Method 1625C Semivolatile Organic Compounds by Isotope Dilution GCMS June 1989 U.S. Environmental Protection Agency Office of Science and Technology Engineering and Analysis Division 401 M Street S.W. Washington, D.C. 20460 ------- Method 1625C Semivolatile Organic Compounds by Isotope Dilution GCMS 1.0 Scope and Application 1.1 This method is designed to meet the survey requirements of the USEPA ITD. The method is used to determine the semivolatile toxic organic pollutants associated with the Clean Water Act (as amended 1987); the Resource Conservation and Recovery Act (as amended 1986); the Comprehensive Environmental Response, Compensation and Liability Act (as amended 1986); and other compounds amenable to extraction and analysis by capillary column gas chromatography-mass spectrometry (GCMS). 1.2 The chemical compounds listed in Tables 1-4 may be determined in waters, soils, and municipal sludges by the method. 1.3 The detection limits of the method are usually dependent on the level of interferences rather than instrumental limitations. The limits in Tables 5 and 6 typify the minimum quantities that can be detected with no interferences present. 1.4 The GCMS portions of the method are for use only by analysts experienced with GCMS or under the close supervision of such qualified persons. Laboratories unfamiliar with analysis of environmental samples by GCMS should run the performance tests in Reference 1 before beginning. TABLE 1. BASE/NEUTRAL EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES Pollutant Labeled Compound CAS EPA- CAS EPA- Compound Storet Registry EGD NPDES Analog Registry EGD acenaphthene 34205 83-32-9 001 B 001 B dio 15067-20-2 201 B acenaphthylene 34200 208-96-8 077 B 002 B d8 93951-97-4 277 B anthracene 34220 120-12-7 078 B 003 B dio 1719-06-8 278 B benzidine 39120 92-87-5 005 B 004 B d8 92890-63-6 205 B benzo (a) anthracene 34526 56-55-3 072 B 005 B diz 1718-53-2 272 B benzo (b) fluoranthene 34230 205-99-2 074 B 007 B diz 93951-98-5 274 B benzo (k) fluoranthene 34242 207-08-9 075 B 009 B diz 93952-01-3 275 B benzo(a)pyrene 34247 50-32-8 073 B 006 B di2 63466-71-7 273 B benzo (ghi) perylene 34521 191-24-2 079 B 008 B di2 93951-66-7 279 B biphenyl (Appendix C) 81513 92-52-4 512 B dio 1486-01-7 612 B bis(2-chloroethyl) ether 34273 111-44-4 018 B 011 B d8 93952-02-4 218 B bis(2-chloroethoxy) methane 34278 111-91-1 043 B 010 B d8 93966-78-0 243 B bis(2-chloroisopropyl) ether 34283 108-60-1 042 B 012 B di2 93951-67-8 242 B bis(2-ethylhexyl) phthalate 39100 117-81-7 066 B 013 B d4 93951-87-2 266 B 2 September 1989 ------- Method 1625C TABLE 1. BASE/NEUTRAL EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES Pollutant Labeled Compound CAS EPA- CAS EPA- Compound Storet Registry EGD NPDES Analog Registry EGD 4-bromophenyl phenyl ether 34636 101-55-3 041 B 014 B d5 93951-83-8 241 B butyl benzyl phthalate 34292 85-68-7 067 B 015 B d4 93951-88-3 267 B n-CIO (Appendix C) 77427 124-18-5 517 B ^22 16416-29-8 617 B n-C12 (Appendix C) 77588 112-40-3 506 B ^26 16416-30-1 606 B n-C14 (Appendix C) 77691 629-59-4 518 B 618 B n-C16 (Appendix C) 77757 544-76-3 519 B ^34 15716-08-2 619 B n-C18 (Appendix C) 77804 593-45-3 520 B 620 B n-C20 (Appendix C) 77830 112-95-8 521 B ^42 62369-67-9 621 B n-C22 (Appendix C) 77859 629-97-0 522 B 622 B n-C24 (Appendix C) 77886 646-31-1 523 B ^50 16416-32-3 623 B n-C26 (Appendix C) 77901 630-01-3 524 B 624 B n-C28 (Appendix C) 78116 630-02-4 525 B 625 B n-C30 (Appendix C) 78117 638-68-6 526 B ^62 93952-07-9 626 B carbazole (4c) 77571 86-74-8 528 B d8 38537-24-5 628 B 2-chloronaphthalene 34581 91-58-7 020 B 016 B d7 93951-84-9 220 B 4-chlorophenyl phenyl ether 34641 7005-72-3 040 B 017 B d5 93951-85-0 240 B chrysene 34320 218-01-9 076 B 018 B diz 1719-03-5 276 B p-cymene (Appendix C) 77356 99-87-6 513 B dM 93952-03-5 613 B dibenzo (a,h) anthracene 34556 53-70-3 082 B 019 B dM 13250-98-1 282 B dibenzofuran 81302 132-64-9 505 B d8 93952-04-6 605 B (Appendix C & 4c) dibenzothiophene (Synfuel) 77639 132-65-0 504 B d8 33262-29-2 604 B di-n-butyl phthalate 39110 84-74-2 068 B 026 B d4 93952-11-5 268 B 1,2-dichlorobenzene 34536 95-50-1 025 B 020 B d4 2199-69-1 225 B 1,3-dichlorobenzene 34566 541-73-1 026 B 021 B d4 2199-70-4 226 B 1,4-dichlorobenzene 34571 106-46-7 027 B 022 B d4 3855-82-1 227 B 3,3'-dichlorobenzidine 34631 91-94-1 028 B 023 B d6 93951-91-8 228 B diethyl phthalate 34336 84-66-2 070 B 024 B d4 93952-12-6 270 B 2,4-dimethylphenol 34606 105-67-9 034 A 003 A d3 93951-75-8 234 A dimethyl phthalate 34341 131-11-3 071 B 025 B d4 93951-89-4 271 B 2,4-dinitrotoluene 34611 121-14-2 035 B 027 B d3 93951-68-9 235 B 2,6-dinitrotoluene 34626 606-20-2 036 B 028 B d3 93951-90-7 236 B di-n-octyl phthalate 34596 117-84-0 069 B 029 B d4 93952-13-7 269 B diphenylamine 77579 122-39-4 507 B dio 37055-51-9 607 B (Appendix C) diphenyl ether 77587 101-84-8 508 B dio 93952-05-7 608 B (Appendix C) 1,2-diphenylhydrazine 34346 122-66-7 037 B 030 B dio 93951-92-9 237 B fluoranthene 34376 206-44-0 039 B 031 B dio 93951-69-0 231 B fluorene 34381 86-73-7 080 B 032 B dio 81103-79-9 280 B hexachlorobenzene 39700 118-74-1 009 B 033 B 13C 93952-14-8 209 B hexachlorobutadiene 34391 87-68-3 052 B 034 B 13c 4 93951-70-3 252 B hexachloroethane 34396 67-72-1 012 B 036 B 13c 93952-15-9 212 B hexachlorocyclopentadiene 34386 77-47-4 053 B 035 B 13c 4 93951-71-4 253 B September 1989 3 ------- Method 1625C TABLE 1. BASE/NEUTRAL EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES Pollutant Labeled Compound CAS EPA- CAS EPA- Compound Storet Registry EGD NPDES Analog Registry EGD indeno(l,2,3-cd)pyrene 34403 193-39-5 083 B 037 B isophorone 34408 78-59-1 054 B 038 B d8 93952-16-0 254 B naphthalene 34696 91-20-3 055 B 039 B d8 1146-65-2 255 B beta-naphthylamine 82553 91-59-8 502 B d7 93951-94-1 602 B (Appendix C) nitrobenzene 34447 98-95-3 056 B 040 B d5 4165-60-0 256 B N-nitrosodimethylamine 34438 62-75-9 061 B 041 B d6 17829-05-9 261 B N-nitrosodi-n-proplyamine 34428 621-64-7 063 B 042 B di4 93951-96-3 263 B N-nitrosodiphenylamine 34433 86-30-6 062 B 043 B d6 93951-95-2 262 B phenanthrene 34461 85-01-8 081 B 044 B dio 1517-22-2 281 B phenol 34694 108-95-2 065 A 010 A d5 4165-62-2 265 A alpha-picoline (Synfuel) 77088 109-06-8 503 B d7 93951-93-0 603 B pyrene 34469 129-00-0 084 B 045 B dio 1718-52-1 284 B styrene (Appendix C) 77128 100-42-5 510 B d5 5161-29-5 610 B alpha-terpineol 77493 98-55-5 509 B d3 93952-06-8 609 B (Appendix C) 1,2,3-trichlorobenzene (4c) 77613 87-61-6 529 B d3 3907-98-0 629 B 1,2,4-trichlorobenzene 34551 120-82-1 008 B 046 B d3 2199-72-6 208 B TABLE 2. ACID EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES Pollutant Labeled Compound CAS EPA- CAS EPA- Compound Storet Registry EGD NPDES Analog Registry EGD 4-chloro-3-methylphenol 34452 59-50-7 022 A 008 A d2 93951-72-5 222 A 2-chlorophenol 34586 95-57-8 024 A 001 A d4 93951-73-6 224 A 2,4-dichlorophenol 34601 120-83-2 031 A 002 A d3 93951-74-7 231 A 2,4-dinitrophenol 34616 51-28-5 059 A 005 A d3 93951-77-0 259 A 2-methyl-4,6-dinitrophenol 34657 534-52-1 060 A 004 A d2 93951-76-9 260 A 2-nitrophenol 34591 88-75-5 057 A 006 A d4 93951-75-1 257 A 4-nitrophenol pentachlorophenol 34646 39032 100-02-7 87-86-5 058 064 A A 007 009 A A d4 13c6 93951-79-2 85380-74-1 258 264 A A 2,3,6-trichlorophenol (4c) 77688 933-75-5 530 A d2 93951-81-6 630 A 2,4,5-trichlorophenol (4c) 95-95-4 531 A d2 93951-82-7 631 A 2,4,6-trichlorophenol 34621 88-06-2 021 A 011 A d2 93951-80-5 221 A 4 September 1989 ------- Method 1625C TABLE 3. BASE/NEUTRAL EXTRACTABLE COMPOUNDS TO BE DETERMINED BY REVERSE SEARCH AND QUANTITATION USING KNOWN RETENTION TIMES, RESPONSE FACTORS, REFERENCE COMPOUND, AND MASS SPECTRA EGD No. Compound CAS Registry 555 acetophenone 98-86-2 556 4-aminobiphenyl 92-67-1 557 aniline 62-53-3 558 o-anisidine 90-04-0 559 aramite 140-57-8 560 benzanthrone 82-05-3 561 l,3-benzenediol(resorcinol) 108-46-3 562 benzenethiol 108-98-5 563 2,3-benzofluorene 243-17-4 564 benzyl alcohol 100-51-6 565 2-bromochlorobenzene 694-80-4 566 3-bromochlorobenzene 108-37-2 567 4-chloro-2-nitroaniline 89-63-4 568 5-chloro-o-toluidine 95-79-4 569 4-chloroaniline 106-47-8 570 3-chloronitrobenzene 121-73-3 571 o-cresol 95-48-7 572 crotoxyphos 7700-17-6 573 2,6-di-tert-butyl-p-benzoquinone 719-22-2 574 2,4-diaminotoluene 95-80-7 575 1,2-dibromo-3-chloropropane 96-12-8 576 2,6-dichloro-4-nitroaniline 99-30-9 577 l,3-dichloro-2-propanol 96-23-1 578 2,3-dichloroaniline 608-27-5 579 2,3-dichloronitro-benzene 3209-22-1 580 l,2:3,4-diepoxybutane 1464-53-5 581 3,3'-dimethoxybenzidine 119-90-4 582 dimethyl sulfone 67-71-0 583 p-dimethylamino-azobenzene 60-11-7 584 7,12-dimethylbenz- (a) anthracene 57-97-6 585 N,N-dimethylformamide 68-12-2 586 3,6-dimethylphenanthrene 1576-67-6 587 1,4-dinitrobenzene 100-25-4 588 diphenyldisulfide 882-33-7 589 ethyl methanesulfonate 62-50-0 590 ethylenethiourea 96-45-7 591 ethynylestradiol3-methyl ether 72-33-3 592 hexachloropropene 1888-71-7 593 2-isopropylnaphthalene 2027-17-0 594 isosafrole 120-58-1 595 longifolene 475-20-7 596 malachite green 569-64-2 597 methapyrilene 91-80-5 598 methyl methanesulfonate 66-27-3 599 2-methylbenzothioazole 120-75-2 900 3-methylcholanthrene 56-49-5 September 1989 5 ------- Method 1625C TABLE 3. BASE/NEUTRAL EXTRACTABLE COMPOUNDS TO BE DETERMINED BY REVERSE SEARCH AND QUANTITATION USING KNOWN RETENTION TIMES, RESPONSE FACTORS, REFERENCE COMPOUND, AND MASS SPECTRA EGD No. Compound CAS Registry 901 4,4'-methylene-bis(2-chloroaniline) 101-14-4 902 4,5-methylene-phenanthrene 203-64-5 903 1 -methy lfluorene 1730-37-6 904 2-methylnaphthalene 91-57-6 905 1 -methy lphenanthrene 832-69-9 906 2-(methylthio)-benzothiazole 615-22-5 907 1,5-naphthalenediamine 2243-62-1 908 1,4-naphthoquinone 130-15-4 909 alpha-naphthylamine 134-32-7 910 5-nitro-o-toluidine 99-55-8 911 2-nitroaniline 88-74-4 912 3-nitroaniline 99-09-2 913 4-nitroaniline 100-01-6 914 4-nitrobiphenyl 92-93-3 915 N-nitrosodi-n-butylamine 924-16-3 916 N-nitrosodiethylamine 55-18-5 917 N-nitrosomethyl-ethylamine 10595-95-6 918 N-nitrosomethyl-phenylamine 614-00-6 919 N-nitrosomorpholine 59-89-2 920 N-nitrosopiperidine 100-75-4 921 pentachlorobenzene 608-93-5 922 pentachloroethane 76-01-7 923 pentamethylbenzene 700-12-9 924 perylene 198-55-0 925 phenacetin 62-44-2 926 phenothiazine 92-84-2 927 1 -phenylnaphthalene 605-02-7 928 2-phenylnaphthalene 612-94-2 929 pronamide 23950-58-5 930 pyridine 110-86-1 931 safrole 94-59-7 932 squalene 7683-64-9 933 1,2,4,5-tetra-chlorobenzene 95-94-3 934 thianaphthene (2,3-benzothiophene) 95-15-8 935 thioacetamide 62-55-5 936 thioxanthone 492-22-8 937 o-toluidine 95-53-4 938 1,2,3-trimethoxybenzene 634-36-6 939 2,4,5-trimethylaniline 137-17-7 940 triphenylene 217-59-4 941 tripropyleneglycolmethyl ether 20324-33-8 942 1,3,5-trithiane 291-21-4 6 September 1989 ------- Method 1625C 2.0 Summary of Method 2.1 The percent solids content of a sample is determined. Stable isotopically labeled analogs of the compounds of interest are added to the sample. If the solids content is less than 1%, a 1 L sample is extracted at pH 12-13, then at pH <2 with methylene chloride using continuous extraction techniques. If the solids content is 30% or less, the sample is diluted to 1% solids with reagent water, homogenized ultrasonically, and extracted at pH 12-13, then at pH <2 with methylene chloride using continuous extraction techniques. If the solids content is greater than 30%, the sample is extracted using ultrasonic techniques. Each extract is dried over sodium sulfate, concentrated to a volume of 5 mL, cleaned up using gel permeation chromatography (GPC), if necessary, and concentrated. Extracts are concentrated to 1 mL if GPC is not performed, and to 0.5 mL if GPC is performed. An internal standard is added to the extract, and a 1 |iL aliquot of the extract is injected into the gas chromatograph (GC). The compounds are separated by GC and detected by a mass spectrometer (MS). The labeled compounds serve to correct the variability of the analytical technique. TABLE 4. ACID EXTRACTABLE COMPOUNDS TO BE DETERMINED BY REVERSE SEARCH AND QUANTITATION USING KNOWN RETENTION TIMES, RESPONSE FACTORS, REFERENCE COMPOUND, AND MASS SPECTRA EGD No. Compound CAS Registry 943 benzoic acid 65-85-0 944 p-cresol 106-44-5 945 3,5-dibromo-4-hydroxybenzonitrile 1689-84-5 946 2,6-dichlorophenol 87-65-0 947 hexanoic acid 142-62-1 948 2,3,4,6-tetrachlorophenol 58-90-2 2.2 Identification of a pollutant (qualitative analysis) is performed in one of three ways: (1) For compounds listed in Tables 1 and 2, and for other compounds for which authentic standards are available, the GCMS system is calibrated and the mass spectrum and retention time for each standard are stored 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) For compounds listed in Tables 3 and 4, and for other compounds for which standards are not available, a compound is identified when the retention time and mass spectrum agree with those specified in this method. (3) For chromatographic peaks which are not identified by (1) and (2) above, the background corrected spectrum at the peak maximum is compared with spectra in the EPA/NIH Mass Spectral File (Reference 2). Tentative identification is established when the spectrum agrees (see Section 13). 