer (probably anti-) elutes after the formaldehyde
       derivative and before the isobutyraldehyde derivative. The second isomer (probably syn-) elutes after
       the isobutyraldehyde derivative.  Experience with this system has shown that the best quantitative
       results (lowest detection limits) are obtained using the area from the first eluted peak rather than that
       from the second peak or the sum of the two areas. This method is for use only by analysts experienced
       with HPLC or under the close supervision of such qualified persons.

1.4     This method is performance-based. The  analyst is permitted to modify the method to overcome
       interferences or to lower the cost of measurements, provided that all performance criteria in this
       method are met. The requirements for establishing method equivalency are given in Section 9.1.2.

2.0    Summary of the Method

2.1     For solid wastes or for aqueous wastes containing significant amounts of solid material, the aqueous
       phase, if any, is separated from the solid phase and stored for later analysis.  If necessary, the particle
       size of the solids in the waste is reduced. The solid phase is extracted with an amount of extraction
       fluid equal to 20 times the weight of the solid  phase.  The extraction fluid employed is a function of
       the alkalinity of the solid phase of the waste. Following extraction, the aqueous extract is separated
       from the solid phase by filtration employing 0.6 to 0.9-(im glass-fiber filter.

2.2     If compatible (i.e., multiple phases will not form on combination), the initial aqueous phase of the
       waste is added to the aqueous extract, and these liquids are analyzed together. If incompatible, the
       liquids are  analyzed  separately  and the  results  are  mathematically combined to yield a
       volume-weighted average concentration.

2.3     A measured volume of aqueous  sample or an appropriate amount of solids leachate is buffered to
       pH=5 and derivatized with 2,4-dinitrophenylhydrazine (DNPH), using either the solid-sorbent or

                                             55                                     July 1998

-------
Method 1667, Revision A
       methylene chloride derivatization/extraction option. If the solid-sorbent option is used, the derivative
       is extracted using solid-sorbent cartridges, followed by elution with ethanol. If the methylene chloride
       option is used, the derivative is extracted with methylene chloride. The methylene chloride extracts
       are concentrated using the Kuderna-Danish (K-D) procedure and solvent exchanged into methanol
       prior to HPLC analysis.  Liquid chromatographic conditions are described that permit the separation
       and measurement  of formaldehyde, isobutyraldehyde, and furfural derivatives in the  extract by
       absorbance detection at 365 nm.

2.4    The quality  of the  analysis is  assured through reproducible  calibration and  testing  of the
       derivatization/extraction procedure and the HPLC system.

3.0   Definitions

       There are no specific definitions unique to this method.

4.0   Interferences

4.1    Method interferences may be caused by contaminants in  solvents, reagents, glassware, and other
       sample processing hardware that lead to discrete artifacts and/or elevated baselines in chromatograms.
       All of these materials must be routinely demonstrated to be free from interferences under the conditions
       of the analysis by analyzing laboratory reagent blanks as described in Section 9.3.

       4.1.1   Glassware must be scrupulously cleaned. Clean all glassware as soon as possible after use
               by rinsing with the last solvent used.  This should be followed by detergent washing with hot
               water, and rinses with tap water and reagent water. It should then be drained, dried, and
               heated  in a laboratory oven at 130°C for several hours before use.  Solvent rinses with
               methanol may be substituted for the oven heating. After drying and cooling, glassware should
               be stored in a clean environment to prevent any accumulation of dust or other contaminants.

       4.1.2   The use of high-purity reagents  and solvents helps to minimize interference problems.
               Purification of solvents by distillation in all-glass systems may be required.

4.2    Analysis of formaldehyde is complicated by its ubiquitous occurrence in the environment. Acetic acid,
       even high-purity acetic acid, is often contaminated with formaldehyde. For this reason, a phthalate
       buffer is used in this method instead of an acetate buffer.  Wherever acetic acid is used, it must be
       demonstrated to be formaldehyde free.

4.3    Matrix interferences may be caused by contaminants that are coextracted from the sample.  The extent
       of matrix interferences will vary considerably from source to source, depending upon the nature and
       diversity of the matrix being sampled. If matrix interferences occur, some additional cleanup may be
       necessary.

4.4    The extent of interferences that may be encountered using liquid chromatographic techniques has not
       been fully assessed.  Although the HPLC conditions described allow for resolution of the specific
       compounds covered by this method, other matrix components may interfere.

July 1998                                       56

-------
                                                                          Method 1667, Revision A
5.0    Safety

5.1     The toxicity or carcinogenicity of each compound or reagent used in this method has not been precisely
       determined; however, each chemical compound should  be treated as a potential health hazard.
       Exposure to these compounds should be reduced to the  lowest possible level.  The laboratory is
       responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling
       of the chemicals specified in this method.  A reference file of material safety data sheets should also
       be made available to all personnel involved in these analyses.  Additional information on laboratory
       safety can be found in References 1 through 3.

5.2     Formaldehyde has been classified as a potential carcinogen.  Primary standards of formaldehyde
       should be prepared in a hood, and a NIOSH/MESA approved toxic gas respirator should be worn
       when high concentrations are handled.

6.0    Apparatus and Materials

       Disclaimer:  The mention of trade names or commercial products in this Method is for illustrative
       purposes only and does not constitute endorsement or recommendation for use by the Environmental
       Protection Agency.  Equivalent performance may be achievable using apparatus, materials, or
       cleaning procedures other than  those  suggested here.   The  laboratory is responsible for
       demonstrating equivalent performance.

6.1     Reaction vessel—250-mL Florence flask.

6.2     Separatory funnel—250-mL, with polytetrafluoroethylene (PTFE) stopcock.

6.3     Kuderna-Danish (K-D) apparatus.

       6.3.1    Concentrator tube—10-mL, graduated (Kontes K-570050 or equivalent).  A ground-glass
               stopper is used to prevent evaporation of extracts.

       6.3.2    Evaporation flask—500-mL (Kontes K-570001-500 or equivalent). Attach to concentrator
               tube with springs, clamps, or equivalent.

       6.3.3    Snyder column—Three-ball macro (Kontes K-503000-0121 or equivalent).

       6.3.4    Snyder column—Two-ball micro (Kontes K569001-0219 or equivalent).

       6.3.5    Springs—!/2", (Kontes K-662750 or equivalent).

6.4     Vials—10- and 25-mL glass, with PTFE-lined screw-caps or crimp-tops.

                                              57                                       July 1998

-------
Method 1667, Revision A
6.5    Boiling chips—Solvent-extracted with methylene chloride, approximately 10/40 mesh (silicon carbide
       or equivalent).

6.6    Balance—Analytical, capable of accurately weighing to the nearest 0.0001 g.

6.7    pH meter—Capable of measuring to the nearest 0.01.

6.8    High-performance liquid chromatograph (modular).

       6.8.1   Pumping system—Isocratic, with constant flow control capable of 1.00 mL/min.

       6.8.2   High-pressure injection valve with 20-(iL loop.

       6.8.3   Column—250 mm  long  x 4.6  mm  inside diameter (i.d.), 5-(im particle  size, C18 (or
               equivalent).

       6.8.4   Absorbance detector—365 nm.

       6.8.5   Strip-chart recorder compatible with the detector. Use of a data system is recommended.

6.9    Glass-fiber filter paper, 0.6 to 0.9-(im.

6.10   Solid-sorbent cartridges—Packed with 500 mg C18 (Baker or equivalent).

6.11   Vacuum manifold—Capable of simultaneous extraction of up to 12 samples (Supelco or equivalent).

6.12   Sample reservoirs—50-mL capacity (Supelco or equivalent).

6.13   Pipet—Capable of accurately delivering 0.10 mL of solution (Pipetman or equivalent).

6.14   Water bath—Heated, with concentric ring cover, capable of temperature control of ± 2 °C at 80-90 °C.
       The bath should be used in a hood.

7.0   Reagents and Standards

7.1    Reagent grade chemicals shall be used in all tests.  Unless otherwise indicated, it is intended that all
       reagents shall conform to the  specifications of the Committee on Analytical Reagents of the American
       Chemical Society, where such specifications are available.  Other grades may be used, provided it is
       first ascertained that the  reagent is of sufficiently high purity to permit its use without lessening the
       accuracy of the determinations.