2.3 Quantitative analysis is performed in one of four ways by GCMS using extracted ion current profile (EICP) areas: (1) For compounds listed in Tables 1 and 2, and for other compounds for which standards and labeled analogs are available, the GCMS system is calibrated and the compound concentration is determined using an isotope dilution technique. (2) For compounds listed in Tables 1 and 2, and for other compounds for which authentic standards but no labeled compounds are available, the GCMS system is calibrated and the compound concentration is determined using an internal standard technique. (3) For compounds listed in Tables 3 and 4, and for other compounds for which standards are not available, compound concentrations are determined using September 1989 7 ------- Method 1625C known response factors. (4) For compounds for which neither standards nor known response factors are available, compound concentration is determined using the sum of the EICP areas relative to the sum of the EICP areas of the internal standard. 2.4 The quality of the analysis is assured through reproducible calibration and testing of the extraction and GCMS systems. TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 solids Solids No.1 Compound (sec) Ref Relative2 (l-ig/L) (l-ig/kg) (l-ig/kg) 164 2,2'-difluorobiphenyl (int std) 1163 164 1.000-1.000 10 930 pyridine 378 164 0.325 261 N-nitrosodimethylamine-d65 378 164 0.286- 0.364 50 361 N-nitrosodimethylamine5 385 261 1.006-1.028 50 16 27 585 N,N-dimethylformamide 407 164 0.350 580 l,2:3,4-diepoxybutane 409 164 0.352 603 alpha picoline-d7 417 164 0.326-0.393 50 703 alpha picoline 426 603 1.006-1.028 50 25 87 917 N-nitrosomethylethylamine 451 164 0.338 598 methyl methanesulfonate 511 164 0.439 610 styrene-d5 546 164 0.450-0.488 10 710 styrene 549 610 1.002-1.009 10 149* 17 916 N-nitrosodiethylamine 570 164 0.490 577 1,3-dichloro-2-propanol 589 164 0.506 589 ethyl methanesulfonate 637 164 0.548 582 dimethyl sulfone 649 164 0.558 562 benzenethiol 667 164 0.574 922 pentachloroethane 680 164 0.585 557 aniline 694 164 0.597 613 p-cymene-d14 742 164 0.624-0.652 10 713 p-cymene 755 613 1.008-1.023 10 426* 912* 265 phenol-d5 696 164 0.584-0.613 10 365 phenol 700 265 0.995-1.010 10 2501* 757* 218 bis(2-chloroethyl) ether-d8 696 164 0.584-0.607 10 318 bis(2-chloroethyl) ether 704 218 1.007-1.016 10 32 22 617 n-C10-d22 698 164 0.585-0.615 10 717 n-CIO 720 617 1.022-1.038 10 299* 1188* 226 1,3-dichlorobenzene-d4 722 164 0.605-0.636 10 326 1,3-dichlorobenzene 724 226 0.998-1.008 10 46 26 227 1,4-dichlorobenzene-d4 737 164 0.601-0.666 10 327 1,4-dichlorobenzene 740 227 0.997-1.009 10 35 20 225 1,2-dichlorobenzene-d4 758 164 0.632-0.667 10 325 1,2-dichlorobenzene 760 225 0.995-1.008 10 63 16 935 thioacetamide 768 164 0.660 564 benzyl alcohol 785 164 0.675 8 September 1989 ------- Method 1625C TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Retention Time Method Detection Limit4 EGD No.1 Compound 242 bis(2-chloroisopropyl) Mean (sec) EGD Ref Relative2 0.664-0.691 1.010-1.016 0.700 0.689-0.716 Minimum Low High Level3 solids Solids (l-ig/L) (ng/kg) (ng/kg) 342 571 263 363 555 212 312 937 919 575 256 356 566 565 941 254 354 942 920 234 334 243 343 208 308 558 255 355 934 609 709 606 706 629 729 252 352 ether-d12 bis(2-chloroisopropyl) ether o-cresol N-nitrosodi-n- propylamine-d145 N-nitrosodi-n-propylamine5 acetophenone hexachloroethane-13C hexachloroethane o-toluidine N-nitrosomorpholine 1,2-dibromo-3-chloropropane nitrobenzene-d5 nitrobenzene 3-bromochlorobenzene 2-bromochlorobenzene tripropylene glycol methyl ether isophorone-d8 isophorone 1,3,5-trithiane N-nitrosopiperidine 2,4-dimethylphenol-d3 2,4-dimethylphenol bis(2-chloroethoxy) methane-d65 bis(2-chloroethoxy) methane5 1,2,4-trichlorobenzene-d3 1,2,4-trichlorobenzene o-anisidine naphthalene-d8 naphthalene thianapthene alpha-terpineol-d3 alpha-terpineol n-C12-d26 n-C12 l,2,3-trichlorobenzene-d35 1,2,3-trichlorobenzene5 hexachlorobutadiene-13C4 hexachlorobutadiene 788 799 814 817 164 242 164 164 10 10 20 24 39 830 263 1.008-1.023 20 46 47 818 164 0.703 819 164 0.690-0.717 10 823 212 0.999-1.001 10 58 55 830 164 0.714 834 164 0.717 839 164 0.721 845 164 0.706-0.727 10 849 256 1.002-1.007 10 39 28 854 164 0.734 880 164 0.757 881 164 0.758 881 164 0.747-0.767 10 889 254 0.999-1.017 10 8 5 889 164 0.764 895 164 0.770 921 164 0.781-0.803 10 924 234 0.999-1.003 10 26 13 933 164 0.792-0.807 10 939 243 1.000-1.013 10 26 23 955 164 0.813-0.830 10 958 208 1.000-1.005 10 49 24 962 164 0.827 963 164 0.819-0.836 10 967 255 1.001-1.006 10 62 42 971 164 0.835 973 164 0.829-0.844 10 975 609 0.998-1.008 10 nd nd 953 164 0.730-0.908 10 981 606 0.986-1.051 10 860* 3885* 1000 164 0.852-0.868 10 1003 629 1.000-1.005 10 260* 164* 1005 164 0.856-0.871 10 1006 252 0.999-1.002 10 46 22 September 1989 9 ------- Method 1625C TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Retention Time Method Detection Limit4 EGD No.1 Compound Mean (sec) EGD Ref Relative; Minimum Low Level3 solids (l-ig/L) (ng/kg) High Solids (l-ig/kg) 918 N -nitrosomethy lphenylamine 1006 164 0.865 592 hexachloropropene 1013 164 0.871 569 4-chloroaniline 1016 164 0.874 570 3-chloronitrobenzene 1018 164 0.875 915 N-nitrosodi-n-butylamine 1063 164 0.914 923 pentamethylbenzene 1083 164 0.931 561 1,3-benzenediol 1088 164 0.936 931 safrole 1090 164 0.937 939 2,4,5-trimethylaniline 1091 164 0.938 904 2-methylnaphthalene 1098 164 0.944 599 2-methylbenzothiazole 1099 164 0.945 568 5-chloro-o-toluidine 1101 164 0.947 938 1,2,3-trimethoxy benzene 1128 164 0.970 933 1,2,4,5-tetr achlorobenzene 1141 164 0.981 253 hexachlorocyclo- pentadiene-13C4 1147 164 0.976-0.986 10 353 hexachlorocyclopentadiene 1142 253 0.999-1.001 10 nd nd 594 isosafrole (cis or trans) 1147 164 0.986 594 isosafrole (cis or trans) 1190 164 1.023 578 2,3-dichloroaniline 1160 164 0.997 574 2,4-diaminotoluene 1187 164 1.021 220 2-chloronaphthalene-d7 1185 164 1.014-1.024 10 320 2-chloronaphthalene 1200 220 0.997-1.007 10 80 59 518 n-C14 1203 164 1.034 10 256 3533 612 biphenyl-d10 1195 164 1.016-1.027 10 712 biphenyl 1205 612 1.001-1.006 10 67 55 608 diphenyl ether-d10 1211 164 1.036-1.047 10 708 diphenyl ether 1216 608 0.997-1.009 10 44 12 579 2,3-dichloronitrobenzene 1214 164 1.044 911 2-nitroaniline 1218 164 1.047 908 1,4-naphthoquinone 1224 164 1.052 595 longifolene 1225 164 1.053 277 acenaphthylene-d8 1265 164 1.080-1.095 10 377 acenaphthylene 1247 277 1.000-1.004 10 57 18 593 2-isopropylnaphthalene 1254 164 1.078 587 1,4-dinitrobenzene 1255 164 1.079 576 2,6-dichloro-4-nitroaniline 1259 164 1.083 271 dimethyl phthalate-d4 1269 164 1.083-1.102 10 371 dimethyl phthalate 1273 271 0.998-1.005 10 62 21 573 2,6-di-t-butyl-p-benzoquinone 1273 164 1.095 236 2,6-dinitrotoluene-d3 1283 164 1.090-1.112 10 336 2,6-dinitrotoluene 1300 236 1.001-1.005 10 55 47 912 3-nitroaniline 1297 164 1.115 10 September 1989 ------- Method 1625C TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 solids Solids No.1 Compound (sec) Ref Relative2 (Pg/L) (l-ig/kg) (l-ig/kg) 201 acenaphthene-d10 1298 164 1.107-1.125 10 301 acenaphthene 1304 201 0.999-1.009 10 64 55 605 dibenzofuran-d8 1331 164 1.134-1.155 10 705 dibenzofuran 1335 605 0.998-1.007 10 77 210* 921 pentachlorobenzene 1340 164 1.152 909 alpha-naphthylamine 1358 164 1.168 235 2,4-dinitrotoluene-d3 1359 164 1.152-1.181 10 335 2,4-dinitrotoluene 1364 235 1.000-1.002 10 65 209* 602 beta-naphthylamine-d7 1368 164 1.163-1.189 50 702 beta-naphthylamine 1371 602 0.996-1.007 50 49 37 590 ethylenethiourea 1381 164 1.187 280 fluorene-d10 1395 164 1.185-1.214 10 380 fluorene 1401 281 0.999-1.008 10 69 61 240 4-chlorophenyl phenyl ether-d5 1406 164 1.194-1.223 10 340 4-chlorophenyl phenyl ether 1409 240 0.990-1.015 10 73 59 270 diethyl phthalate-d4 1409 164 1.197-1.229 10 370 diethyl phthalate 1414 270 0.996-1.006 10 52 16 906 2- (methyl thio) benzothiazole 1415 164 1.217 567 4-chloro-2-nitroaniline 1421 164 1.222 910 5-nitro-o-toluidine 1422 164 1.223 913 4-nitroaniline 1430 164 1.230 619 n-C16-d34 1447 164 1.010-1.478 10 719 n-C16 1469 619 1.013-1.020 10 116* 644* 237 l,2-diphenylhydrazine-d8 1433 164 1.216-1.248 20 337 1,2-diphenylhydrazine6 1439 237 0.999-1.009 20 48 27 607 diphenylamine-d10 1437 164 1.213-1.249 20 707 diphenylamine 1439 607 1.000-1.007 20 58 54 262 N-nitrosodiphenylamine-d6 1447 164 1.225-1.252 20 362 N-nitrosodiphenylamine7 1464 262 1.000-1.002 20 55 36 241 4-bromophenyl phenyl ether-d55 1495 164 1.271-1.307 10 341 4-bromophenyl phenyl ether5 1498 241 0.990-1.015 10 55 17 925 phenacetin 1512 164 1.300 903 1 -methy lfluorene 1514 164 1.302 209 hexachlorobenzene-13C6 1521 164 1.288-1.327 10 309 hexachlorobenzene 1522 209 0.999-1.001 10 51 48 556 4-aminobiphenyl 1551 164 1.334 929 pronamide 1578 164 1.357 281 phenanthrene-d10 1578 164 1.334-1.380 10 520 n-C18 1580 164 1.359 10 134* 844* 381 phenanthrene 1583 281 1.000-1.005 10 42 22 278 anthracene-d10 1588 164 1.342-1.388 10 September 1989 11 ------- Method 1625C TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 solids Solids No.1 Compound (sec) Ref Relative2 (l-ig/L) (l-ig/kg) (l-ig/kg) 378 anthracene 1592 278 0.998-1.006 10 52 21 604 dibenzothiophene-d8 1559 164 1.314-1.361 10 704 dibenzothiophene 1564 604 1.000-1.006 10 72 71 588 diphenyldisulfide 1623 164 1.396 914 4-nitrobiphenyl 1639 164 1.409 927 1 -pheny lnaphthalene 1643 164 1.413 628 carbazole-d85 1645 164 1.388-1.439 20 728 carbazole5 1650 628 1.000-1.006 20 47 24 621 n-C20-d42 1655 164 1.184-1.662 10 721 n-C20 1677 621 1.010-1.021 10 83 229* 907 1,5-naphthalenediamine 1676 164 1.441 902 4,5-methylenephenanthrene 1690 164 1.453 905 1 -methy lphenanthrene 1697 164 1.459 268 di-n-butyl phthalate-d4 1719 164 1.446-1.510 10 368 di-n-butyl phthalate 1723 268 1.000-1.003 10 64 80 928 2-phenylnaphthalene 1733 164 1.490 586 3,6-dimethylphenanthrene 1763 164 1.516 597 methapyrilene 1781 164 1.531 926 phenothiazine 1796 164 1.544 239 fluoranthene-d10 1813 164 1.522-1.596 10 339 fluoranthene 1817 239 1.000-1.004 10 54 22 572 crotoxyphos 1822 164 1.567 936 thioxanthone 1836 164 1.579 284 pyrene-d10 1844 164 1.523-1.644 10 384 pyrene 1852 284 1.001-1.003 10 40 48 205 benzidine-d8 1854 164 1.549-1.632 50 305 benzidine 1853 205 1.000-1.002 50 nd nd 522 n-C22 1889 164 1.624 10 432* 447* 559 aramite 1901 164 1.635 559 aramite 1916 164 1.647 583 p-dimethylaminoazobenzene 1922 164 1.653 563 2,3-benzofluorene 1932 164 1.661 623 n-C24-d50 1997 164 1.671-1.764 10 723 n-C24 2025 612 1.012-1.015 10 — — 932 squalene 2039 164 1.753 267 butylbenzyl phthalate-d45 2058 164 1.715-1.824 10 367 butylbenzyl phthalate5 2060 267 1.000-1.002 10 60 65 276 chrysene-d12 2081 164 1.743-1.837 10 376 chrysene 2083 276 1.000-1.004 10 51 48 901 4,4'methylenebis (2-chloroaniline) 2083 164 1.791 272 benzo(a)anthracene-d12 2082 164 1.735-1.846 10 372 benzo (a) anthracene 2090 272 0.999-1.007 10 61 47 12 September 1989 ------- Method 1625C TABLE 5. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 solids Solids No.1 Compound (sec) Ref Relative2 (l-ig/L) (l-ig/kg) (l-ig/kg) 381 3,3'-dimethoxybenzidine 2090 164 1.797 228 3,3'-dichlorobenzidine-d6 2088 164 1.744-1.848 50 328 3,3'-dichlorobenzidine 2086 228 1.000-1.001 50 62 111 940 triphenylene 2088 164 1.795 560 benzan throne 2106 164 1.811 266 bis(2-ethylhexyl) phthalate-d4 2123 164 1.771-1.880 10 366 bis(2-ethylhexyl) phthalate 2124 266 1.000-1.002 10 553* 1310* 524 n-C26 2147 164 1.846 10 609* 886* 591 ethynylestradiol 3-methyl ether 2209 164 1.899 269 di-n-octyl phthalate-d4 2239 164 1.867-1.982 10 369 di-n-octyl phthalate 2240 269 1.000-1.002 10 72 62 525 n-C28 2272 164 1.954 10 492* 1810* 584 7,12-dimethylbenz(a)- anthracene 2284 164 1.964 274 benzo (b) fluoranthene-dj 2 2281 164 1.902-2.025 10 374 benzo (b) fluoranthene 2293 274 1.000-1.005 10 54 30 275 benzo (k) fluor anthene-dj 2 2287 164 1.906-2.033 10 375 benzo (k) fluoranthene 2293 275 1.000-1.005 10 95 20 924 perylene 2349 164 2.020 273 benzo (a) pyrene-dj 2 2351 164 1.954-2.088 10 373 benzo(a)pyrene 2350 273 1.000-1.004 10 52 15 626 n-C30-d62 2384 164 1.972-2.127 10 726 n-C30 2429 626 1.011-1.028 10 252* 658* 596 malachite green 2382 164 2.048 900 3-methylcholanthrene 2439 164 2.097 083 indeno(l,2,3-cd)pyrene 2650 164 2.279 20 67 263* 282 dibenzo(a,h)anthracene-d145 2649 164 2.107-2.445 20 382 dibenzo (a,h) anthracene5 2660 282 1.000-1.007 20 49 125 279 benzo(ghi)perylene-d12 2741 164 2.187-2.524 20 379 benzo (ghi) perylene 2750 279 1.001-1.006 20 44 nd 'Reference numbers beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal standard method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope dilution. 2Single values in this column are based on single laboratory data. 3This is a minimum level at which the analytical system shall give recognizable mass spectra (background corrected) and acceptable calibration points. The concentration in the aqueous or solid phase is determined using the equations in Section 14.0. September 1989 13 ------- Method 1625C 4Method detection limits determined in digested sludge (low solids) and in filter cake or compost (high solids). Specification derived from related compound. 6Detected as azobenzene. 7Detected as diphenylamine. nd = not detected when spiked into the sludge tested *Background levels of these compounds were present in the sludge tested, resulting in higher than expected MDL's. The MDL for these compounds is expected to be approximately 50 Hg/kg with no interferences present. Column: 30 ±2 m x 0.25 ±0.02 mm i.d. 94% methyl, 4% phenyl, 1% vinyl bonded phase fused silica capillary. Temperature program: Five minutes at 30°C; 30-280°C at 8°C per min; isothermal at 280°C until benzo(ghi)perylene elutes. Gas velocity: 30 ±5 cm/sec at 30°C. TABLE 6. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR ACID EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 Solids Solids No.1 Compound (sec) Ref Relative 2 (l-ig/L) (l-ig/kg) (l-ig/kg) 164 2,2'-difluorobiphenyl (int std) 1163 164 1.000-1.000 10 224 2-chlorophenol-d4 701 164 0.587-0.618 10 324 2-chlorophenol 705 224 0.997-1.010 10 18 10 947 hexanoic acid 746 164 0.641 944 p-cresol 834 164 0.717 257 2-nitrophenol-d4 898 164 0.761-0.783 20 357 2-nitrophenol 900 257 0.994-1.009 20 39 44 231 2,4-dichlorophenol-d3 944 164 0.802-0.822 10 331 2,4-dichlorophenol 947 231 0.997-1.006 10 24 116 943 benzoic acid 971 164 0.835 946 2,6-dichlorophenol 981 164 0.844 222 4-chloro-3-methylphenol-d2 1086 164 0.930-0.943 10 322 4-chloro-3-methylphenol 1091 222 0.998-1.003 10 41 62 221 2,4,6-trichlorophenol-d2 1162 164 0.994-1.005 10 46 111 321 2,4,6-trichlorophenol 1165 221 0.998-1.004 10 631 2,4,5-trichlorophenol-d25 1167 164 0.998-1.009 10 731 2,4,5-trichlorophenol 1170 631 0.998-1.004 10 32 55 530 2,3,6-trichlorophenol 1195 164 1.028 10 58 37 259 2,4-dinitrophenol-d3 1323 164 1.127-1.149 50 359 2,4-dinitrophenol 1325 259 1.000-1.005 50 565 642 258 4-nitrophenol-d4 1349 164 1.147-1.175 50 14 September 1989 ------- Method 1625C TABLE 6. GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR ACID EXTRACTABLE COMPOUNDS Method Detection Retention Time Limit4 Minimum Low High EGD Mean EGD Level3 Solids Solids No.1 Compound (sec) Ref Relative 2 (l-ig/L) (l-ig/kg) (l-ig/kg) 358 4-nitrophenol 1354 2^8 0.997-1.006 50 287 11 948 2,3,4,6-tetrachlorophenol 1371 164 1.179 260 2-methyl-4,6- dinitrophenol-d2 1433 164 1.216-1.249 20 360 2-methyl-4,6-dinitrophenol 1435 260 1.000-1.002 20 385 83 945 3,5-dibromo- 4-hydroxybenzonitrile 1481 164 1.273 264 pentachlorophenol-13C6 1559 164 1.320-1.363 50 364 pentachlorophenol 1561 264 0.998-1.002 50 51 207 Reference numbers beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal standard method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope dilution. 2Single values in this column are based on single laboratory data. 3This is a minimum level at which the analytical system shall give recognizable mass spectra (background corrected) and acceptable calibration points. The concentration in the aqueous or solid phase is determined using the equations in section 14. 4Method detection limits determined in digested sludge (low solids) and in filter cake or compost (high solids). Specification derived from related compound. Column: 30 ±2 m x 0.25 ±0.02 mm i.d. 94% methyl, 4% phenyl, 1% vinyl bonded phase fused silica capillary. Temperature program: Five minutes at 30°C; 30-250°C or until pentachlorophenol elutes. Gas velocity: 30 ±5 cm/sec at 30°C. 3.0 Contamination And Interferences 3.1 Solvents, reagents, glassware, and other sample processing hardware may yield artifacts and/or elevated baselines causing misinterpretation of chromatograms and spectra. All materials used in the analysis shall be demonstrated to be free from interferences under the conditions of analysis by running method blanks initially and with each sample lot (samples started through the extraction process on a given eight hour shift, to a maximum of 20). Specific selection of reagents and purification of solvents by distillation in all-glass systems may be required. Glassware and, where possible, reagents are cleaned by solvent rinse and baking at 450°C for one hour minimum. September 1989 15 ------- Method 1625C 3.2 Interferences coextracted from samples will vary considerably from source to source, depending on the diversity of the site being sampled. 4.0 Safety 4.1 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 data handling sheets should also be made available to all personnel involved in these analyses. Additional information on laboratory safety can be found in References 3-5. 4.2 The following compounds covered by this method have been tentatively classified as known or suspected human or mammalian carcinogens: benzo(a)anthracene, 3,3'-dichlorobenzidine, dibenzo(a,h)anthracene, benzo(a)pyrene, N-nitrosodimethylamine, and beta-naphthylamine. Primary standards of these compounds shall be prepared in a hood, and a NIOSH/MESA approved toxic gas respirator should be worn when high concentrations are handled. 5.0 Apparatus And Materials 5.1 Sampling Equipment—For discrete or composite sampling. 5.1.1 Sample bottles and caps 5.1.1.1 Liquid samples (waters, sludges and similar materials that contain less than 5% solids)—Sample bottle, amber glass, 1.1 L minimum, with screw cap. 5.1.1.2 Solid samples (soils, sediments, sludges, filter cake, compost, and similar materials that contain more than 5% solids)—Sample bottle, wide mouth, amber glass, 500 mL minimum. 5.1.1.3 If amber bottles are not available, samples shall be protected from light. 5.1.1.4 Bottle caps—Threaded to fit sample bottles. Caps shall be lined with Teflon. 5.1.1.5 Cleaning 5.1.1.5.1 Bottles are detergent water washed, then solvent rinsed or baked at 450°C for one hour minimum before use. 5.1.1.5.2 Cap liners are washed with detergent and water, rinsed with reagent water (see Section 6.5.1) and then solvent, and then baked for at least one hour at approximately 200°C. 5.1.2 Compositing equipment—Automatic or manual compositing system incorporating glass containers cleaned per bottle cleaning procedure above. Sample containers 16 September 1989 ------- Method 1625C are kept at 0-4°C during sampling. Only glass or Teflon tubing shall be used. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used only in the pump. Before use, the tubing shall be thoroughly rinsed with methanol, followed by repeated rinses with reagent water (Section 6.5.1) to minimize sample contamination. An integrating flow meter is used to collect proportional composite samples. 5.2 Equipment—For determining percent moisture. 5.2.1 Oven—Capable of maintaining a temperature of 110 ±5°C. 5.2.2 Desiccator. 5.3 Sonic Disruptor—375 watt with pulsing capability and 3/4 in. disruptor horn (Ultrasonics, Inc, Model 375C, or equivalent). 5.4 Extraction Apparatus 5.4.1 Continuous liquid-liquid extractor—Teflon or glass connecting joints and stopcocks without lubrication, 1.5-2 L capacity (Hershberg-Wolf Extractor, Ace Glass 6841-10, or equivalent). 5.4.2 Beakers 5.4.2.1 1.5-2 L borosilicate glass beakers calibrated to 1 L. 5.4.2.2 400-500 mL borosilicate glass beakers. 5.4.2.3 Spatulas—Stainless steel. 5.4.3 Filtration apparatus 5.4.3.1 Glass funnel—125-250 mL. 5.4.3.2 Filter paper for above (Whatman 41, or equivalent) 5.5 Drying Column—15-20 mm i.d. Pyrex chromatographic column equipped with coarse glass frit or glass wool plug. 5.6 Concentration Apparatus 5.6.1 Concentrator tube—Kuderna-Danish (K-D) 10 mL, graduated (Kontes K-570050- 1025, or equivalent) with calibration verified. Ground glass stopper (size 19/22 joint) is used to prevent evaporation of extracts. 5.6.2 Evaporation flask—Kuderna-Danish (K-D) 500 mL (Kontes K-570001-0500, or equivalent), attached to concentrator tube with springs (Kontes K-662750-0012). 5.6.3 Snyder column—Kuderna-Danish (K-D) three-ball macro (Kontes K-503000-0232, or equivalent). September 1989 17 ------- Method 1625C 5.6.4 Snyder column—Kuderna-Danish (K-D) two-ball micro (Kontes K-469002-0219, or equivalent). 5.6.5 Boiling chips—Approximately 10/40 mesh, extracted with methylene chloride and baked at 450°C for one hour minimum. 5.6.6 Nitrogen evaporation device—Equipped with a water bath that can be maintained at 35-40°C. The N-Evap by Organomation Associates, Inc., South Berlin, MA (or equivalent) is suitable. 5.7 Water Bath—Heated, with concentric ring cover, capable of temperature control (±2°C), installed in a fume hood. 5.8 Sample Vials—Amber glass, 2-5 mL with Teflon-lined screw cap. 5.9 Balances 5.9.1 Analytical—Capable of weighing 0.1 mg. 5.9.2 Top loading—Capable of weighing 10 mg. 5.10 Automated Gel Permeation Chromatograph—Analytical Biochemical Labs, Inc., Columbia, MO, Model GPC Autoprep 1002, or equivalent. 5.10.1 Column—600-700 mm x 25 mm i.d., packed with 70 g of SX-3 Bio-beads (Bio-Rad Laboratories, Richmond, CA). 5.10.2 UV detectors—254 mu, preparative or semi-prep flow cell: 5.10.2.1 Schmadzu—5 mm path length. 5.10.2.2 Beckman—Altex 152W, 8 |iL micro-prep flow cell, 2 mm path. 5.10.2.3 Pharmacia UV-1— 3 mm flow cell. 5.10.2.4 LDC Milton-Roy UV-3—Monitor #1203. 5.11 Gas Chromatograph—Shall have splitless or on-column injection port for capillary column, temperature program with 30°C hold, and shall meet all of the performance specifications in Section 12. 5.11.1 Column—30 ±5 m x 0.25 ±0.02 mm i.d. 5% phenyl, 94% methyl, 1% vinyl silicone bonded phase fused silica capillary column (J&W DB-5, or equivalent). 5.12 Mass Spectrometer—70 eV electron impact ionization, shall repetitively scan from 35-450 amu in 0.95-1.00 second, and shall produce a unit resolution (valleys between m/z 441- 442 less than 10 percent of the height of the 441 peak), background corrected mass spectrum from 50 ng decafluorotriphenylphosphine (DFTPP) introduced through the GC inlet. The spectrum shall meet the mass-intensity criteria in Table 7 (Reference 6). The mass spectrometer shall be interfaced to the GC such that the end of the capillary column terminates within one centimeter of the ion source but does not intercept the electron or 18 September 1989 ------- Method 1625C ion beams. All portions of the column which connect the GC to the ion source shall remain at or above the column temperature during analysis to preclude condensation of less volatile compounds. TABLE 7. DFTPP MASS-INTENSITY SPECIFICATIONS* Mass Intensity Required 51 8-82% of m/z 198 68 less than 2% of m/z 69 69 11-91% of m/z 198 70 less than 2% of m/z 69 127 32-59% of m/z 198 197 less than 1% of m/z 198 198 base peak, 100% abundance 199 4-9% of m/z 198 275 11-30% of m/z 198 441 44-110% of m/z 443 442 30-86% of m/z 198 443 14-24% of m/z 442 *Reference 6. 5.13 Data System—Shall collect and record MS data, store mass-intensity data in spectral libraries, process GCMS data, generate reports, and shall compute and record response factors. 5.13.1 Data acquisition—Mass spectra shall be collected continuously throughout the analysis and stored on a mass storage device. 5.13.2 Mass spectral libraries—User created libraries containing mass spectra obtained from analysis of authentic standards shall be employed to reverse search GCMS runs for the compounds of interest (Section 7.2). 5.13.3 Data processing—The data system shall be used to search, locate, identify, and quantify the compounds of interest in each GCMS analysis. Software routines shall be employed to compute retention times and peak areas. Displays of spectra, mass chromatograms, and library comparisons are required to verify results. 5.13.4 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 multi-point calibration curves (Section 7). Computations of relative standard deviation (coefficient of variation) are used for testing calibration linearity. Statistics on initial (Section 8.2) and on-going (Section 12.7) performance shall be computed and maintained. September 1989 19 ------- Method 1625C 6.0 Reagents and Standards 6.1 Reagents for Adjusting Sample pH 6.1.1 Sodium hydroxide—Reagent grade, 6 N in reagent water. 6.1.2 Sulfuric acid—Reagent grade, 6 N in reagent water. 6.2 Sodium Sulfate—Reagent grade, granular anhydrous, rinsed with methylene chloride (20 mL/g), baked at 450°C for one hour minimum, cooled in a desiccator, and stored in a pre-cleaned glass bottle with screw cap which prevents moisture from entering. 6.3 Methylene Chloride—Distilled in glass (Burdick and Jackson, or equivalent). 6.4 GPC Calibration Solution—Containing 300 mg/mL corn oil, 15 mg/mL bis(2-ethylhexyl) phthalate, 1.4 mg/mL pentachlorophenol, 0.1 mg/mL perylene, and 0.5 mg/mL sulfur. 6.5 Reference Matrices 6.5.1 Reagent water—Water in which the compounds of interest and interfering compounds are not detected by this method. 6.5.2 High solids reference matrix—Playground sand or similar material in which the compounds of interest and interfering compounds are not detected by this method. 6.6 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 compute the concentration of the standard. When not being used, standards are stored in the dark at -20 to -10°C in screw-capped vials with Teflon-lined lids. A mark is placed on the vial at the level of the solution so that solvent evaporation loss can be detected. The vials are brought to room temperature prior to use. Any precipitate is redissolved and solvent is added if solvent loss has occurred. 6.7 Preparation of Stock Solutions—Prepare in methylene chloride, benzene, p-dioxane, or a mixture of these solvents per the steps below. Observe the safety precautions in Section 4. The large number of labeled and unlabeled acid and base/neutral compounds used for combined calibration (Section 7) and calibration verification (Section 12.5) require high concentrations (approximately 40 mg/mL) when individual stock solutions are prepared, so that dilutions of mixtures will permit calibration with all compounds in a single set of solutions. The working range for most compounds is 10-200 |ig/mL. Compounds with a reduced MS response may be prepared at higher concentrations. 