7.2    Reagent water—Water in which the compounds of interest and interfering compounds are not detected
       by this method. It may be generated by any of the methods in this subsection.
July 1998                                       58

-------
                                                                            Method 1667, Revision A
       7.2.1   Activated  carbon—Pass  tap  water through a  carbon bed  (Calgon Filtrasorb-300, or
               equivalent).

       7.2.2   Water purifier—Pass tap water through a purifier (Millipore Super Q, or equivalent).

       7.2.3   Boil and purge—Heat tap water to 90-100°C and bubble contaminant-free inert gas through
               it for approximately 1 hour. While still hot, transfer the water to screw-cap bottles and seal
               with a PTFE-lined cap.

7.3    Methylene chloride—HPLC grade or equivalent.

7.4    Methanol—HPLC grade or equivalent.

7.5    Ethanol (absolute)—HPLC grade  or equivalent.

7.6    2,4-Dinitrophenylhydrazine (DNPH, 70% w/w) in reagent water.

7.7    Formalin (37.6% w/w) in reagent  water.

7.8    Acetic acid (glacial), demonstrated to be formaldehyde-free.

7.9    Potassium acid phthalate.

7.10   Sodium hydroxide solutions, 1 N,  and  5 N.

7.11   Sodium chloride.

7.12   Sodium sulfate solution, 0.1 M.

7.13   Hydrochloric acid, 0.1 N.

7.14   Extraction fluid—Dilute 64.3 mL of 1.0 N sodium hydroxide and 5.7 mL of glacial acetic acid to 900
       mL with reagent water.  Further dilute  to 1 L with reagent water. The pH should be 4.93 ± 0.02. If
       not,  adjust with acid or base.

7.15   Stock standard solutions.

       7.15.1  Stock formaldehyde (approximately 1.00 mg/mL)—Prepare by diluting 265 (iL formalin to
               100 mL with reagent water.

               Standardization of formaldehyde stock solution—Transfer a 25 -mL aliquot of a 0.1 M sodium
               sulfite solution to a beaker and record the pH. Add a 25-mL aliquot of the formaldehyde stock
               solution (Section 7.15.1) and record the pH. Titrate this mixture back to the original pH
               using 0.1 N hydrochloric acid.  The formaldehyde concentration is  calculated using the
               following equation:

                                                59                                        July 1998

-------
Method 1667, Revision A
                     Concentration (mg/mL) = 30.03 x  (N HCl) x (mL HCl)  x 25

                     where'.

                     N HCl = Normality  of the HCl solution

                     mL HCl = mL of standardised HCl solution', and

                     30.03 = Molecular  weight of formaldehyde.
        7.15.2  Stock formaldehyde, isobutyraldehyde, and furfural—Prepare by adding 265 (iL of formalin,
               0.100 g of isobutyraldehyde, and 0.100 g of furfural to 90 mL of reagent water and dilute to
               100 mL.  The concentrations of isobutyraldehyde and furfural in this solution are 1.00
               mg/mL. Calculate the concentration of formaldehyde in this solution using the results of the
               assay performed in Section 7.15.1.

        7.15.3  Stock standard solutions must be replaced after six months, or sooner if comparison with
               check standards indicates a problem.

        7.15.4  Aqueous performance standard—An aqueous performance standard containing formaldehyde
               (nominally 100 (ig/L), isobutyraldehyde at 100 (ig/L, and furfural at 100  (ig/L shall be
               prepared daily and analyzed each shift to demonstrate performance  (Section 9).

        7.15.5  Preparation of calibration standards.

               7.15.5.1       Prepare  calibration standard solutions of formaldehyde, isobutyraldehyde,
                              and furfural in reagent water from stock standard solution (Section 7.15.2).
                              Prepare these solutions at the following concentrations (in (ig/mL) by serial
                              dilution  of the stock standard solution:  50, 20,  10. Prepare additional
                              calibration standard solutions at the following concentrations, by dilution of
                              the appropriate 50, 20, or 10 (ig/mL standard:  5, 0.5, 2, 0.2, 1, 0.1. Make
                              further dilutions if appropriate.

7.16    Reaction  solutions.

        7.16.1  DNPH (1.00 mg/mL)—Dissolve 142.9mg70%(w/w)reagentin 100 mL of absolute ethanol.
               Slight heating or sonication may be necessary to effect dissolution.

        7.16.2  Phthalate  buffer (0.1 N)—Prepare by dissolving 20.42 g of potassium acid phthalate in 1 L
               of reagent water.  Adjust pH to 5 by addition of sodium hydroxide  or hydrochloric acid, as
               necessary.

        7.16.3  Sodium chloride solution (saturated)—Prepare by mixing an excess of the reagent-grade solid
               with reagent water.
July 1998                                        60

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                                                                            Method 1667, Revision A
8.0    Sample Collection, Preservation, and Storage

8.1    Grab samples are collected in glass containers having a total volume greater than 20 mL. For aqueous
       samples that pour freely, fill sample bottles so that no air bubbles pass through the sample as the bottle
       is filled and seal each bottle so that no air bubbles are entrapped. Maintain the hermetic seal on the
       sample bottle until time of analysis.

8.2    Samples are maintained at 0-4°C from the time of collection until analysis.  Samples must be
       derivatized within five days of collection and analyzed within three days of derivatization.

9.0    Quality Control

9.1    Each laboratory that uses this method is required to operate a formal quality assurance program
       (Reference 4).  The minimum requirements of this program consist of an initial demonstration of
       laboratory capability and analysis of standards  and  blanks as tests  of continued performance.
       Laboratory performance is compared to established performance criteria to determine if the results of
       analyses meet the performance characteristics of the method.

       9.1.1   The analyst shall make an initial demonstration of the ability to generate acceptable accuracy
               and precision with this method.  This ability is established as described in Section 9.2.

       9.1.2   In recognition of advances that are occurring in analytical technology, and to allow the analyst
               to overcome sample matrix interferences, the analyst is permitted certain options to improve
               separations or lower the costs of measurements. These options include alternative extraction,
               concentration, cleanup procedures, and changes in columns  and  detectors.   Alternative
               techniques, such as  substitution of immunoassay,  and  changes  that degrade method
               performance are not allowed. If an analytical technique other than the techniques specified
               in this method is used, that technique must have a specificity equal to or better than the
               specificity of the techniques in this method for the analytes of interest.

               9.1.2.1 Each time a modification is made to this method, the analyst is required to repeat the
                      procedure in Section 9.2. If the detection limit of the method will be affected by the
                      change, the laboratory is required to demonstrate that the  method detection limit
                      (MDL; 40  CFR Part 136, Appendix B) is  lower  than one-third the regulatory
                      compliance level. If calibration will be affected by the  change, the analyst must
                      recalibrate the instrument per Section 10.

               9.1.2.2 The laboratory is required to maintain records of modifications made to this method.
                      These records include the information below, at a minimum.

                      9.1.2.2.1       The  names, titles,  addresses, and telephone  numbers of the
                                     analyst(s) who performed the analyses and modification, and of the
                                     quality control officer who witnessed and will verify the analyses
                                     and modification.
                                               61                                       July 1998

-------
Method 1667, Revision A
                       9.1.2.2.2       A list of pollutant(s) measured, including name and CAS Registry
                                      Number.

                       9.1.2.2.3       A narrative stating the reason(s) for the modification.

                       9.1.2.2.4       Results from all quality control (QC) tests comparing the modified
                                      method to this method, including:

                                      (a)      Calibration (Section 10.1.2)

                                      (b)      Calibration verification (Section 10.1.2.2)

                                      (c)      Initial precision and accuracy (Section 9.2)

                                      (d)      Analysis of blanks (Section 9.3)

                                      (e)      Accuracy assessment (Section 9.5)

                       9.1.2.2.5       Data that will allow an independent reviewer  to validate each
                                      determination by tracing the instrument output (peak height, area, or
                                      other signal) to the final result.  These data are to include:

                                      (a)      Sample numbers and other identifiers

                                      (b)      Extraction dates

                                      (c)      Analysis dates and times

                                      (d)      Analysis sequence/run chronology

                                      (e)      Sample weight or volume (Section 11)

                                      (f)      Extract volume prior to each cleaning step (Section 11.1.2)

                                      (g)      Final extract volume prior to injection (Section 11.3.4.5 or
                                              Section 11.3.5.5)

                                      (h)      Injection volume (Section 12)

                                      (I)      Dilution data, differentiating between dilution of a sample
                                              or an extract

                                      (j)      Instrument and operating conditions
July 1998                                        62

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                                                                            Method 1667, Revision A
                                     (k)     Column  and operating conditions  (nature  of column,
                                             dimensions, flow rates, solvents, etc.)