6.7.1 Dissolve an appropriate amount of assayed reference material in a suitable solvent. For example, weigh 400 mg naphthalene in a 10 mL ground glass stoppered volumetric flask and fill to the mark with benzene. After the naphthalene is completely dissolved, transfer the solution to a 15 mL vial with Teflon-lined cap. 20 September 1989 ------- Method 1625C 6.7.2 Stock standard solutions should be checked for signs of degradation prior to the preparation of calibration or performance test standards. Quality control check samples that can be used to determine the accuracy of calibration standards are available from the US Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268. 6.7.3 Stock standard solutions shall be replaced after six months, or sooner if comparison with quality control check standards indicates a change in concentration. 6.8 Labeled Compound Spiking Solution—From stock standard solutions prepared as above, or from mixtures, prepare the spiking solution at a concentration of 200 \ig/mL, or at a concentration appropriate to the MS response of each compound. 6.9 Secondary Standard—Using stock solutions (Section 6.7), prepare a secondary standard containing all of the compounds in Tables 1 and 2 at a concentration of 400 |ig/mL, or higher concentration appropriate to the MS response of the compound. 6.10 Internal Standard Solution—Prepare 2,2'-difluorobiphenyl (DFB) at a concentration of 10 mg/mL in benzene. 6.11 DFTPP Solution—Prepare at 50 |ig/mL in acetone. 6.12 Solutions for Obtaining Authentic Mass Spectra (Section 7.2)—Prepare mixtures of compounds at concentrations which will assure authentic spectra are obtained for storage in libraries. 6.13 Calibration Solutions—Combine 5 aliquots of 0.5 mL each of the solution in Section 6.8 with 25, 50, 125, 250, and 500 |iL of the solution in Section 6.9 and bring to 1.00 mL total volume each. This will produce calibration solutions of nominal 10, 20, 50, 100 and 200 |ig/mL of the pollutants and a constant nominal 100 |ig/mL of the labeled compounds. Spike each solution with 10 |iL of the internal standard solution (Section 6.10). These solutions permit the relative response (labeled to unlabeled) to be measured as a function of concentration (Section 7.4). 6.14 Precision and Recovery Standard—Used for determination of initial (Section 8.2) and on- going (Section 12.7) precision and recovery. This solution shall contain the pollutants and labeled compounds at a nominal concentration of 100 |ig/mL. 6.15 Stability of Solutions—All standard solutions (Sections 6.8 through 6.14) shall be analyzed within 48 hours of preparation and on a monthly basis thereafter for signs of degradation. Standards will remain acceptable if the peak area at the quantitation mass relative to the DFB internal standard remains within ±15% of the area obtained in the initial analysis of the standard. 7.0 Calibration 7.1 Assemble the GCMS and establish the operating conditions in Table 5. Analyze standards per the procedure in Section 11 to demonstrate that the analytical system meets the minimum levels in Tables 5 and 6, and the mass-intensity criteria in Table 7 for 50 ng DFTPP. September 1989 21 ------- Method 1625C 12 Mass Spectral Libraries—Detection and identification of compounds of interest are dependent upon spectra stored in user created libraries. 7.2.1 Obtain a mass spectrum of each pollutant, labeled compound, and the 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. 7.2.2 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 masses or introduce other distortion. 7.2.3 The authentic reference spectrum is obtained under DFTPP tuning conditions (Section 7.1 and Table 7) to normalize it to spectra from other instruments. 7.2.4 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 5.12, the mass spectrometer may be scanned to an m/z lower than 35 to gain additional spectral information. The spectrum obtained is stored for reverse search and for compound confirmation. 7.2.5 For the compounds in Tables 3 and 4 and for other compounds for which the mass spectra, quantitation m/z's, and retention times are known but the instrument is not to be calibrated, add the retention time and reference compound (Tables 5 and 6); the response factor and the quantitation m/z (Tables 8 and 9); and spectrum (Appendix A) to the reverse search library. Edit the spectrum per Section 7.2.4, if necessary. 7.3 Analytical Range—Demonstrate that 20 ng anthracene or phenanthrene produces an area at m/z 178 approx 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, and to diagnose instrument sensitivity problems (Section 15.3). The 20 |ig/mL calibration standard (Section 6.13) can be used to demonstrate this performance. 7.3.1 Polar compound detection—Demonstrate that unlabeled pentachlorophenol and benzidine are detectable at the 50 |ig/mL level (per all criteria in Section 13). The 50 |ig/mL calibration standard (Section 6.13) can be used to demonstrate this performance. 22 September 1989 ------- Method 1625C TABLE 8. CHARACTERISTIC M/Z's AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS Compound Labeled Analog Primary m/z1 Response Factor2 acenaphthene dio 154/164 acenaphthylene d8 152/160 acetophenone 105 0.79 4-aminobiphenyl 169 0.81 aniline 93 1.04 o-anisidine 108 0.43 anthracene dio 178/188 aramite 185 0.19 benzanthrone 230 0.15 1,3-benzenediol 110 0.78 benzenethiol 110 0.18 benzidine d8 184/192 benzo (a) anthracene diz 228/240 benzo (b) fluoranthene diz 252/264 benzo (k) fluoranthene d^ 252/264 benzo(a)pyrene d^ 252/264 benzo (ghi) perylene d^ 276/288 2,3-benzofluorene 216 0.35 benzoic acid 105 0.16 benzyl alcohol 79 0.47 biphenyl dio 154/164 bis(2-chloroethyl) ether d8 93/101 bis(2-chloroethoxy)methane d6 93/99 bis(2-chloroisopropyl) ether d^ 121/131 bis(2-ethylhexyl) phthalate d4 149/153 2-bromochlorobenzene 111 0.33 3-bromochlorobenzene 192 0.40 4-bromophenyl phenyl ether d5 248/253 butyl benzyl phthalate d4 149/153 n-CIO d22 57/82 n-C12 d26 57/66 n-C14 57 n-C16 d34 57/66 n-C18 57 n-C20 d42 57/66 n-C22 57 n-C24 dso 57/66 n-C26 57 n-C28 57 n-C30 d62 57/66 carbazole d8 167/175 4-chloro-2-nitroaniline 172 0.20 5-chloro-o-toluidine 106 0.50 4-chloroaniline 127 0.73 2-chloronaphthalene d7 162/169 3-chloronitrobenzene 157 0.18 4-chlorophenyl phenyl ether d5 204/209 September 1989 23 ------- Method 1625C TABLE 8. CHARACTERISTIC M/Z's AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS Compound Labeled Analog Primary m/z1 Response 3-chloropropionitrile 54 0.42 chrysene diz 228/240 o-cresol 108 0.59 crotoxyphos 127 0.017 p-cymene dM 119/130 2,6-di-tert-butyl- 220 0.078 p-benzoquinone di-n-butyl phthalate d4 149/153 2,4-diaminotoluene 122 0.059 dibenzo (a,h) anthracene dM 278/292 dibenzofuran d8 168/176 dibenzothiophene d8 184/192 1,2-dibromo-3-chloropropane 157 0.22 2,6-dichloro-4-nitroaniline 124 0.019 l,3-dichloro-2-propanol 79 0.68 2,3-dichloroaniline 161 0.47 1,2-dichlorobenzene d4 146/152 1,3-dichlorobenzene d4 146/152 1,4-dichlorobenzene d4 146/152 3,3'-dichlorobenzidine d6 252/258 2,2'-difluorobiphenyl (int std) 190 2,3-dichloronitrobenzene 191 0.11 l,2:3,4-diepoxybutane 55 0.27 diethyl phthalate d4 149/153 3,3'-dimethoxybenzidine 244 0.19 dimethyl phthalate d4 163/167 dimethyl sulfone 79 0.40 p-dimethylaminoazobenzene 120 0.23 7,12-dimethylbenz(a) 256 0.58 anthracene N,N-dimethylformamide 73 0.51 3,6-dimethylphenanthrene 206 0.72 2,4-dimethylphenol d3 122/125 1,4-dinitrobenzene 168 0.24 2,4-dinitrotoluene d3 165/168 2,6-dinitrotoluene d3 165/167 di-n-octyl phthalate d4 149/153 diphenylamine dio 169/179 diphenyl ether dio 170/180 diphenyldisulfide 218 0.25 1,2-diphenylhydrazine3 dio 77/82 ethyl methanesulfonate 109 0.28 ethylenethiourea 102 0.22 ethynylestradiol 3-methyl ether 227 0.28 fluoranthene dio 202/212 fluorene dio 166/176 hexachlorobenzene 13C 284/292 24 September 1989 ------- Method 1625C TABLE 8. CHARACTERISTIC M/Z's AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS Compound Labeled Analog Primary m/z1 Response Factor2 hexachlorobutadiene 4 225/231 hexachloroethane 13c 201/204 hexachlorocyclopentadiene 13C4 237/241 hexachloropropene 213 0.23 indeno(l,2,3-cd)pyrene 276 isophorone d8 82/88 2-isopropylnaphthalene 170 0.32 isosafrole 162 0.33 longifolene 161 0.14 malachite green 330 methapyrilene 97 0.43 methyl methanesulfonate 80 0.20 2-methylbenzothiazole 149 0.59 3-methylcholanthrene 268 0.59 4,4'-methylenebis 231 0.21 (2-chloroaniline) 4,5-methylenephenanthrene 190 0.44 1 -methy lfluorene 180 0.37 2-methylnaphthalene 142 0.99 1 -methy lphenanthrene 192 0.65 2-(methylthio)benzothiazole 181 0.42 naphthalene d8 128/136 1,5-naphthalenediamine 158 0.085 1,4-naphthoquinone 158 0.021 alpha-naphthylamine 143 0.89 beta-naphthylamine d7 143/150 5-nitro-o-toluidine 152 0.31 2-nitroaniline 138 0.39 3-nitroaniline 138 0.27 4-nitroaniline 138 0.11 nitrobenzene d5 123/128 4-nitrobiphenyl 199 0.35 N-nitrosodi-n-butylamine 84 0.47 N-nitrosodi-n-propylamine dM 70/78 N-nitrosodiethylamine 102 0.45 N-nitrosodimethylamine d6 74/80 N-nitrosodiphenylamine4 d6 169/175 N-nitrosomethylethylamine 88 0.33 N-nitrosomethylphenylamine 106 0.024 N-nitrosomorpholine 56 0.49 N-nitrosopiperidine 114 0.41 pentachlorobenzene 248 0.25 pentachloroethane 117 0.20 pentamethylbenzene 148 0.42 perylene 252 0.30 phenacetin 108 0.38 phenanthrene dio 178/188 September 1989 25 ------- Method 1625C TABLE 8. CHARACTERISTIC M/Z's AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS Compound Labeled Analog Primary m/z1 Response Factor2 phenol d5 94/71 phenothiazine 199 0.15 1 -pheny lnaphthalene 204 0.48 2-phenylnaphthalene 204 0.73 alpha-picoline d7 93/100 pronamide 173 0.31 pyrene dio 202/212 pyridine 79 0.68 safrole 162 0.45 squalene 69 0.042 styrene d5 104/109 alpha-terpineol d3 59/62 1,2,4,5-tetrachlorobenzene 216 0.43 thianaphthene 134 1.52 thioacetamide 75 0.28 thioxanthone 212 0.23 o-toluidine 106 1.04 1,2,3-trichlorobenzene d3 180/183 1,2,4-trichlorobenzene d3 180/183 1,2,3-trimethoxy benzene 168 0.48 2,4,5-trimethylaniline 120 0.28 triphenylene 228 1.32 tripropylene glycol methyl 59 0.092 ether 1,3,5-trithiane 138 0.15 Referenced to 2,2'-difluorobiphenyl 3Detected as azobenzene 4Detected as diphenylamine NOTE: Because the composition and purity of commercially-supplied isotopically labeled standards may vary, the primary m/z of the labeled analogs given in this table should be used as guidance. The appropriate m/z of the labeled analogs should be determined prior to use for sample analysis. Deviations from the m/z's listed here must be documented by the laboratory and submitted with the data. 26 September 1989 ------- Method 1625C TABLE 9. CHARACTERISTIC M/Z'S AND RESPONSE FACTORS OF ACID EXTRACTABLE COMPOUNDS Compound Labeled Analog Primary m/z1 Response Factor2 benzoic acid 105 0.16 4-chloro-3-methylphenol d2 107/109 2-chlorophenol d4 128/132 p-cresol 108 0.61 3,5-dibromo-4-hydroxybenzonitrile 277 0.12 2,4-dichlorophenol d3 162/167 2,6-dichlorophenol 162 0.42 2,4-dinitrophenol d3 184/187 hexanoic acid 60 0.62 2-methyl-4,6-dinitrophenol d2 198/200 2-nitrophenol d4 65/109 4-nitrophenol d4 65/109 pentachlorophenol 13c6 266/272 2,3,4,6-tetrachlorophenol 232 0.17 2,3,6-trichlorophenol d2 196/200 2,4,5-trichlorophenol d2 196/200 2,4,6-trichlorophenol d2 196/200 Native/labeled. Referenced to 2,2'-difluorobiphenyl. NOTE: Because the composition and purity of commercially-supplied isotopically labeled standards may vary, the primary m/z of the labeled analogs given in this table should be used as guidance. The appropriate m/z of the labeled analogs should be determined prior to use for sample analysis. Deviations from the m/z's listed here must be documented by the laboratory and submitted with the data. 7.4 Calibration with Isotope Dilution—Isotope dilution is used when 1) labeled compounds are available, 2) interferences do not preclude its use, and 3) the quantitation m/z (Tables 8 and 9) extracted ion current profile (EICP) area for the compound is in the calibration range. Alternate labeled compounds and quantitation m/z's may be used based on availability. If any of the above conditions preclude isotope dilution, the internal standard method (Section 7.5) is used. 7.4.1 A calibration curve encompassing the concentration range is prepared for each compound to be determined. The relative response (pollutant to labeled) vs concentration in standard solutions is plotted or computed using a linear regression. The example in Figure 1 shows a calibration curve for phenol using phenol-d5 as the isotopic diluent. Also shown are the ±10% error limits (dotted lines). Relative Response (RR) is determined according to the procedures described below. A minimum of five data points are employed for calibration. September 1989 27 ------- Method 1625C 2 10 20 50 100 200 CONCENTRATION (ug/mL) FIGURE 1 Relative Response Calibration Curve for Phenol. The Dotted Lines Enclose a ± lO Per- cent Error Window. 7.4.2 The relative response of a pollutant to its labeled analog is determined from isotope ratio values computed from acquired data. Three isotope ratios are used in this process: Rx = the isotope ratio measured for the pure pollutant. Ry = the isotope ratio measured for the labeled compound. Rm = the isotope ratio of an analytical mixture of pollutant and labeled compounds. The m/z's are selected such that Rx > Ry. If is not between 2^ and 0.5^ , the method does not apply and the sample is analyzed by the internal standard method. 28 September 1989 ------- Method 1625C 7.4.3 Capillary columns usually separate the pollutant-labeled pair, with the labeled compound eluted first (Figure 2). For this case, AREA AT FIGURE 2 Extracted Ion Current Profiles for Chromatographically Resolved Labeled (m2/z) and Unlabeled (rr^/z) Pairs. [area m /z (at RT )] R = - — X 1 1 R = y [area m /z (at RT )] R [area m^/z (at RT^] m [area mjz (at RT )] as measured in the mixture of the pollutant and labeled compounds (Figure 2), and RR = Rm. 7.4.4 Special precautions are taken when the pollutant-labeled pair is not separated, or when another labeled compound with interfering spectral masses overlaps the pollutant (a case which can occur with isomeric compounds). In this case, it is necessary to determine the respective contributions of the pollutant and labeled compounds to the respective EICP areas. If the peaks are separated well enough to permit the data system or operator to remove the contributions of the compounds to each other, the equations in Section 7.4.3 apply. This usually occurs when the height of the valley between the two GC peaks at the same m/z is less than 10% of the height of the shorter of the two peaks. If significant GC and spectral overlap occur, RR is computed using the following equation: September 1989 29 ------- Method 1625C RR = _ (Ry - Rm) (Rx + 1) (Rm " Rx) (Ry +D where, Rx = Measured as shown in Figure 3A. Ry = Measured as shown in Figure 3B. Rm = Measured as shown in Figure 3C. For the example, R. = = 9.644 4780 = _2650^ = 0 06()78 y 43600 R = = 1.019 m 48300 RR = 1.115 The data from these analyses are reported to three significant figures (see Section 14.6). Therefore, 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. 7.4.5 To calibrate the analytical system by isotope dilution, analyze a 1.0 |iL aliquot of each of the calibration standards (Section 6.13) using the procedure in Section 11.0. Compute the RR at each concentration. 7.4.6 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 5 point calibration range. 30 September 1989 ------- Method 1625C (3A) AREA = 46100 AREA = 4780 FIGURE 3 Extracted Ion Current Profiles for (3A) Unlabeled Compound, (3B) Labeled Com- pound, and (3C) Equal Mixture of Unlabeled and Labeled Compounds. 7.5 Calibration by Internal Standard—Used when criteria for isotope dilution (Section 7.4) cannot be met. The internal standard to be used for both acid and base/neutral analyses is 2,2'-difluorobi-phenyl. The internal standard method is also applied to determination of compounds having no labeled analog, and to measurement of labeled compounds for intra-laboratory statistics (Sections 8.4 and 12.7.4). 7.5.1 Response factors—Calibration requires the determination of response factors (RF) which are defined by the following equation: (\ x cj RF = —- — (Ais x Cs) where, As = The area of the characteristic mass for the compound in the daily standard. Ais = The area of the characteristric mass for the internal standard. Cis = The concentration of the internal standard (]ig/mL). Cs = The concentration of the compound in the daily standard (]ig/mL). September 1989 31 ------- Method 1625C 7.5.1.1 The response factor is determined for at least five concentrations appropriate to the response of each compound (Section 6.13); nominally, 10, 20, 50, 100, and 200 |ig/mL. The amount of internal standard added to each extract is the same (100 |ig/mL) so that Cis remains constant. The RF is plotted vs concentration for each compound in the standard (CJ to produce a calibration curve. 7.5.1.2 Linearity—If the response factor (RF) for any compound is constant (less than 35% coefficient of variation) over the five-point calibration range, an averaged response factor may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the five- point range. 7.6 Combined Calibration—By using calibration solutions (Section 6.13) containing the pollutants, labeled compounds, and the internal standard, 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 12.5) by analyzing the 100 |ig/mL calibration standard (Section 6.13). Re-calibration is required only if calibration verification (Section 12.5) criteria cannot be met. 8.0 Quality Assurance/Quality Control 8.1 Each laboratory that uses this method is required to operate a formal quality assurance program (Reference 7). 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. If the method is to be applied routinely to samples containing high solids with very little moisture (e.g., soils, filter cake, compost), the high solids reference matrix (Section 6.5.2) is substituted for the reagent water (Section 6.5.1) in all performance tests, and the high solids method (Section 10) is used for these tests. 8.1.1 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 8.2. 8.1.2 The analyst is permitted to modify this method to improve separations or lower the costs of measurements, provided all performance specifications are met. Each time a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2 to demonstrate method performance. 8.1.3 Analyses of blanks are required to demonstrate freedom from contamination. The procedures and criteria for analysis of a blank are described in Section 8.5. 8.1.4 The laboratory shall spike all samples with labeled compounds to monitor method performance. This test is described in Section 8.3. When results of these spikes indicate atypical method performance for samples, the samples are diluted to bring method performance within acceptable limits (Section 15). 32 September 1989 ------- Method 1625C 8.1.5 The laboratory shall, on an on-going basis, demonstrate through calibration verification and the analysis of the precision and recovery standard (Section 6.14) that the analysis system is in control. These procedures are described in Sections 12.1, 12.5, and 12.7. 8.1.6 The laboratory shall maintain records to define the quality of data that is generated. Development of accuracy statements is described in Section 8.4. 8.2 Initial Precision and Accuracy—To establish the ability to generate acceptable precision and accuracy, the analyst shall perform the following operations: 8.2.1 For low solids (aqueous samples), extract, concentrate, and analyze two sets of four 1 L aliquots (eight aliquots total) of the precision and recovery standard (Section 6.14) according to the procedure in Section 10. For high solids samples, two sets of four 30 g aliquots of the high solids reference matrix are used. 8.2.2 Using results of the first set of four analyses, compute the average recovery (X) in |ig/mL and the standard deviation of the recovery(s) in |ig/mL for each compound, by isotope dilution for pollutants with a labeled analog, and by internal standard for labeled compounds and pollutants with no labeled analog. 8.2.3 For each compound, compare s and X with the corresponding limits for initial precision and accuracy in Table 10. 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 10 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 can be attributed to probability, proceed as follows: 8.2.4 Using the results of the second set of four analyses, compute s and X for only those compounds which failed the test of the first set of four analyses (Section 8.2.3). 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 these compounds. In this event, correct the problem and repeat the entire test (Section 8.2.1). 8.3 The laboratory shall spike all samples with labeled compounds to assess method performance on the sample matrix. 8.3.1 Analyze each sample according to the method beginning in Section 10. 8.3.2 Compute the percent recovery (P) of the labeled compounds using the internal standard method (Section 7.5). September 1989 33 ------- Method 1625C 8.3.3 Compare the labeled compound recovery for each compound with the corresponding limits in Table 10. If the recovery of any compound falls outside its warning limit, method performance is unacceptable for that compound in that sample. Therefore, the sample is complex. Water samples are diluted, and smaller amounts of soils, sludges, and sediments are reanalyzed per Section 15. 8.4 As part of the QA program for the laboratory, method accuracy for samples shall be assessed and records shall be maintained. After the analysis of five samples of a given matrix type (water, soil, sludge, sediment) for which the labeled compounds pass the tests in Section 8.3, 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 + 2^ for each matrix. For example: If P = 90% and sp = 10% for five analyses of compost, the accuracy interval is expressed as 70-110%. Update the accuracy assessment for each compound in each matrix on a regular basis (e.g., after each 5-10 new accuracy measurements). TABLE 10. ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS Labeled and native Labeled and compound initial Labeled native precision and compound Calibration compound accuracy recovery verification ongoing (Section 8.2.3) (Sections 8.3 _ (Section accuracy EGD No.1 (ue/L) and 14.2) 12.5) (Section 12.7) Compound s X P (%) (l-ig/L) R (ng/L) 301 acenaphthene 21 79-134 80-125 72-144 201 acenaphthene-d10 38 38-147 20-270 71-141 30-180 377 acenaphthylene 38 69-186 60-166 61-207 277 acenaphthylene-d8 31 39-146 23-239 66-152 33-168 378 anthracene 41 58-174 60-168 50-199 278 anthracene-d10 49 31-194 14-419 58-171 23-242 305 benzidine 119 16-518 34-296 11-672 205 benzidine-d8 269 ns2-ns ns-ns ns-ns ns-ns 372 benzo (a) anthracene 20 65-168 70-142 62-176 272 benzo (a) anthracene-dj 2 41 25-298 12-605 28-357 22-329 374 benzo (b) fluoranthene 183 32-545 61-164 20-ns 274 benzo (b) fluoranthene-dj 2 168 11-577 ns-ns 14-ns ns-ns 375 benzo (k) fluoranthene 26 59-143 13-ns 53-155 275 benzo (k) fluoranthene-dj 2 114 15-514 ns-ns 13-ns ns-685 373 benzo(a)pyrene 26 62-195 78-129 59-206 273 benzo(a)pyrene-d12 24 35-181 21-290 12-ns 32-194 379 benzo (ghi)perylene 21 72-160 69-145 58-168 279 benzo (ghi) pery lene-dj 2 45 29-268 14-529 13-ns 25-303 712 biphenyl (Appendix C) 41 75-148 58-171 62-176 612 biphenyl-d10 43 28-165 ns-ns 52-192 17-267 318 bis (2-chlor oethy 1) ether 34 55-196 61-164 50-213 218 bis(2-chloroethyl) ether d8 33 29-196 15-372 52-194 25-222 343 bis(2-chloroethoxy) methane 27 43-153 44-228 39-166 34 September 1989 ------- Method 1625C TABLE 10. ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS Labeled and native Labeled and compound initial Labeled native precision and compound Calibration compound accuracy recovery verification ongoing (Section 8.2.3) (Sections 8.3 _ (Section accuracy (ue/L) and 14.2) 12.5) (Section 12.7) EjVjL) No.1 Compound s X P (%) (l-ig/L) R (ng/L) 243 bis(2-chloroethoxy) 33 29-196 15-372 52-194 25-222 methane3 342 bis(2-chloroisopropyl) ether 17 81-138 67-148 77-145 242 bis(2-chloroisopropyl) 27 35-149 20-260 44-229 30-169 ether-d12 366 bis(2-ethylhexyl) phthalate 31 69-220 76-131 64-232 266 bis(2-ethylhexyl) phthalate- A 29 32-205 18-364 43-232 28-224 341 4 4-bromophenyl phenyl 44 44-140 52-193 35-172 ether 241 4-bromophenylphenyl 52 40-161 19-325 57-175 29-212 ether-d53 367 butyl benzyl phthalate 31 19-233 22-450 35-170 267 butyl benzyl phthalate-d43 29 32-205 18-364 43-232 28-224 717 n-CIO (Appendix C) 51 24-195 42-235 19-237 617 n-C10-d22 70 ns-298 ns-ns 44-227 ns-504 706 n-C12 (Appendix C) 74 35-369 60-166 29-424 606 n-C12-d26 53 ns-331 ns-ns 41-242 ns-408 518 n-C14 (Appendix C)3 109 ns-ns 37-268 ns-ns 719 n-C16 (Appendix C) 33 80-162 72-138 71-181 619 n-C16-d34 46 37-162 18-308 54-186 28-202 520 n-C18 (Appendix C)3 39 42-131 40-249 35-167 721 n-C20 (Appendix C) 59 53-263 54-184 46-301 621 n-C20-d42 34 34-172 19-306 62-162 29-198 522 n-C22 (Appendix C)3 31 45-152 40-249 39-195 723 n-C24 (Appendix C) 11 80-139 65-154 78-142 623 n-C24-d50 28 27-211 15-376 50-199 25-229 524 n-C26 (Appendix C)3 35 35-193 26-392 31-212 525 n-C28 (Appendix C)3 35 35-193 26-392 31-212 726 n-C30 (Appendix C) 32 61-200 66-152 56-215 626 n-C30-d62 41 27-242 13-479 24-423 23-274 728 carbazole (4c) 38 36-165 44-227 31-188 628 carbazole-d83 31 48-130 29-215 69-145 40-156 320 2-chloronaphthalene 100 46-357 58-171 35-442 220 2-chloronaphthalene-d7 41 30-168 15-324 72-139 24-204 322 4-chloro-3-methylphenol 37 76-131 85-115 62-159 222 4-chloro-3-methylphenol-d2 111 30-174 ns-613 68-147 14-314 324 2-chlorophenol 13 79-135 78-129 76-138 224 2-chlorophenol-d4 24 36-162 23-255 55-180 33-176 340 4-chlorophenyl phenyl 42 75-166 71-142 63-194 September 1989 35 ------- Method 1625C TABLE 10. ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS Labeled and native Labeled and compound initial Labeled native precision and compound Calibration compound accuracy recovery verification ongoing (Section 8.2.3) (Sections 8.3 _ (Section accuracy (ue/L) and 14.2) 12.5) (Section 12.7) EjVjL) No.1 Compound s X P (%) (l-ig/L) R (ng/L) 240 4-chlorophenyl phenyl 62 40-161 19-325 57-175 29-212 ether-d5 376 chrysene 51 59-186 70-142 48-221 276 chrysene-d12 69 33-219 13-512 24-411 23-290 713 p-cymene (Appendix C) 18 76-140 79-127 72-147 613 p-cymene-d14 67 ns-359 ns-ns 66-152 ns-468 382 dibenzo (a,h) anthracene 55 23-299 13-761 19-340 282 dibenzo(a.h) 45 29-268 14-529 13-ns 25-303 anthracene-d143 705 dibenzofuran (Appendix C) 20 85-136 73-136 79-146 605 dibenzofuran-d8 31 47-136 28-220 66-150 39-160 704 dibenzothiophene (Synfuel) 31 79-150 72-140 70-168 604 dibenzothiophene-d8 31 48-130 29-215 69-145 40-156 368 di-n-butyl phthalate 15 76-165 71-142 74-169 268 di-n-butyl phthalate-d4 23 23-195 13-346 52-192 22-209 325 1,2-dichlorobenzene 17 73-146 74-135 70-152 225 1,2-dichlorobenzene-d4 35 14-212 ns-494 61-164 11-247 326 1,3-dichlorobenzene 43 63-201 65-154 55-225 226 l,3-dichlorobenzene-d4 48 13-203 ns-550 52-192 ns-260 327 1,4-dichlorobenzene 42 61-194 62-161 53-219 227 l,4-dichlorobenzene-d4 48 15-193 ns-474 65-153 11-245 328 3,3'-dichlorobenzidine 26 68-174 77-130 64-185 228 3,3'-dichlorobenzidine-d6 80 ns-562 ns-ns 18-558 ns-ns 331 2,4-dichlorophenol 12 85-131 67-149 83-135 231 2,4-dichlorophenol-d3 28 38-164 24-260 64-157 34-182 370 diethyl phthalate 44 75-196 74-135 65-222 270 diethyl phthalate-d4 78 ns-260 ns-ns 47-211 ns-ns 334 2,4-dimethylphenol 13 62-153 67-150 60-156 234 2,4-dimethylphenol-d3 22 15-228 ns-449 58-172 14-242 371 dimethyl phthalate 36 74-188 73-137 67-207 271 dimethyl phthalate-d4 108 ns-640 ns-ns 50-201 ns-ns 359 2,4-dinitrophenol 18 72-134 75-133 68-141 259 2,4-dinitrophenol-d3 66 22-308 ns-ns 39-256 17-378 335 2,4-dinitrotoluene 18 75-158 79-127 72-164 235 2,4-dinitrotoluene-d3 37 22-245 10-514 53-187 19-275 336 2,6-dinitrotoluene 30 80-141 55-183 70-159 236 2,6-dinitrotoluene-d3 59 44-184 17-442 36-278 31-250 369 di-n-octyl phthalate 16 77-161 71-140 74-166 269 di-n-octyl phthalate-d4 46 12-383 ns-ns 21-467 10-433 707 diphenylamine (Appendix n 45 58-205 57-176 51-231 607 diphenylamine-d10 42 27-206 11-488 59-169 21-249 36 September 1989 ------- Method 1625C TABLE 10. ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS Labeled and native Labeled and Labeled native compound Calibration compound recovery verification ongoing (Sections 8.3 _ (Section accuracy and 14.2) 12.5) (Section 12.7) No.1 Compound s X P (%) (|Jg/L) R (pg/L) 708 diphenyl ether (Appendix n 19 82-136 83-120 77-144 608 diphenyl ether-d10 37 36-155 19-281 77-129 29-186 337 1,2-dipheny lhydrazine 73 49-308 75-134 40-360 237 l,2-diphenylhy-drazine-d10 35 31-173 17-316 58-174 26-200 339 fluoranthene 33 71-177 67-149 64-194 239 fluoranthene-d10 35 36-161 20-278 47-215 30-187 380 fluorene 29 81-132 74-135 70-151 280 fluorene-d10 43 51-131 27-238 61-164 38-172 309 hexachlorobenzene 16 90-124 78-128 85-132 209 hexachlorobenzene-13C6 81 36-228 13-595 38-265 23-321 352 hexachlorobutadiene 56 51-251 74-135 43-287 252 hexachlorobutadiene-13C4 63 ns-316 ns-ns 68-148 ns-413 312 hexachloroethane 227 21-ns 71-141 13-ns 212 hexachloroethane-13C 77 ns-400 ns-ns 47-212 ns-563 353 hexachlorocyclo-pentadiene 15 69-144 77-129 67-148 253 hexachlorocyclo- 60 ns-ns ns-ns 47-211 ns-ns pentadiene-13C4 083 ideno(l,2,3-cd)pyrene3 55 23-299 13-761 19-340 354 isophorone 25 76-156 70-142 70-168 254 isophorone-d8 23 49-133 33-193 52-194 44-147 360 2-methyl-4,6-dinitrophenol 19 77-133 69-145 72-142 260 2-methyl-4,6-dinitrophenol- A 64 36-247 16-527 56-177 28-307 355 2 naphthalene 20 80-139 73-137 75-149 255 naphthalene-d8 39 28-157 14-305 71-141 22-192 702 beta-naphthylamine 49 10-ns 39-256 ns-ns (Appendix C) 602 beta-naphthylamine-d7 33 ns-ns ns-ns 44-230 ns-ns 356 nitrobenzene 25 69-161 85-115 65-169 256 nitrobenzene-d5 28 18-265 ns-ns 46-219 15-314 357 2-nitrophenol 15 78-140 77-129 75-145 257 2-nitrophenol-d4 23 41-145 27-217 61-163 37-158 358 4-nitrophenol 42 62-146 55-183 51-175 258 4-nitrophenol-d4 188 14-398 ns-ns 35-287 ns-ns 361 N-nitrosodimethylamine 49 10-ns 39-256 ns-ns 261 N-nitrosodimethyl-amine- A 3 33 ns-ns ns-ns 44-230 ns-ns 363 6 N-nitrosodi-n-propylamine 45 65-142 68-148 53-173 263 N-nitrosodi-n-propylamine3 37 54-126 26-256 59-170 40-166 362 N-nitrosodiphenylamine 45 65-142 68-148 53-173 compound initial precision and accuracy (Section 8.2.3) lug/Ll September 1989 37 ------- Method 1625C TABLE 10. ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS EGD No.1 Compound Labeled and native compound initial precision and accuracy (Section 8.2.3) lUg/Ll s X Labeled compound Calibration recovery verification (Sections 8.3 _ (Section and 14.2) 12.5) P (%) (pg/L) Labeled and native compound ongoing accuracy (Section 12.7) R (pg/L) 262 N -nitrosodiphenyl-amine- 37 54-126 d6 364 pentachlorophenol 21 76-140 264 pentachlorophenol-13C6 49 37-212 381 phenanthrene 13 93-119 281 phenanthrene-d10 40 45-130 365 phenol 36 77-127 265 phenol-d5 161 21-210 703 alpha-picoline (Synfuel) 38 59-149 603 alpha-picoline-d7 138 11-380 384 pyrene 19 76-152 284 pyrene-d10 29 32-176 710 styrene (Appendix C) 42 53-221 610 styrene-d5 49 ns-281 709 alpha-terpineol (Appendix 44 42-234 C) 609 alpha-terpineol-d3 48 22-292 729 1,2,3-trichloro-benzene (4c) 69 15-229 629 l,2,3-trichloro-benzene-d33 57 15-212 308 1,2,4-trichlorobenzene 19 82-136 208 l,2,4-trichlorobenzene-d3 57 15-212 530 2,3,6-trichloro-phenol (4c)3 30 58-137 731 2,4,5-trichlorophenol (4c) 30 58-137 631 2,4,5-trichlorophenol-d23 47 43-183 321 2,4,6-trichlorophenol 57 59-205 221 2,4,6-trichlorophenol-d2 47 43-183 26-256 18-412 24-241 ns-ns ns-ns 18-303 ns-ns ns-672 ns-592 ns-592 21-363 21-363 59-170 77-130 42-237 75-133 67-149 65-155 48-208 60-165 31-324 76-132 48-210 65-153 44-228 54-186 20-502 60-167 61-163 78-128 61-163 56-180 56-180 69-144 81-123 69-144 40-166 71-150 29-254 87-126 34-168 62-154 ns-ns 50-174 ns-608 72-159 28-196 48-244 ns-348 38-258 18-339 11-297 10-282 77-144 10-282 51-153 51-153 34-226 48-244 34-226 Reference numbers beginning with 0, 1 or 5 indicate a pollutant quantified by the internal standard method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope dilution. 2ns = no specification: limit is outside the range that can be measured reliably. 3This compound is to be determined by internal standard; specification is derived from related compound. Blanks—Reagent water and high solids reference matrix blanks are analyzed to demonstrate freedom from contamination. 8.5.1 Extract and concentrate a 1 L reagent water blank or a high solids reference matrix blank with each sample lot (samples started through the extraction process 38 September 1989 ------- Method 1625C on the same eight hour shift, to a maximum of 20 samples). Analyze the blank immediately after analysis of the precision and recovery standard (Section 6.14) to demonstrate freedom from contamination. 8.5.2 If any of the compounds of interest (Tables 1-4) or any potentially interfering compound is found in an aqueous blank at greater than 10 Hg/L, or in a high solids reference matrix blank at greater than 100 \ig/kg (assuming a response factor of 1 relative to the internal standard for compounds not listed in Tables 1- 4), analysis of samples is halted until the source of contamination is eliminated and a blank shows no evidence of contamination at this level. 8.6 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 12.5), and for initial (Section 8.2) and on-going (Section 12.7) precision and recovery should be identical, so that the most precise results will be obtained. The GCMS instrument in particular will provide the most reproducible results if dedicated to the settings and conditions required for the analyses of semivolatiles by this method. 8.7 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. 9.0 Sample Collection, Preservation, and Handling 9.1 Collect samples in glass containers following conventional sampling practices (Reference 8). Aqueous samples which flow freely are collected in refrigerated bottles using automatic sampling equipment. Solid samples are collected as grab samples using wide mouth jars. 9.2 Maintain samples at 0-4°C from the time of collection until extraction. If residual chlorine is present in aqueous samples, add 80 mg sodium thiosulfate per liter of water. EPA Methods 330.4 and 330.5 may be used to measure residual chlorine (Reference 9). 9.3 Begin sample extraction within seven days of collection, and analyze all extracts within 40 days of extraction. 10.0 Sample Extraction, Concentration, and Cleanup Samples containing 1% solids or less are extracted directly using continuous liquid/liquid extraction techniques (Section 10.2.1 and Figure 4). Samples containing 1-30% solids are diluted to the 1% level with reagent water (Section 10.2.2) and extracted using continuous liquid/liquid extraction techniques. Samples containing greater than 30% solids are extracted using ultrasonic techniques (Section 10.2.5) 10.1 Determination of Percent Solids 10.1.1 Weigh 5-10 g of sample into a tared beaker. 10.1.2 Dry overnight (12 hours minimum) at 110 ±5°C, and cool in a desiccator. September 1989 39 ------- Method 1625C 10.1.3 Determine percent solids as follows: % solids = weight of dry sample x 1Q0 weight of wet sample 10.2 Preparation of Samples for Extraction 10.2.1 Samples containing 1% solids or less—Extract sample directly using continuous liquid/liquid extraction techniques. 10.2.1.1 Measure 1.00 ±0.01 L of sample into a clean 1.5-2.0 L beaker. 10.2.1.2 Dilute aliquot—For samples which are expected to be difficult to extract, concentrate, or clean-up, measure an additional 100.0 ±1.0 mL into a clean 1.5-2.0 L beaker and dilute to a final volume of 1.00 ±0.1 L with reagent water. 10.2.1.3 Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into the sample aliquots. Proceed to preparation of the QC aliquots for low solids samples (Section 10.2.3). 40 September 1989 ------- Method 1625C STANDARD BLANK SAMPLE [10.2.3.1] [10.2.1.3,10.2.3.2] [10.2.3.3] [10.2.4] [10.3.2] [10.3.4] [10.5] SPIKE 1.0 mL OF STANDARDS STIR AND EQUILIBRATE STANDARD OR BLANK EXTRACT BASE NEUTRAL ORGANIC AQUEOUS CONCENTRATE TO 2-4 mL EXTRACT ACID CONCENTRATE TO 2-4 mL 1 L REAGENT WATER SPIKE 500 jjL OF 200 jjg/mL ISOTOPES STIR AND EQUILIBRATE 1 L ALIQUOT SPIKE 500 pL OF 200 ng/mL ISOTOPES ORGANIC > STIR EQUILI ' AND BRATE EXTRACT BASE/ NEUTRAL AQUEOUS 1 J, > ' ' [10.6] CONCENTRATE TO 1.0 mL CONCENTRATE T01.0 mL CONCENTRATE TO 1.0 mL * r . _ f f [11.3] ADD INTERNAL STANDARD ADD INTERNAL STANDARD ADD INTERNAL STANDARD / N ' t [11.41 INJECT INJECT INJECT FIGURE 4 Flow Chart for Extraction/Concentration of Low Solids Precision and Recovery Standard, Blank, and Sample by Method 1625. Numbers in Brackets [ ] Refer to Section Numbers in the Method. September 1989 41 ------- Method 1625C 10.2.2 Samples containing 1-30% solids 10.2.2.1 Mix sample thoroughly. 10.2.2.2 Using the percent solids found in Section 10.1.3, determine the weight of sample required to produce 1 L of solution containing 1% solids as follows: sample weight, (grams) = % solids 10.2.2.3 Discard all sticks, rocks, leaves and other foreign material prior to weighing. Place the weight determined in Section 10.2.2.2 in a clean 1.5-2.0 L beaker. 10.2.2.4 Dilute aliquot—For samples which are expected to be difficult to extract, concentrate, or clean up, weigh an amount of sample equal to one-tenth the amount determined in Section 10.2.2.2 into a second clean 1.5-2.0 L beaker. When diluted to 1.0 L, this dilute aliquot will contain 0.1% solids. 10.2.2.5 Bring the sample aliquot(s) above to 100-200 mL volume with reagent water. 10.2.2.6 Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into each sample aliquot. 10.2.2.7 Using a clean metal spatula, break any solid portions of the sample into small pieces. 10.2.2.8 Place the 3/4 inch horn on the ultrasonic probe approx Vz inch below the surface of each sample aliquot and pulse at 50% for three minutes at full power. If necessary, remove the probe from the solution and break any large pieces using the metal spatula or a stirring rod and repeat the sonication. Clean the probe with methylene chloride:acetone (1:1) between samples to preclude cross-contamination. 10.2.2.9 Bring the sample volume to 1.0 ±0.1 L with reagent water. 10.2.3 Preparation of QC aliquots for samples containing low solids (<30%). 10.2.3.1 For each sample or sample lot (to a maximum of 20) to be extracted at the same time, place three 1.0 ±0.01 L aliquots of reagent water in clean 1.5-2.0 L beakers. 10.2.3.2 Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into one reagent water aliquot. This aliquot will serve as the blank. 42 September 1989 ------- Method 1625C 10.2.3.3 Spike 1.0 mL of the precision and recovery standard (Section 6.14) into the two remaining reagent water aliquots. 10.2.4 Stir and equilibrate all sample and QC solutions for one to two hours. Extract the samples and QC aliquots per Section 10.3. 10.2.5 Samples containing 30% solids or greater 10.2.5.1 Mix the sample thoroughly. 10.2.5.2 Discard all sticks, rocks, leaves and other foreign material prior to weighing. Weigh 30 ±0.3 g into a clean 400-500 mL beaker. 10.2.5.3 Dilute aliquot—For samples which are expected to be difficult to extract, concentrate, or clean-up, weigh 3 ±0.03 g into a clean 400-500 mL beaker. 10.2.5.4 Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into each sample aliquot. 10.2.5.5 QC aliquots—For each sample or sample lot (to a maximum of 20) to be extracted at the same time, place three 30 ±0.3 g aliquots of the high solids reference matrix in clean 400-500 mL beakers. 10.2.5.6 Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into one high solids reference matrix aliquot. This aliquot will serve as the blank. 10.2.5.7 Spike 1.0 mL of the precision and recovery standard (Section 6.14) into the two remaining high solids reference matrix aliquots. Extract, concentrate, and clean up the high solids samples and QC aliquots per Sections 10.4 through 10.8. 10.3 Continuous Extraction of Low Solids (Aqueous) Samples—Place 100-150 mL methylene chloride in each continuous extractor and 200-300 mL in each distilling flask. 10.3.1 Pour the sample(s), blank, and QC aliquots into the extractors. Rinse the glass containers with 50-100 mL methylene chloride and add to the respective extractors. Include all solids in the extraction process. 10.3.2 Base/neutral extraction—Adjust the pH of the waters in the extractors to 12-13 with 6 N NaOH while monitoring with a pH meter. Begin the extraction by heating the flask until the methylene chloride is boiling. When properly adjusted, one to two drops of methylene chloride per second will fall from the condensor tip into the water. Test and adjust the pH of the waters during the first to second hour and during the fifth to tenth hour of extraction. Extract for 24-48 hours. 