                                     (1)      Detector operating conditions (wavelength, etc.)

                                     (m)     Chromatograms, printer tapes, and other recording of raw
                                             data

                                     (n)     Quantitation reports, data system outputs, and other data
                                             necessary to link raw data to the results reported

       9.1.3   Analyses of blanks are required to demonstrate freedom from contamination  and that the
               compounds of interest and interfering compounds have not been carried over from a previous
               analysis (Section 4).  The procedures and criteria for analysis of a blank are described  in
               Section 9.3.

       9.1.4   The laboratory shall, on an ongoing basis, demonstrate through the analysis of the aqueous
               performance standard (Section 7.15.4) that the analysis system is in control. This procedure
               is described in Section 10.

       9.1.5   The laboratory shall maintain records to define the quality of data that is generated.

9.2    Initial precision and accuracy—To establish the ability to generate acceptable precision and accuracy,
       the analyst shall perform the following operations for compounds to be calibrated.

       9.2.1   Analyze four aliquots of the aqueous performance standard (Section 7.15.4) according to the
               method beginning in Section 11.  Use the solid-sorbent option or the methylene chloride
               option, whichever will be used routinely.

       9.2.2   Using results from Section 9.2.1, compute the average percent recovery (X) and the standard
               deviation of the recovery (s) for each compound.

       9.2.3   For each compound, compare s and X with the corresponding limits for initial precision and
               recovery found in Table 3. If s and X for all compounds meet the acceptance criteria, system
               performance is acceptable and analysis of blanks and samples may begin. If, however, any
               individual s exceeds the  precision limit or any individual X  falls outside the  range for
               accuracy, system performance is unacceptable for that compound. This is an indication that
               the analytical system is not performing properly for the compound(s) in question. In this
               event, correct the problem and repeat the entire test (Section 9.2.1).

9.3    Blanks—Reagent water blanks are analyzed to demonstrate freedom from contamination.

       With each sample lot (samples analyzed  on the same 12-hour shift), a blank shall be analyzed
       immediately after analysis  of the aqueous performance standard (Section 9.1.4) to demonstrate
       freedom from contamination.  If  any of the compounds of interest  or any potentially interfering

                                               63                                        July 1998

-------
Method 1667, Revision A
       compound is found in a blank at greater than 10 (ig/L, analysis of samples is halted until the source
       of contamination is eliminated and a blank shows no evidence of contamination at this level.

9.4    The specifications contained in this method can be met if the apparatus used is calibrated properly,
       then maintained in a calibrated state. The standards used for calibration (Section 7.15.5), calibration
       verification (Section 10.1.2.2) and for initial (Section 9.2) and ongoing (Section 9.1.4) precision and
       accuracy should be identical, so that the most precise results will be obtained.

9.5    Depending on specific program requirements, field replicates may be collected to  determine the
       precision of the sampling technique, and spiked samples may be required to determine the accuracy
       of the analysis.

10.0  Calibration

10.1   Establish liquid chromatographic operating parameters to produce a retention time equivalent to that
       indicated in Table 2 for formaldehyde derivative. Suggested chromatographic conditions are provided
       in Section 12.1.  Prepare derivatized calibration standards according to the procedure in  Section
       10.1.1.  Calibrate the chromatographic system using the external standard technique (Section 10.1.2).

       10.1.1  Process each calibration standard  solution through the derivatization option used for sample
               processing (Section 11.3.4 or 11.3.5).

       10.1.2  External standard calibration procedure.

               10.1.2.1        Analyze each derivatized calibration standard using the chromatographic
                              conditions  specified in Section  12.1,  and  tabulate peak area  against
                              concentration injected. The results may be used to prepare calibration curves
                              for formaldehyde, isobutyraldehyde, and furfural.

               10.1.2.2       The working calibration curve must be verified at the beginning of each 12-
                              hour shift  or  every 20 samples,  whichever is  more  frequent,  by the
                              measurement of one or more calibration standards. If the response for any
                              analyte varies from the previously established responses by more than 10%,
                              the test must be repeated using a fresh calibration standard after it is verified
                              that the analytical  system  is in control.  Alternatively, a new calibration
                              curve may be prepared for that compound.  If an autosampler is available,
                              it is convenient to prepare a calibration curve daily by analyzing standards
                              along with test samples.

11.0  Sample Extraction,  Cleanup, and Derivatization

11.1   Extraction of solid samples.

       11.1.1  All solids must be homogeneous. When the sample is not dry, determine the dry weight of the
               sample using a representative aliquot.

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                                                                            Method 1667, Revision A
               11.1.1.1        Determination of dry weight—In certain cases, sample results are desired
                              based on a dry weight basis. When such data is desired, a portion of the
                              sample is weighed out at the same time as the portion used for the analytical
                              determination.


Warning:      The  drying oven should be contained in a hood or  vented.  Significant laboratory
               contamination may result from drying a heavily contaminated hazardous waste sample.

               11.1.1.2        Immediately after weighing the sample for extraction, weigh 5-10 g of the
                              sample into a tared crucible.  Determine the percent dry weight of the sample
                              by drying overnight at 105 °C.   Allow to cool in a desiccator before
                              weighing.

                                              g of dry sample
                                                g of sample
        11.1.2  Measure 25 g of solid into a 500-mL bottle with a PTFE-lined screw-cap or crimp-top, and
               add 500 mL of extraction fluid (Section 6.13). Extract the solid by rotating the bottle at
               approximately 30 rpm for 18 hours. Filter the extract through glass-fiber filter paper and
               store in a sealed bottle at 4°C.  Each mL of extract represents 0.050 g of solid.

11.2    Cleanup and separation.

        11.2.1  Cleanup procedures may not be necessary for a relatively clean sample matrix. The cleanup
               procedures recommended in this method have been used for the analysis of various sample
               types.  If particular circumstances demand the  use of an alternative cleanup procedure, the
               analyst must meet the specifications in Section 9.1.2.

        11.2.2  If the sample  is not clean, or the  complexity is unknown, the entire  sample should be
               centrifuged at 2500 rpm for 10 minutes.  Decant the supernatant liquid from the centrifuge
               bottle and filter through glass-fiber filter paper into a container that can be tightly sealed.

11.3    Derivatization.

        11.3.1  For aqueous samples, measure a 50-to 100-mL aliquot of sample. Quantitatively transfer the
               sample aliquot to the reaction vessel (Section 6.1).

        11.3.2  For solid samples, 1-10 mL of leachate (Section  11.1.2 or Section 11.2.2) will usually be
               required. The amount used for a particular sample must be determined through preliminary
               experiments.

        11.3.3  Derivatization and extraction of the derivative can be accomplished using the solid-sorbent
               (Section 11.3.4) or methylene chloride option (Section 11.3.5).
                                               65                                        July 1998

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Method 1667, Revision A
        11.3.4  Solid Sorbent Option

               11.3.4.1        Add 4 mL of phthalate buffer (Section 7.16.2) and adjust the pH to 5.0±0.1
                              with sodium hydroxide or hydrochloric acid.  Add 10 mL of DNPH reagent,
                              adjust the total volume to approximately 100 mL with reagent water, seal the
                              container and place on a wrist-action shaker at room temperature for 1 hour.
                              Samples or standards containing high analyte  concentrations may require
                              more DNPH reagent for complete reaction.

               11.3.4.2        Assemble the vacuum manifold and connect to a water aspirator or vacuum
                              pump. Assemble solid sorbent cartridges containing a minimum of 1.5 g of
                              C18 sorbent, using connectors supplied by the manufacturer, and attach the
                              sorbent train to the vacuum manifold. Condition each cartridge by passing
                              10 mL dilute phthalate buffer (10 mL 5 N phthalate buffer dissolved in 250
                              mL of reagent water) through the sorbent cartridge train.
               11.3.4.3        Remove the reaction vessel from the shaker and  add 10  mL of saturated
                              sodium chloride solution to the vessel.