10.3.3 Remove the distilling flask, estimate and record the volume of extract (to the nearest 100 mL), and pour the contents through a drying column containing 7-10 cm anhydrous sodium sulfate. Rinse the distilling flask with 30-50 mL of methylene chloride and pour through the drying column. Collect the solution in September 1989 43 ------- Method 1625C a 500 mL K-D evaporator flask equipped with a 10 mL concentrator tube. Seal, label as the base/neutral fraction, and concentrate per Sections 10.5 through 10.6. 10.3.4 Acid extraction—Adjust the pH of the waters in the extractors to 2 or less using 6 N sulfuric acid. Charge clean distilling flasks with 300-400 mL of methylene chloride. Test and adjust the pH of the waters during the first one to two hours and during the fifth to tenth hour of extraction. Extract for 24-48 hours. Repeat Section 10.3.3, except label as the acid fraction. 10.4 Ultrasonic Extraction of High Solids Samples 10.4.1 Add 60 g of anhydrous sodium sulfate the sample and QC aliquot(s) (Section 10.2.5) and mix thoroughly. 10.4.2 Add 100 ±10 mL of acetone:methylene chloride (1:1) to the sample and mix thoroughly. 10.4.3 Place the 3/4 in. horn on the ultrasonic probe approx Vz in. below the surface of the solvent but above the solids layer and pulse at 50% for three minutes at full power. If necessary, remove the probe from the solution and break any large pieces using the metal spatula or a stirring rod and repeat the sonication. 10.4.4 Decant the extracts through Whatman 41 filter paper using glass funnels and collect in 500-1000 mL graduated cylinders. 10.4.5 Repeat the extraction steps (Sections 10.4.2 through 10.4.4) twice more for each sample and QC aliquot. On the final extraction, swirl the sample or QC aliquot, pour into its respective glass funnel, and rinse with acetone:methylene chloride. Record the total extract volume. 10.4.6 Pour each extract through a drying column containing 7-10 cm of anhydrous sodium sulfate. Rinse the graduated cylinder with 30-50 mL of methylene chloride and pour through the drying column. Collect each extract in a 500 mL K-D evaporator flask equipped with a 10 mL concentrator tube. Seal and label as the high solids semivolatile fraction. Concentrate and clean up the samples and QC aliquots per Sections 10.5 through 10.8. 10.5 Macro Concentration—Concentrate the extracts in separate 500 mL K-D flasks equipped with 10 mL concentrator tubes. 10.5.1 Add one to two clean boiling chips to the flask and attach a three-ball macro Snyder column. Prewet the column by adding approx 1 mL of methylene chloride through the top. Place the K-D apparatus in a hot water bath so that the entire lower rounded surface of the flask is bathed with steam. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15-20 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid has reached an apparent volume of 1 mL, remove the K-D apparatus from the bath and allow the solvent to drain and cool for at least 10 minutes. Remove the Snyder column and rinse the flask and its lower joint into the 44 September 1989 ------- Method 1625C concentrator tube with 1-2 mL of methylene chloride. A 5 mL syringe is recommended for this operation. 10.5.2 For performance standards (Sections 8.2 and 12.7) and for blanks (Section 8.5), combine the acid and base/neutral extracts for each at this point. Do not combine the acid and base/neutral extracts for aqueous samples. 10.6 Micro Concentration 10.6.1 Kuderna-Danish (K-D)—Add a clean boiling chip and attach a two-ball micro Snyder column to the concentrator tube. Prewet the column by adding approx 0.5 mL methylene chloride through the top. Place the apparatus in the hot water bath. Adjust the vertical position and the water temperature as required to complete the concentration in 5-10 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid reaches an apparent volume of approx 0.5 mL, remove the apparatus from the water bath and allow to drain and cool for at least 10 minutes. Remove the micro Snyder column and rinse its lower joint into the concentrator tube with approx 0.2 mL of methylene chloride. Adjust the final volume to 5.0 mL if the extract is to be cleaned up by GPC, to 1.0 mL if it does not require clean-up, or to 0.5 mL if it has been cleaned up. 10.6.2 Nitrogen blowdown—Place the concentrator tube in a warm water bath (35°C) and evaporate the solvent volume using a gentle stream of clean, dry nitrogen (filtered through a column of activated carbon). CAUTION: New plastic tubing must not be used between the carbon trap and the sample, since it may introduce interferences. The internal wall of the tube must be rinsed down several times with methylene chloride during the operation. During evaporation, the tube solvent level must be kept below the water level of the bath. The extract must never be allowed to become dry. Adjust the final volume to 5.0 mL if the extract is to be cleaned up by GPC, to 1.0 mL if it does not require clean-up, or to 0.5 mL if it has been cleaned up. 10.7 Transfer the concentrated extract to a clean screw-cap vial. Seal the vial with a Teflon- lined lid, and mark the level on the vial. Label with the sample number and fraction, and store in the dark at -20 to -10°C until ready for analysis. 10.8 GPC Setup and Calibration 10.8.1 Column packing 10.8.1.1 Place 75 ±5 g of SX-3 Bio-beads in a 400-500 mL beaker. 10.8.1.2 Cover the beads and allow to swell overnight (12 hours minimum). 10.8.1.3 Transfer the swelled beads to the column and pump solvent through the column, from bottom to top, at 4.5-5.5 mL/min prior to connecting the column to the detector. September 1989 45 ------- Method 1625C 10.8.1.4 After purging the column with solvent for one to two hours, adjust the column head pressure to 7-10 psig, and purge for four to five hours to remove air from the column. Maintain a head pressure of 7-10 psig. Connect the column to the detector. 10.8.2 Column calibration 10.8.2.1 Load 5 mL of the calibration solution (Section 6.4) into the sample loop. 10.8.2.2 Inject the calibration solution and record the signal from the detector. The elution pattern will be corn oil, bis(2-ethylhexyl) phthalate, pentachlorophenol, perylene, and sulfur. 10.8.2.3 Set the "dump time" to allow >85% removal of the corn oil and >85% collection of the phthalate. 10.8.2.4 Set the "collect time" to the peak minimum between perylene and sulfur. 10.8.2.5 Verify the calibration with the calibration solution after every 20 extracts. Calibration is verified if the recovery of the pentachlorophenol is greater than 85%. If calibration is not verified, the system shall be recalibrated using the calibration solution, and the previous 20 samples shall be re-extracted and cleaned up using the calibrated GPC system. 10.9 Extract Cleanup 10.9.1 Filter the extract or load through the filter holder to remove particulates. Load the 5.0 mL extract onto the column. The maximum capacity of the column is 0.5- 1.0 g. If necessary, split the extract into multiple aliquots to prevent column overload. 10.9.2 Elute the extract using the calibration data determined in Section 10.8.2. Collect the eluate in a clean 400-500 mL beaker. 10.9.3 Concentrate the cleaned up extract to 5.0 mL per Section 10.5. 10.9.4 Rinse the sample loading tube thoroughly with methylene chloride between extracts to prepare for the next sample. 10.9.5 If a particularly dirty extract is encountered, a 5.0 mL methylene chloride blank shall be run through the system to check for carry-over. 10.9.6 Concentrate the extract to 0.5 mL and transfer to a screw-cap vial per Sections 10.6 and 10.7. Concentrating extracts cleaned up by GPC to 0.5 mL will place the analytes in the same part of the GCMS calibration range as in samples not subjected to GPC. 11.0 GCMS Analysis 46 September 1989 ------- Method 1625C 11.1 Establish the operating conditions given in Tables 5 or 6 for analysis of the base/neutral or acid extracts, respectively. For analysis of combined extracts (Sections 10.5.2 and 10.9.6), use the operating conditions in Table 5. 11.2 Bring the concentrated extract (Section 10.7) or standard (Sections 6.13 through 6.14) to room temperature and verify that any precipitate has redissolved. Verify the level on the extract (Sections 6.6 and 10.7) and bring to the mark with solvent if required. 11.3 Add the internal standard solution (Section 6.10) to the extract (use 1.0 pL of solution per 0.1 mL of extract) immediately prior to injection to minimize the possibility of loss by evaporation, adsorption, or reaction. Mix thoroughly. 11.4 Inject a volume of the standard solution or extract such that 100 ng of the internal standard will be injected, using on-column or splitless injection. For 1 mL extracts, this volume will be 1.0 |iL. Start the GC column initial isothermal hold upon injection. Start MS data collection after the solvent peak elutes. Stop data collection after the benzo(ghi)perylene or pentachlorophenol peak elutes for the base/neutral (or semi- volatile) or acid fraction, respectively. Return the column to the initial temperature for analysis of the next sample. 12.0 System and Laboratory Performance 12.1 At the beginning of each 8 hr shift during which analyses are performed, GCMS system performance and calibration are verified for all pollutants and labeled compounds. For these tests, analysis of the 100 |ig/mL calibration standard (Section 6.13) shall be used to verify all performance criteria. Adjustment and/or recalibration (per Section 7) shall be performed until all performance criteria are met. Only after all performance criteria are met may samples, blanks, and precision and recovery standards be analyzed. 12.2 DFTPP Spectrum Validity—Inject 1 |iL of the DFTPP solution (Section 6.11) either separately or within a few seconds of injection of the standard (Section 12.1) analyzed at the beginning of each shift. The criteria in Table 7 shall be met. 12.3 Retention Times—The absolute retention time of 2,2'-difluorobiphenyl shall be within the range of 1078-1248 seconds and the relative retention times of all pollutants and labeled compounds shall fall within the limits given in Tables 5 and 6. 12.4 GC Resolution—The valley height between anthracene and phenanthrene at m/z 178 (or the analogs at m/z 188) shall not exceed 10 percent of the taller of the two peaks. 12.5 Calibration Verification—Compute the concentration of each pollutant (Tables 1 and 2) by isotope dilution (Section 7.4) for those compounds which have labeled analogs. Compute the concentration of each pollutant which has no labeled analog by the internal standard method (Section 7.5). Compute the concentration of the labeled compounds by the internal standard method. These concentrations are computed based on the calibration data determined in Section 7. 12.5.1 For each pollutant and labeled compound being tested, compare the concentration with the calibration verification limit in Table 10. If all compounds meet the acceptance criteria, calibration has been verified and analysis of blanks, samples, and precision and recovery standards may proceed. If, however, any compound September 1989 47 ------- Method 1625C fails, the measurement system is not performing properly for that compound. In this event, prepare a fresh calibration standard or correct the problem causing the failure and repeat the test (Section 12.1), or recalibrate (Section 7). 12.6 Multiple Peaks—Each compound injected shall give a single, distinct GC peak. 12.7 On-going Precision and Accuracy 12.7.1 Analyze the extract of one of the pair of precision and recovery standards (Section 10) prior to analysis of samples from the same lot. 12.7.2 Compute the concentration of each pollutant (Tables 1 and 2) by isotope dilution (Section 7.4) for those compounds which have labeled analogs. Compute the concentration of each pollutant which has no labeled analog by the internal standard method (Section 7.5). Compute the concentration of the labeled compounds by the internal standard method. 12.7.3 For each pollutant and labeled compound, compare the concentration with the limits for on-going accuracy in Table 10. If all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may proceed. If, however, any individual concentration falls outside of the range given, system performance is unacceptable for that compound. NOTE: The large number of compounds in Table 10 present a substantial probability that one or more will fail when all compounds are analyzed. To determine if the extraction/concentration system is out of control or if the failure is caused by probability, proceed as follows: 12.7.3.1 Analyze the second aliquot of the pair of precision and recovery standards (Section 10). 12.7.3.2 Compute the concentration of only those pollutants or labeled compounds that failed the previous test (Section 12.7.3). If these compounds now pass, the extraction/concentration processes are in control and analysis of blanks and samples may proceed. If, however, any of the same compounds fail again, the extraction/concentration processes are not being performed properly for these compounds. In this event, correct the problem, re-extract the sample lot (Section 10) and repeat the on-going precision and recovery test (Section 12.7). 