               11.3.4.4        Add the reaction solution to the sorbent train and apply a vacuum so that the
                              solution is drawn through the cartridges at a rate of 3 to 5 mL/min. After the
                              solution has eluted,  allow  air to  be  drawn through the cartridge for
                              approximately 2 minutes to remove all  traces  of solution, then release the
                              vacuum.

               11.3.4.5        Elute each cartridge train with approximately 9 mL of absolute ethanol,
                              directly into a 10-mL volumetric flask.  Dilute the solution to volume with
                              absolute ethanol, mix thoroughly, and  place in a tightly  sealed vial until
                              analyzed.

        11.3.5  Methylene chloride option.

               11.3.5.1        Add 5 mL of phthalate buffer (Section 7.16.2) and adjust the pH to 5.0±0.1
                              with sodium hydroxide or hydrochloric acid.  Add 10 mL of DNPH reagent,
                              adjust the volume to  approximately 100 mL with reagent water, seal the
                              container, and place on a wrist-action shaker at room temperature for 1 hour.
                              Samples or standards with high analyte concentrations may require more
                              DNPH reagent for complete reaction.

               11.3.5.2        Extract the solution with three 20-mL portions of methylene chloride, using
                              a 250-mL separatory funnel, and combine the methylene chloride layers.  If
                              an emulsion forms upon extraction,  remove the entire  emulsion  and
                              centrifuge at 2000 rpm for 10 minutes. Separate the layers and proceed with
                              the next extraction.
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                                                                           Method 1667, Revision A
               11.3.5.3       Assemble a K-D concentrator by attaching a 10-mL concentrator tube to a
                             500-mL  evaporator flask.  Wash the K-D  apparatus with 25  mL of
                             extraction solvent to complete the quantitative transfer.

               11.3.5.4       Add one or two clean boiling chips to the evaporation flask and attach a
                             three-ball Snyder column. Prewet the Snyder column by adding about 1 mL
                             of methylene chloride to the top.  Place the K-D apparatus on a hot water
                             bath (80-90 °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 10-15 minutes. 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 the liquid reaches 10 mL, remove the K-D apparatus and  allow it
                             to drain and cool for at least 10 minutes.

               11.3.5.5       Prior to liquid chromatographic analysis, the solvent must be exchanged to
                             methanol. The analyst must ensure  quantitative transfer  of the  extract
                             concentrate.  The exchange is performed as described below.

11.4   After cooling and draining as  described in Section 11.3.5.4, momentarily remove the Snyder  column
       and add 5 mL of methanol and a new boiling chip. Attach the micro Snyder column. Concentrate the
       extract using 1 mL of methanol to prewet the Snyder column. Place the K-D apparatus on the water
       bath so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position
       of the apparatus and the water temperature, as required, to complete the concentration. When the
       apparent volume of the liquid reaches less than 5 mL, remove the K-D apparatus and allow it  to drain
       and cool for at least 10 minutes.

       Remove the  Snyder column and rinse the flask and its lower joint with 1-2 mL of methanol and add
       to the concentrator tube.  A 5-mL syringe is recommended for this operation.  Adjust the extract
       volume to 10-mL with methanol.  Stopper the concentrator tube and store refrigerated at  4  °C if
       further processing will not be performed immediately. If the extract will be stored longer than two
       days, it should be transferred to a vial with a PTFE-lined screw-cap or crimp-top. Proceed with the
       liquid chromatographic analysis if further cleanup is not required.

12.0  High-Performance Liquid Chromatography

12.1   Chromatographic conditions.

       Column: C18, 250 mm long x 4.6 mm i.d., 5-(im particle size (or equivalent).

       Mobile Phase:  Methanol/water, 75:25 (v/v), isocratic  at 30 °C.

       Flow Rate:   1.0 mL/min.
                                              67                                       July 1998

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Method 1667, Revision A
       UV Detector:  365 nm.

       Injection Vol.:  20 (iL.

12.2   Analysis.

       12.2.1  Analyze samples by HPLC using conditions described in Section 12.1.  Table 2 lists the
               retention times and MLs that were obtained under these conditions.  Other HPLC columns,
               chromatographic conditions, or detectors may be used if the requirements of Section 9 are met.

       12.2.2  The width of the retention-time window used to make identifications should be based upon
               measurements of actual retention-time variations of standards over the course of a day. Three
               times the standard deviation of the retention time for a compound can be used to calculate a
               suggested window size; however, the experience of the analyst should weigh heavily in the
               interpretation of chromatograms.

       12.2.3  If the peak area exceeds the linear range of the calibration curve, a smaller sample volume
               should be used.  Alternatively, the final solution may be diluted with ethanol or methanol, as
               appropriate, and reanalyzed.

       12.2.4  If the peak area measurement is prevented by the presence of observed interferences, further
               cleanup may be required.

12.3   Calculations.

       12.3.1  Calculate the calibration factor (CF) at each concentration and the mean calibration factor
               (CFm) as follows (mean value based on 5 points):


                                              area response (A]
                                        CF =	=
                                              concentration (C)


                                                         ± CF
                                      mean CF = CF  =	
        12.3.2  Aqueous samples—Calculate the concentration of each analyte as follows:
                                             A  * V * DF
                                             —	'-	
                                               CF  * V
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                                                                           Method 1667, Revision A
where:
       RFm is the mean response factor
       As is the area signal from the analyte
       Ve is the extract volume
       DF is the dilution factor; e.g. 10, if the sample is diluted by a factor of 10
       Vs is the sample volume

       12.3.3  Solid samples—Calculate the concentration of each analyte using the equation below.  A
               factor must be included in the equation to account for the weight of the sample used and, if
               desired, to correct for dry weight.
                                             A  * V  * DF
                                   mglkg =	—
where:
       Ws is the sample weight
       %m is the percent moisture of the sample
       the other symbols are the same as in Section 12.3.2

13.0  Method Performance

13.1   The MDLs listed in Table 2 were obtained using reagent water and methylene chloride extraction.
       Similar results can be obtained using the solid-sorbent method.

13.2   This method has been tested for linearity of recovery from spiked reagent water and  has been
       demonstrated to be applicable over the range from the ML to 50 times the ML.

13.3   A representative chromatogram is presented as Figure 1.
14.0   Pollution  Prevention

14.1    Pollution prevention encompasses any technique that reduces or eliminates the quantity or toxicity of
        waste at the point of generation. Many opportunities for pollution prevention exist in laboratory
        operation. EPA has established a preferred hierarchy of environmental management techniques that
        places pollution prevention as the management option of first choice. Whenever feasible, laboratory
        personnel should use pollution prevention techniques to address their waste generation. When wastes
        cannot be reduced feasibly at the source, the Agency recommends recycling as the next best option.
        The acids used in this Method should be reused as practicable by purifying by electrochemical
        techniques. The only other chemicals used in this Method are the neat materials used in preparing

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Method 1667, Revision A
       standards.  These standards are used in extremely small amounts  and pose little threat to the
       environment when managed properly.  Standards should be prepared in volumes consistent with
       laboratory use to minimize the disposal of excess volumes of expired standards.

14.2   For  information about pollution prevention that may be applied to laboratories  and research
       institutions, consult Less is Better:  Laboratory Chemical Management for Waste Reduction,
       available from the American Chemical Society's Department of Governmental Relations and Science
       Policy, 1155  16th Street NW, Washington DC 20036, 202/872-4477.

15.0   Waste Management

15.1   It is the laboratory's responsibility to comply with all Federal, State, and local regulations governing
       waste management, particularly the hazardous waste identification rules and land-disposal restrictions.
       In addition it is the laboratory's responsibility to protect air, water, and land resources by minimizing
       and controlling all releases from fume hoods and bench operations. Also, compliance is required with
       any sewage discharge permits and regulations.

15.2   Samples containing acids at a pH of less than 2 are hazardous and must be neutralized before being
       poured down a drain or must be handled as hazardous waste.

15.3   For  further  information on waste  management, consult The  Waste Management Manual for
       Laboratory Personnel and Less is Better: Laboratory Chemical Management for Waste Reduction,
       both available from the American Chemical Society's Department of Government Relations and
       Science Policy, 1155 16th Street NW, Washington, DC  20036.
July 1998                                       70

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                                                                        Method 1667, Revision A
16.0   References

1.      "Working with Carcinogens," DREW, PHS, NIOSH, Publication 77-206 (1977).

2.      "OSHA Safety and Health Standards, General Industry," 29 CFR 1910, OSHA 2206, (1976).

3.      "Safety in Academic Chemistry Laboratories," American Chemical Society Publication, Committee
       on Chemical Safety (1979).

4.      "Handbook of Analytical Quality Control in Water and Wastewater Laboratories," U.S. EPA, EMSL
       Cincinnati, OH 45268, EPA-600/4-79-019 (March 1979).
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Method 1667, Revision A
17.0 Tables

Table 1. PMI Analytes to Which This Method Applies


                      PMI Analyte                     CASRN1

                      Formaldehyde                      50-00-0
                      Furfural                           98-01-1
                      Isobutyraldehyde                   78-84-2
                      1 Chemical Abstracts Service Registry Number.



Table 2. Retention Times and Minimum Levels (MLs) for PMI Analytes
       PMI Analyte                          Retention Time1           ML2
                                               (seconds)
       Formaldehyde                              326                  50

       Furfural                                   495                  50

       Isobutyraldehyde                            714                  50

       1  Retention times are for the DNPH derivative.

       2  This is the minimum level at which the entire analytical system shall give a
         recognizable signal and an acceptable calibration point, taking into account method-
         specific sample and injection volumes.


Table 3. Quality  Control Acceptance Criteria for Initial Precision and Recovery
PMI Analyte
Formaldehyde
Furfural
Spike
Level (jig/L)
50
100
Average Percent
Recovery (X)
25-187
70-102
Standard E
(s)
81
16
July 1998                                     72

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                                                                      Method 1667, Revision A
Isobutyraldehyde                 50              45-121                  38
                                          73                                       July 1998

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250 —
200 —
150 —
100 —
 SO
                                  10 PPM STANDARD.         Amount: 1JOOO.
                                  Acqured on 17-08-9 4 a I 00:43:45  Reported on 08-17-94 a 110:40:44
                                         I
                                         10
20
 I
35
                 Figure 1. Chiomaliogramofthe2,4-DNPH OerJvafe of Forma tie hyde,
                         Furlural, and Isobutpaldehyde
                                               75
             July 1998

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July 1998
76

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                                 Method 1671

Volatile Organic Compounds Specific to the Pharmaceutica
                     Manufacturing Industry by GC/FID
                                     Revision A, July 1998

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                          Method 1671,  Revision A
 Volatile Organic Compounds Specific to the Pharmaceutical Manufacturing
                                  Industry by GC/FID


1.0    Scope and Application

1.1     This method is for surveying and monitoring under the Clean Water Act. The method is used to
       determine  certain  non-purgeable  volatile  organic  pollutants  specific  to  the  pharmaceutical
       manufacturing industry (PMI) that are amenable to direct aqueous injection gas chromatography (GC)
       and detection by a flame ionization detector (FID).

1.2     The PMI analytes listed in Table 1 may be determined in waters, soils, and municipal sludges by this
       method.

1.3     The detection limits of Method 1671 are usually dependent on the level of interferences rather than
       instrumental limitations. The minimum levels (MLs) in Table 2 are the level that can be attained with
       no interferences present.

1.4     This method is recommended for use by, or under the supervision of, analysts experienced in the
       operation of gas chromatographs and in the interpretation of chromatograms.

1.5     This method is performance-based.  The analyst is permitted to modify the method to overcome
       interferences or to lower the cost of measurements, provided that  all performance criteria in this
       method are met. The requirements for establishing method equivalency are given in Section 9.2.

2.0    Summary of the Method

2.1     The percent solids content of the sample is determined. If the solids content is less than l%,aninternal
       standard(s) is added to a 5-mL sample. If the solids content of the sample is greater than 1%, 5 mL
       of reagent water and an internal standard(s) is added to a 5-g aliquot of sample.

       The mixture is sonicated in a centrifuge tube with little or no headspace for 5 minutes. During this
       period the analytes and the internal standard will equilibrate between the solid and aqueous phases.
       In some cases, additional sonication will be necessary to establish equilibrium.  The  resulting
       suspension is centrifuged and the supernatant liquid analyzed.

2.2     An appropriate amount of the aqueous solution (or supernate) is injected into the GC. The compounds
       are separated by the GC and detected by the FID.

3.0    Definitions

       There are no definitions specific to this method.
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Method 1671, Revision A
4.0    Interferences

4.1    Impurities in the carrier gas, organic compounds outgassing from the GC plumbing, and solvent
       vapors in the laboratory account for the majority of contamination problems encountered with this
       method.  The analytical system is demonstrated to be free from interferences under conditions of the
       analysis by analyzing reagent water blanks initially and with each sample batch (samples analyzed on
       the same 12-hour shift), as described in Section 9.4.

4.2    Samples can be contaminated by diffusion of volatile organic compounds through the bottle seal during
       shipment and storage. A field blank  prepared from  reagent water and carried through the sampling
       and handling protocol may serve as a check on such contamination.

4.3    Contamination by carryover  can occur when high-level  and low-level samples  are  analyzed
       sequentially. To reduce carryover, the syringe is cleaned or replaced with a new syringe after each
       sample is analyzed. When an unusually concentrated sample is encountered, it is followed by analysis
       of a reagent water blank to check for carryover. Syringes are cleaned by washing with soap solution,
       rinsing with tap and distilled water, and drying in an oven at  100-125 °C. Other parts of the system
       are also subject to contamination; therefore, frequent bakeout and purging of the entire system may
       be required.

4.4    Interferences resulting from samples will vary considerably from source to source, depending on the
       diversity of the site being sampled.

5.0    Safety

       The toxicity or carcinogenicity of each analyte, compound, or reagent used in this method has not been
       precisely determined; however, each chemical compound should be treated as apotential health hazard.
       Exposure to these  compounds should be reduced to the lowest possible level.  The laboratory is
       responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling
       of the chemicals specified in this method.  A reference file of material safety data sheets should also
       be made available to all personnel involved in these  analyses. Additional information on  laboratory
       safety can be found in References 2-4.

6.0    Equipment and Supplies

6.1    Sample bottles and septa

       6.1.1   BottlesS25- to 40-mL with polytetrafluoroethylene (PTFE)-lined screw-cap (Pierce  13075,
               or equivalent). Detergent wash, rinse with tap and distilled water, and dry at > 105 °C  for a
               minimum of 1 hour before use.

       6.1.2   SeptaSPTFE-faced silicone (Pierce 12722, or equivalent), cleaned as above and baked at 100-
               200 °C for a minimum of 1 hour.
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                                                                           Method 1671, Revision A
6.2    Gas chromatographS Shall be linearly temperature programmable with initial and final holds, and shall
       produce  results  which meet the calibration  (Section  10), quality  assurance  (Section 9),  and
       performance tests (Section 13) of this method.

       6.2.1   ColumnSSO m long x 0.32 mm i.d. fused-silicamicrobore column coated with 4-(im of bonded
               poly(dimethylpolysiloxane) (Supelco SPB-1 Sulfur, or equivalent).

       6.2.2   GC operating conditions.

       Temperatures:

       ColumnS2 minutes at 40°C, 10°C per minute to 180°C.

       Injection portS200°C

       FIDS300°C

       Carrier gasSHydrogen at a head pressure of 10 psig.

       An injector split may be used in order to optimize peak shape and repeatability.

6.3    SyringesS5-mL, gas-tight glass hypodermic, with Luer-lok tips.

6.4    Micro syringesSlO-, 25-, and 100-(iL.

6.5    Syringe valvesS2-way with Luer ends, PTFE.

6.6    BottlesS15-mL, screw-cap with PTFE liner.

6.7    Balances.

       6.7.1   Analytical, capable of weighing 0.1 mg.

       6.7.2   Top-loading, capable of weighing 10 mg.

6.8    Equipment for determining percent moisture.

       6.8.1   Oven, capable of being temperature-controlled at 110 ° C (±5 ° C).

       6.8.2   Desiccator.

       6.8.3   BeakersS50-, 100-mL.

6.9    Centrifuge apparatus.


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Method 1671, Revision A
       6.9.1   Centrifuge capable of rotating 10-mL centrifuge tubes at 5000 rpm.

       6.9.2   Centrifuge tubes, 10-mL, with screw-caps (PTFE-lined) to fit centrifuge.

6.10   Sonication apparatus capable of sonicating 10-mL centrifuge tubes and thoroughly agitating contents.


7.0   Reagents and Standards

7.1    Reagent water: Water in which the compounds of interest and interfering compounds are not detected
       by this method. It may be generated by any of the following methods:

       7.1.1   Activated carbonSpass tap water through a carbon bed (Calgon Filtrasorb-3 00, or equivalent).

       7.1.2   Water purifierSPass tap water through a purifier (Millipore Super Q, or equivalent).

       7.1.3   Boil and purgeSHeat tap water to between 90 and  100 °C and bubble contaminant-free inert
               gas through it for approximately 1 hour. While  still  hot, transfer the water to screw-cap
               bottles and seal with a PTFE-lined cap.

7.2    Sodium thiosulfateSACS granular.

7.3    Standard solutionsSPurchased as solutions or mixtures with certification to their purity, concentration,
       and authenticity, or prepared from materials of known purity and composition.  If compound purity
       is 96% or greater, the weight may be used without correction to calculate the concentration of the
       standard.

       7.3.1   Place approximately 8 mL of reagent water in a 10-mL ground-glass-stoppered volumetric
               flask.  Allow the flask to stand unstoppered for approximately 10 minutes or until all welted
               surfaces have dried.  For each  analyte, weigh the stoppered flask, add the compound,
               restopper,  then  immediately reweigh to prevent evaporation losses from affecting the
               measurement.

       7.3.2   LiquidsSUsing a microsyringe, add sufficient liquid (about 100 mg) so that the final solution
               will have a concentration of about 10 mg/mL.

       7.3.3   GasesSFill  a valved 5-mL gas-tight syringe with the compound.  Lower the needle to
               approximately 5 mm above the meniscus. Slowly introduce the compound above the surface
               of the meniscus. The gas will dissolve in the solvent.  Repeat if necessary to reach desired
               concentration.

       7.3.4   Fill the  flask to  volume, stopper, then mix by  inverting several times. Calculate the
               concentration in milligrams per milliliter (mg/mL, equivalent to micrograms per microliter
               [|ig/(iL]) from the weight gain.


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                                                                           Method 1671, Revision A
       7.3.5   Transfer the stock solution to a  PTFE-sealed screw-cap bottle.  Store,  with  minimal
               headspace, in the dark at approximately 4°C. Do not freeze.

       7.3.6   Replace standards after one month, or sooner if comparison with check standards indicate a
               change in concentration.  Quality control check standards that can be used to determine the
               accuracy of calibration standards may be available from the National Institute of Standards
               and Technology, Gaithersburg, MD.

7.4    Secondary standardsSUsing standard solutions (Section 7.3), prepare a secondary standard to contain
       each pollutant at a concentration of 100 mg/L or 500 mg/L for compounds with higher MLs. Where
       necessary, a concentration of 1000 mg/L may be used.

       7.4.1   Aqueous calibration standardsSUsing a syringe or a microsyringe, add sufficient secondary
               standard (Section 7.4) to five reagent water aliquots to produce concentrations in the range
               of interest.

       7.4.2   Aqueous performance standardSAn aqueous standard containing all pollutants and internal
               standard(s) is prepared daily, and analyzed each  shift to demonstrate performance (Section
               13).  This standard shall contain  concentrations of pollutants and internal standard(s), as
               appropriate, within a factor of 1 to 5 times the MLs of the pollutants listed in Table 1. It may
               be one of the aqueous calibration standards described in Section 7.4.1.

8.0    Sample Collection, Preservation,  and Handling

8.1    Grab samples are collected in glass containers having a total volume greater than 20 mL.  For aqueous
       samples that pour freely, fill sample bottles so that no air bubbles pass through the sample as the bottle
       is filled and seal each bottle so that no air bubbles are entrapped.  Maintain the hermetic seal on the
       sample bottle until time of analysis.

8.2    Maintain samples at 4 °C from the time of collection until analysis. Do not freeze.  If an aqueous
       sample contains residual chlorine, add sodium thiosulfate preservative  (10 mg/40 mL) to the empty
       sample bottles just prior to shipment to the sample site. EPA Methods 330.4 and 330.5 may be used
       for measurement of residual chlorine (Reference 5). If preservative has been added, shake the bottle
       vigorously for 1 minute immediately after filling.

8.3    For aqueous samples, experimental evidence indicates that some PMI analytes are susceptible to rapid
       biological degradation  under  certain environmental conditions.  Refrigeration alone  may not be
       adequate to preserve these compounds in wastewaters for more than seven days.  For this reason, a
       separate sample should be collected, acidified, and analyzed when compounds susceptible to  rapid
       biological degradation are to be determined. Collect about 500 mL of sample in a clean container.
       Adjust the pH of the sample to about 2 by adding hydrochloric acid (1:1) while stirring. Check pH
       with narrow range (1.4 to 2.8)  pH paper. Fill a sample bottle as described in Section 8.1. If residual
       chlorine is present, add sodium thiosulfate to a separate sample bottle and fill as in Section 8.1.

8.4    All samples shall be analyzed  within 14 days of collection.

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Method 1671, Revision A
9.0    Quality Assurance/Quality Control

9.1     Each laboratory that uses this method is required to operate a formal quality assurance program
        (Reference 6).  The minimum requirements of this program consist of an initial demonstration of
        laboratory capability (Section 9.5) and analysis of standards (Sections 9.6 and 13) and blanks (Section
        9.4) as tests of continued performance. Each time a batch of samples is analyzed or there is a change
        in reagents or procedures, a method blank must be analyzed as a safeguard against contamination.

9.2     In recognition of advances that are occurring  in analytical technology, and to allow the  analyst to
        overcome sample matrix interferences, the analyst is permitted certain options to improve separations
        or lower the  costs of measurements.  These options include alternative concentration and cleanup
        procedures, and changes in columns and detectors.  Alternative techniques, such as the substitution
        of spectroscopy or immunoassay, and changes that degrade method performance are not allowed. If
        an analytical technique other than the techniques specified in this method is used, that technique must
        have a specificity equal to or better than the specificity of the techniques in this method for the analytes
        of interest.

        9.2.1   If the detection limit of the method will be affected by the change, the laboratory is required
               to demonstrate that the method detection limit (MDL; 40 CFR 136, Appendix B) is lower than
               one-third the regulatory compliance level. If calibration will be affected by the change, the
               analyst must recalibrate the instrument per Section 10.

        9.2.2   The laboratory is required to maintain records of modifications made to this method.  These
               records include  the information in this subsection,  at a minimum.

               9.2.2.1  The names, titles, addresses, and telephone numbers of the analyst(s) who performed
                       the analyses and modification, and of the quality control officer who witnessed and
                       will verify the analyses and modification.

               9.2.2.2  A listing of pollutant(s) measured, by name and CAS Registry Number.

               9.2.2.3  A narrative stating the reason(s) for the  modification.

               9.2.2.4  Results from all quality control (QC) tests comparing the modified method to this
                       method including:
                       (a)     calibration (Section 10);
                       (b)     calibration verification (Section 13);
                       (c)     initial precision and accuracy (Section 9.5);
                       (d)     analysis of blanks (Section 9.4); and
                       (e)     accuracy assessment (Section 9.6 and 13).

               9.2.2.5  Data that will allow an independent reviewer to validate each determination by tracing
                       the instrument output (peak height, area, or other signal)  to the final result.  These
                       data are to include:

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                                                                            Method 1671, Revision A
                      (a)     sample numbers and other identifiers;
                      (b)     analysis dates and times;
                      (c)     injection logs;
                      (d)     analysis sequence/run chronology;
                      (e)     sample weight or volume;
                      (f)     sample volume prior to each cleanup step, if applicable;
                      (g)     sample volume after each cleanup step, if applicable;
                      (h)     final sample volume prior to injection;
                      (I)     injection volume;
                      (j)     dilution data, differentiating between dilution of a sample or an extract;
                      (k)     instrument and operating conditions;
                      (1)     column (dimensions, liquid phase, solid support, film thickness, etc.);
                      (m)     operating conditions (temperature, temperature program, flow rates, etc.);
                      (n)     detector (type, operating condition, etc.);
                      (o)     chromatograms, printer tapes, and other recording of raw data; and
                      (p)     quantitation reports, data system outputs, and other data necessary to link
                              raw data to the results reported.

9.3    With each sample batch, a matrix spike (MS) and matrix spike duplicate (MSB) are analyzed to assess
       precision and accuracy of the analysis. The relative percent difference (RPD) between the MS and
       MSB shall be less than 30% and compound recoveries shall fall within the limits specified in Table
       3.   If the recovery  of any  compound falls  outside its  warning limit, method performance  is
       unacceptable for that compound in that sample and the results may not be reported for regulatory
       compliance purposes.

9.4    Analyses of blanks are required to demonstrate freedom from contamination and that the compounds
       of interest and interfering compounds have not been  carried over from a previous analysis (Section
       4.3).

9.4.1   With each sample batch (samples analyzed on the same 12-hour shift), a blank shall be analyzed
       immediately after analysis of the aqueous performance standard (Sections 9.6 and 13) to demonstrate
       freedom from contamination.  If any  of the compounds of interest or any  potentially interfering
       compound is found in a blank at greater than the ML  (assuming a response factor of 1 relative to the
       nearest-eluted internal standard for compounds not listed in Table 1), analysis of samples is halted
       until the source of contamination is eliminated and a blank shows no evidence of contamination at this
       level.

9.5    Initial precision and recovery—To establish the ability to generate acceptable precision and accuracy,
       the analyst shall perform the following operations for compounds to be calibrated.

9.5.1   Analyze two sets of four 5-mL aliquots (eight aliquots total) of the aqueous performance standard
       (Section 7.4.2) containing the PMI analytes listed in Table 1.

9.5.2   Using the first set of four analyses, compute the average recovery (X) in percent of spike level and
       standard deviation of the recovery (s) in percent of spike level, for each compound.

                                               85                                        July 1998

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Method 1671, Revision A
9.5.3   For each compound, compare s and X with the corresponding limits for initial precision and accuracy
       found in Table 3. If s and X for all compounds meet the acceptance criteria, system performance is
       acceptable and analysis of blanks and samples may begin. If, however, any individual s exceeds the
       precision limit or any individual X falls outside the range for accuracy, system performance is
       unacceptable for that compound.

9.5.4   Using the results of the second set of analyses, compute s and X for only those compounds that failed
       the test of the first set of four analyses (Section 9.5.3). If these compounds now pass, the system
       performance is acceptable for all compounds, and analysis of blanks and samples may begin.  If,
       however, any of the same compounds fail again, the analysis system is not performing properly for the
       compound(s) in question. In this event, correct the problem and repeat the entire test (Section 9.5).
9.6    The laboratory shall, on an ongoing  basis, demonstrate through the analysis of the aqueous
       performance standard (Section 7.4.2) that the analysis system is in  control.  This procedure is
       described in Section 13.

9.7    Where available, field replicates may be used to validate the precision of the sampling technique.

9.8    The laboratory shall maintain records to define the quality of data that is generated.

10.0  Calibration

10.1   Inject standards into the GC and adjust the sensitivity to detect an amount of each compound less than
       or equal to one-third of the ML listed in Table 2 for the analyte.

10.2   Internal standard calibration procedure. The analyst must select one or more internal standards that
       are similar in analytical behavior to the compounds of interest.  The analyst must further demonstrate
       that the measurement of the internal standard(s) is not affected by method or matrix interferences.
       Because of these limitations, no internal standard that would be applicable to all samples can be
       required in the method.  The method was developed using tetrahydrofuran (THF) as an internal
       standard. Where THF is not present in the sample matrix and no interference precludes its use, THF
       is to be used as an internal standard  for application of this method. If interferences preclude use of
       THF and other internal standards, external standard calibration may be used.

       10.2.1  Prepare aqueous calibration standards at a minimum of five concentration levels for each
               analyte by carefully adding an appropriate amount of secondary standard to reagent water or
               to the matrix under study. One of the concentrations should be at or below the ML. The
               concentration range should bracket the concentrations expected in the samples and should not
               exceed the dynamic range of the GC/FID instrument. These aqueous standards must be
               prepared daily.

       10.2.2  Prepare a spiking solution containing the internal standard(s) using the procedures described
               in Sections 7.3 and 7.4 and add an appropriate amount of internal standard to each aqueous
               calibration standard.

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                                                                           Method 1671, Revision A
       10.2.3  Using injections appropriate to optimize system sensitivity and separation of the analytes,
               analyze  each calibration  standard and  tabulate peak height or area responses  against
               concentration for each compound and internal standard. Calculate response factors (RF) for
               each compound as follows:
                                               As x cs
               where:
               As  = Response for the analyte to be measured
               Ais = Response for the nearest e luting internal standard
               Cis = Concentration of the nearest eluting internal standard
               Cs = Concentration of the analyte to be measured

               If the RF value over the working range is  a constant (less than 10% relative standard
               deviation), 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 relative
               response, AS*C1S/A1S, against analyte concentration (Cs).

11.0  Sample  Preparation

       Samples containing less than 1% solids are analyzed directly as aqueous samples. Samples containing
       1 % solids or greater are analyzed after equilibration with reagent water containing internal standard(s) .

11.1   Determination of percent solids.

       11.1.1  Weigh 5 - 1 0 g of sample into a tared beaker.

       11.1.2  Dry overnight (12 hours minimum) at 1 10±5 °C, and cool in a desiccator.

       11.1.3  Determine the percent solids as follows:
                             % solids =  ^9ht of sample dry  x 1QQ
                                         weight of sample wet
11.2   Remove standards and samples from cold storage and bring to 20-25 °C.

11.3   Samples containing less than 1% solids.

       11.3.1  Allow solids to settle and remove 5 mL of sample.

       11.3.2  Add an appropriate amount of internal standard spiking solution.

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Method 1671, Revision A
        11.3.3  Inject a sample directly into the GC. The temperature of the injection block should be great
               enough to immediately vaporize the entire sample.  An example of the separations achieved
               by the column listed is shown in Figure 1.

Note:   Use of a 0.2-(iL injection has been found to improve method sensitivity  over a larger injection
        combined with a split sample.  Where possible, splitless injection should be used. All requirements
        of this Method must be met regardless of type of injection used.

11.4    Samples containing 1% solids or greater.

        11.4.1  Mix the sample thoroughly using a clean spatula and remove rocks, twigs, sticks, and other
               foreign matter.

        11.4.2  Add 5±1 g of sample to a tared 10-mL centrifuge tube. Using a clean metal spatula, break
               up any lumps of sample. Record the sample weight to three significant figures.

        11.4.3  Add  an appropriate amount of internal standard spiking solution to  the sample in the
               centrifuge tube.

        11.4.4  Add a measured quantity (Y ± 0.1 mL) of reagent water to the tube  so as to minimize head
               space.

        11.4.5  Place a cap on the centrifuge tube leaving little or no headspace.  Place the tube in the
               sonicator for a minimum of 5 minutes, turning occasionally. For most samples this should be
               sufficient time to distribute the analytes and standard(s) between the solid and aqueous phases
               and to establish equilibrium.  Some sample matrices may require more sonication.
        11.4.6  On completion of sonication, centrifuge the sample and inject the same amount of supernate
               into the GC that was injected for the calibration standards.

11.5    For liquid samples  containing  high-solids  concentrations, such as sludges  or muds, weigh
        approximately 5 g (to three significant figures) into a 10-mL centrifuge tube, add an appropriate
        amount of internal standard solution, sonicate, centrifuge, and inject as in Section 11.4.6.

12.0   Quantitative Determination

12.1    The calibration curve or averaged response factor determined during calibration  is used to calculate
        the concentration.  For calculation using the averaged RF, the equation below is used, and the terms
        are as defined in Section 10.2.3.

                                                    As x C,s
                                     Concentration = —	-
                                                   As x RF
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                                                                           Method 1671, Revision A
12.2   The concentration of the pollutant in the solid phase of the sample is computed using the concentration
       of the pollutant detected in the aqueous solution, as follows:


          Concentration in  solid(mg/kg) = YL x aclueous conc (m9/L) x percent solids x DF
                                               sample wt (kg)


              where:
              percent solids is from Section 11.1
              Y = Volume of water in liters (L) from 11.4.4
              DF = Dilution factor (as a decimal number), if necessary

12.3   Sample dilution—If the calibration range of the system is exceeded, the sample is diluted by successive
       factors of 10 until the sample concentration is within the calibration range.

12.4   Report results for all pollutants  found in standards, blanks, and samples to three significant figures.
       For samples containing less than 1% solids, the units are milligrams per liter (mg/L); and for samples
       containing 1% solids or greater, units are milligrams per kilogram (mg/kg).

13.0  System Performance

13.1   At the beginning of each 12-hour shift during which analyses are performed, system calibration and
       performance shall be verified.  Acceptance criteria for each compound (R) are found in Table 3.
       Adjustment and/or recalibration shall be performed until all performance criteria are met. Only after
       all performance criteria are met may blanks and samples be analyzed.

13.2   Where THF is used as the  internal standard, the absolute retention time of THF shall be 416 seconds
       (± 30 seconds). The relative retention times of all pollutants shall fall within 10% of the value given
       in Table 2.

14.0  Method Performance

14.1   This method was developed and validated in a single laboratory.

14.2   A chromatogram of the aqueous performance standard is shown in Figure 1.

15.0  Pollution Prevention

15.1   Pollution prevention encompasses any technique that reduces or eliminates the quantity or toxicity of
       waste at the point of generation.  Many opportunities for pollution prevention exist in laboratory
       operation. EPA has established a preferred hierarchy of environmental management techniques that
       places pollution prevention as the management option of first choice. Whenever feasible, laboratory
       personnel should use pollution prevention techniques to address their waste generation. When wastes
       cannot be reduced feasibly at the source, the Agency recommends recycling as the  next best option.


                                              89                                      July 1998

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Method 1671, Revision A
       The acids used in this Method should be reused as practicable by purifying by electrochemical
       techniques. The only other chemicals used in this Method are the neat materials used in preparing
       standards.  These standards are used  in extremely small amounts and pose  little threat to the
       environment when managed properly.  Standards should be prepared  in volumes consistent with
       laboratory use to minimize the disposal  of excess volumes of expired standards.

15.2   For information about pollution prevention that may be applied to laboratories and research
       institutions, consult Less is Better:  Laboratory Chemical Management for Waste Reduction,
       available from the American Chemical Society's Department of Governmental Relations and Science
       Policy, 1155 16th Street NW, Washington DC 20036, 202/872-4477.

16.0  Waste Management

16.1   It is the laboratory's responsibility to comply with all Federal, State, and local regulations governing
       waste management, particularly the hazardous waste identification rules and land-disposal restrictions.
       In addition, it is the laboratory's responsibility to protect air, water, and land resources by minimizing
       and controlling all releases from fume hoods and bench operations. Also, compliance is required with
       any sewage discharge permits and regulations.

16.2   Samples containing acids at a pH of less than 2 are hazardous and must be neutralized before being
       poured down a drain or must be handled as hazardous waste.

16.3   For further information on waste management, consult The  Waste Management Manual for
       Laboratory Personnel and Less is Better: Laboratory Chemical Management for Waste Reduction,
       both available from  the American Chemical Society's Department of Government Relations and
       Science Policy, 1155 16th Street NW, Washington, DC  20036.
July 1998                                      90

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                                                                       Method 1671, Revision A
17.0  References

1.      "Standard  Test  Method  for  Volatile  Alcohols  in  Water by Direct  Aqueous-Injection  Gas
       Chromatography." 1994 Annual Book of ASTM Standards, Volume 11.02 (Water (II)). ASTM, 1916
       Race Street, Philadelphia, PA  19103-1187.

2.      "Working with Carcinogens," DREW, PHS, NIOSH, Publication 77-206 (1977).

3.      "OSHA Safety and Health Standards, General Industry," 29 CFR 1910, OSHA 2206 (1976).

4.      "Safety in Academic Chemistry Laboratories," American Chemical Society Publication, Committee
       on Chemical Safety (1979).

5.      "Methods 330.4 and 330.5 for Total Residual Chlorine," USEPA, EMSL Cincinnati, OH 45268.

6.      "Method of Analytical Quality Control in Water and Wastewater Laboratories," USEPA, EMSL
       Cincinnati, OH 45268, EPA-4-79-019 (March, 1979).

7.      Technical Report to PhRMA from Tichler & Kocurek by Malcolm Pirnie Laboratory, EPA Water
       Docket for Pharmaceutical Manufacturing Industry rule proposed May 2,  1995 (60 FR 21592),
       Document Control Number 8166 at Record Section 13.2.4. (February 13,  1997).
                                             91                                      July 1998

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Method 1671, Revision A
18.0  Tables

Table 1.  Non-purgeable Water Soluble PMI Analytes to be  Analyzed  by Direct Aqueous
          Injection GC/FID and Internal Standard Techniques
         PMI Analyte

         Acetonitrile

         Diethylamine

         Dimethylamine

         Dimethyl sulfoxide

         Ethanol

         Ethylene glycol

         Formamide

         Methanol

         Methylamine

         Methyl Cellosolve® (2-methoxyethanol)

         n-Propanol

         Triethylamine
          CASRN1

           75-05-8

          109-89-7

          124-40-3

           67-68-5

           64-17-5

          107-21-1

           75-12-7

           67-56-1

           74-89-5

          109-86-4

           71-23-8

          121-44-8
EPA-EGD

      972

      986

      987

     1037

      134

     1038

      988

      135

      989

     1040

      955

      990
 Chemical Abstracts Service Registry Number
July 1998
92

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                                                                             Method 1671, Revision A
Table 2.
EGD
No.
989
135
987
134
972
955
986
975
1040
988
1038
990
1037
Gas Chromatographic Retention Times and Minimum Levels for
Soluble PMI Analytes by Direct Aqueous Injection GC/FID
Non-purgeable Water
Retention Time
PMI Analyte
Methylamine
Methanol
Dimethylamine
Ethanol
Acetonitrile
n-Propanol
Diethylamine
Tetrahydrofuran (int std)
Methyl Cellosolve®
Formamide
Ethylene glycol
Triethylamine
Dimethyl sulfoxide
Mean (sec)
128
139
165
188
203
307
341
416
429
473
495
518
676
EGD Ref
975
975
975
975
975
975
975
975
975
975
975
975
975
Relative
0.307
0.334
0.396
0.452
0.488
0.737
0.819
1.000
1.030
1.136
1.189
1.244
1.624
ML1
(mg/L)
50
2(2)
50
2(2)
50
50
50

20
100
100
50
20
1        This is a minimum level at which the entire analytical system shall give an acceptable calibration point,
taking into account method-specific sample and injection volumes. The concentration in the aqueous or solid
phase is determined using the equations in Section  12.
2        The minimum level for this analyte was developed from data provided in Reference 7.
                                                93
July 1998

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Method 1671, Revision A
Table
3. Acceptance Criteria for Performance Tests
Acceptance Criteria (%
Initial Precision and
Accuracy
EGD
No.
972
986
987
1037
134
1038
988
135
989
1040
955
990
PMI Analyte
Acetonitrile
Diethylamine
Dimethylamine
Dimethyl sulfoxide
Ethanol
Ethylene glycol
Formamide
Methanol
Methylamine
Methyl Cellosolve®
n-Propanol
Triethylamine
Spike
Level
50
50
50
50
50
100
200
50
50
50
50
50
s
30
20
27
20
20
22
20
21
20
20
25
47

70
65
70
31
70
70
70
70
70
64
70
70
X
- 146
- 130
- 153
- 130
- 131
- 149
- 130
- 130
- 130
- 130
- 137
- 165
of Spike Level)
On-going
Accuracy

70
70
70
30
70
70
70
70
70
64
70
68
R
- 148
- 130
- 155
- 130
- 132
- 150
- 130
- 130
- 130
- 130
- 139
- 168
July 1998
94

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                                                              Method 1671, Revision A
100% -,
 FS   -
   0
                                       Aialysis :4MDLJ,a, 1
                                       Crated a UCMficn Of/DscA4
                                       Sample* :S
                                       hjeciori*: 1
                                       Sample Name: MDL#3
           2     3    45    678    9     10    11     12
                 Figure 1.  C h ro matog ra m o f Aqueous Be rtor ma nee
                           Standard of Anatytes torn Table 1
                                      95
July 1998

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