12.7.4 Add results which pass the specifications in Section 12.7.3 to initial and previous on-going data for each compound in each matrix. Update QC charts to form a graphic representation of continued laboratory performance (Figure 5). Develop a statement of laboratory accuracy for each pollutant and labeled compound in each matrix type 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+2§. For example, if R = 95% anjd s = 5%, the accuracy is 85- 105%. 48 September 1989 ------- Method 1625C s N 2 K < < LL) CC < * < UJ (V 45,000 35,000 -<~ J 1 L I I i ANTHRACENED,,, J L 25,000 1 1 1 1 1 , j , 1 r 123456789 10 ANALYSIS NUMBER • + 3s 3s 8| P UJ < cr oc »- z < 1 10 1 00 _L _L ANTHRACENE g go 1 1 , , 1 1 , , p 6/1 6/1 6/1 6/1 6/2 6/2 6/3 6/3 6/4 6/5 DATE ANALYZED ¦ + 3s - 3s FIGURE 5 Quality Control Charts Showing Area (top graph) and Relative Response of Anthracene to Anthracene-d10 (lower graph) Plotted as a Function of Time or Analysis Number. 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. For unidentified GC peaks, the spectrum is compared to spectra in the EPA/NIH mass spectral file per Section 13.3. 13.1 Labeled Compounds and Pollutants Having No Labeled Analog (Tables 1-4) 13.1.1 The signals for all characteristic m/z's stored in the spectral library (Section 7.2.4) 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 two (one-half to two times) for all masses stored in the library. 13.1.3 For the compounds for which the system has been calibrated (Tables 1 and 2), the retention time shall be within the windows specified in Tables 5 and 6, or within September 1989 49 ------- Method 1625C ±15 scans or ±15 seconds (whichever is greater) for compounds for which no window is specified. 13.1.4 The system has not been calibrated for the compounds listed in Tables 3 and 4, however, the relative retention times and mass spectra of these compounds are known. Therefore, for a compound in Table 3 or 4 to be identified, its retention time relative to the internal standard 2,2'-difluorobiphenyl must fall within a retention time window of ±30 seconds, or ±30 scans (whichever is greater) of the nominal retention time of the compound specified in Table 5 or 6. 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 7.2.4) 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 two for all masses stored in the spectral library. 13.2.3 The relative retention time between the pollutant and its labeled analog shall be within the windows specified in Tables 5 and 6. 13.3 Unidentified GC Peaks 13.3.1 The signals for masses specific to a GC peak shall all maximize within ±1 scan. 13.3.2 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 two with the masses stored in the EPA/NIH Mass Spectral File. 13.4 The m/z's present in the experimental mass spectrum that are not present in the reference mass spectrum shall be accounted for by contaminant or background ions. If the experimental 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 extraction, concentration, and 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 extraction. Relative response (RR) values for sample mixtures are used in conjunction with the calibration curves described in Section 7.4 to determine concentrations directly, so long as labeled compound spiking levels are constant. For the phenol example given in Figure 1 (Section 7.4.1), RR would be equal to 1.114. For this RR value, the phenol calibration curve given in Figure 1 indicates a concentration of 27 \ig/mL in the sample extract (Cex). 14.2 Internal Standard—Compute the concentration in the extract using the response factor determined from calibration data (Section 7.5) and the following equation: 50 September 1989 ------- Method 1625C (A x C.) Cex (MgtoL) = ' " (A. x RF) where, Cex = The concentration of the compound in the extract, and the other terms are as defined in Section 7.5.1. 14.3 The concentration of the pollutant in the solid phase of the sample is computed using the concentration of the pollutant in the extract and the weight of the solids (Section 10), as follows: (C x V ) Concentration in solid (ug/kg) = —— — W where, Vex = The extract volume in mL, and Ws is the sample weight in kg. 14.4 Dilution of Samples—If the EICP area at the quantitation m/z for any compound exceeds the calibration range of the system, the extract of the dilute aliquot (Section 10) is analyzed by isotope dilution. For water samples, where the base/neutral and acid extracts are not combined, re-analysis is only required for the extract (B/N or A) in which the compound exceeds the calibration range. If further dilution is required and the sample holding time has not been exceeded, a smaller sample aliquot is extracted per Sections 14.4.1 through 14.4.3. If the sample holding time has been exceeded, the sample extract is diluted by successive factors of 10, internal standard is added to give a concentration of 100 \ig/mL in the diluted extract, and the diluted extract is analyzed by the internal standard method. 14.4.1 For samples containing one percent solids or less for which the holding time has not been exceeded, dilute 10 mL, 1.0 mL, 0.1 mL etc. of sample to one liter with reagent water and extract per Section 10.2.1. 14.4.2 For samples containing 1-30% solids for which the holding time has not been exceeded, extract an amount of sample equal to 1/100 the amount determined in Section 10.2.2.2. Extract per Section 10.2.2. 14.4.3 For samples containing 30% solids or greater for which the holding time has not been exceeded, extract 0.30 ±0.003 g of sample per Section 10.2.5. 14.5 Dilution of samples containing high concentrations of compounds to be identified per Section 13.3—When the EICP area of the quantitation m/z of a compound to be identified per Section 13.3 exceeds the linear range of the GCMS system, or when any peak is saturated, dilute the sample per Sections 14.4.1 through 14.4.3. September 1989 51 ------- Method 1625C 14.6 Results are reported to three significant figures for all pollutants, labeled compounds, and tentatively identified compounds found in all standards, blanks, and samples. For aqueous samples, the units are Hg/L, and for samples containing one percent solids or greater (soils, sediments, filter cake, compost), the units are |ig/kg, based on the dry weight of the solids. 14.6.1 Results for samples which 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 15.4). 15.0 Analysis of Complex Samples 15.1 Some samples may contain high levels (>1000 Hg/L) of the compounds of interest, interfering compounds, and/or polymeric materials. Some samples will not concentrate to 1 mL (Section 10.6); others will overload the GC column and/or mass spectrometer. 15.2 Analyze the dilute aliquot (Section 10) when the sample will not concentrate to 1.0 mL. If a dilute aliquot was not extracted, and the sample holding time (Section 9.3) has not been exceeded, dilute an aliquot of an aqueous sample with reagent water, or weigh a dilute aliquot of a high solids sample and re-extract (Section 10); otherwise, dilute the extract (Section 14.4) and analyze by the internal standard method (Section 14.2). 15.3 Recovery of Internal Standard—The EICP area of the internal standard should be within a factor of two of the area in the shift standard (Section 12.1). If the absolute areas of the labeled compounds are within a factor of two of the respective areas in the shift standard, and the internal standard area is less than one-half of its respective area, then loss of the internal standard in the extract has occurred. In this case, use one of the labeled compounds (preferably a polynuclear aromatic hydrocarbon) to compute the concentration of a pollutant with no labeled analog. 15.4 Recovery of Labeled Compounds—In most samples, labeled compound recoveries will be similar to those from reagent water or from the high solids reference matrix (Section 12.7). If the labeled compound recovery is outside the limits given in Table 10, the extract from the dilute aliquot (Section 10) is analyzed as in Section 14.4. If the recoveries of all labeled compounds and the internal standard are low (per the criteria above), then a loss in instrument sensitivity is the most likely cause. In this case, the 100 |ig/mL calibration standard (Section 12.1) shall be analyzed and calibration verified (Section 12.5). If a loss in sensitivity has occurred, the instrument shall be repaired, the performance specifications in Section 12 shall be met, and the extract reanalyzed. If a loss in instrument sensitivity has not occurred, the method does not apply to the sample being analyzed, and the result may not be reported for regulatory compliance purposes. 16.0 Method Performance 16.1 Interlaboratory performance for this method is detailed in Reference 10. Reference mass spectra, retention times, and response factors are from References 11 and 12. Results of initial tests of this method on municipal sludge can be found in Reference 13. 52 September 1989 ------- Method 1625C 16.2 A chromatogram of the 100 |ig/mL acid/base/neutral calibration standard (Section 6.13) is shown in Figure 6. References 1. "Performance Tests for the Evaluation of Computerized Gas Chromatography/Mass Spectrometry Equipment and Laboratories" USEPA, EMSL Cincinnati, Ohio 45268, EPA 600/4-80-025 (April 1980). 2. National Standard Reference Data System, "Mass Spectral Tape Format", US National Bureau of Standards (1979 and later attachments). 3. "Working with Carcinogens," DHEW, PHS, CDC, NIOSH, Publication 77-206, (August 1977). 4. "OSHA Safety and Health Standards, General Industry" OSHA 2206, 29 CFR 1910 (January 1976). 5. "Safety in Academic Chemistry Laboratories," ACS Committee on Chemical Safety (1979). 6. "Inter-laboratory Validation of U. S. Environmental Protection Agency Method 1625A, Addendum Report", SRI International, Prepared for Analysis and Evaluation Division (WH-557), USEPA, 401 M St SW, Washington, DC 20460 (January 1985). 7. "Handbook of Analytical Quality Control in Water and Wastewater Laboratories," USEPA, EMSL, Cincinnati, OH 45268, EPA 600/4-79-019 (March 1979). 8. "Standard Practice for Sampling Water," ASTM Annual Book of Standards, ASTM, Philadelphia, PA, 76 (1980). 9. "Methods 330.4 and 330.5 for Total Residual Chlorine," USEPA, EMSL, Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979). 10. "Inter-laboratory Validation of US Environmental Protection Agency Method 1625," USEPA, Effluent Guidelines Division, Washington, DC 20460 (June 15, 1984). 11. "Narrative for Episode 1036: Paragraph 4© Mass Spectra, Retention Times, and Response Factors", U S Testing Co, Inc, Prepared for W. A. Telliard, Industrial Technology Division (WH-552), USEPA, 401 M St SW, Washington, DC 20460 (October 1985). 12. "Narrative for SAS 109: Analysis of Extractable Organic Pollutant Standards by Isotope Dilution GC/MS", S-CUBED Division of Maxwell Laboratories, Inc., Prepared for W.A. Telliard, Industrial Technology Division (WH-552), USEPA, 401 M St SW, Washington, DC 20460 (July 1986). 13. Colby, Bruce N., and Ryan, Philip W. "Initial Evaluation of Methods 1634 and 1635 for the analysis of Municipal Wastewater Treatment Sludges by Isotope Dilution GCMS", Pacific Analytical Inc., Prepared for W.A. Telliard, Industrial Technology Division (WH- 552), USEPA, 401 M St SW, Washington DC 20460 (July 1986). September 1989 53 ------- Method 1625C SCANS 100.0 RIC DATA: ABNID116S »1 93/13/84 5:24:80 CALIs ABN1DI166 #1 SAMPLE: AB,G,UER,00100,00,C,NA:Hh.NAS CONDS.: 1S25A,30^0.251111,5630,30-28088,156280,30CIVSI RANGE: G 1,3200 LABEL: N 2, 3.0 GUAN: A 2, 2.0 J 0 BASE: U 20, 1 TO 3200 RIC V- u 715776. 11 Ul 500 7:55 1000 15:50 1500 23:45 2000 31:48 2500 39:35 3006 47:30 SCAN TIME FIGURE 6 Chromatogram of Combined Acid/Base/Neutral Standard. 54 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 555 acetophenone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 42 21 43 245 49 19 50 221 51 524 52 75 61 13 62 26 63 422 65 31 73 13 74 64 75 36 76 62 77 941 78 11 89 12 91 22 105 1000 106 87 120 479 121 38 556 4-aminobiphenyl m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 55 63 65 72 82 83 73 85 163 115 142 139 65 141 132 167 163 168 280 169 1000 170 216 557 aniline int. m/z int. m/z int. m/z int. m/z int. m/z int. m/z 40 65 41 66 42 16 46 11 47 75 50 40 51 47 52 54 53 12 54 40 61 17 62 28 63 59 64 33 65 226 66 461 74 11 78 14 91 10 92 136 93 1000 94 73 558 o- anisidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 22 41 43 42 10 50 60 51 106 52 202 53 286 54 39 61 12 62 25 63 43 64 24 65 142 66 20 76 13 77 36 68 32 79 25 80 915 81 41 92 47 93 14 94 18 105 18 108 1000 109 55 122 123 844 124 56 559 aramite m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 606 57 758 59 328 63 782 65 285 74 113 77 155 91 339 105 153 107 239 121 107 123 120 163 143 175 182 185 1000 187 328 191 346 197 191 319 270 334 137 560 benzanthrone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 74 69 75 71 87 97 88 160 99 69 100 215 101 278 150 58 174 67 199 63 200 350 201 236 202 762 203 126 230 1000 231 177 September 1989 55 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 561 1,3-benzenediol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 64 41 19 52 42 43 36 49 11 50 43 51 54 52 29 53 184 54 89 55 97 61 15 62 27 63 74 64 61 65 13 68 56 69 119 71 16 81 201 82 251 95 13 109 11 110 1000 111 51 562 benzenethiol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 128 50 149 51 205 65 175 66 505 69 114 77 161 84 259 109 316 110 1000 111 102 563 2,3-benzofluorene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 74 52 81 69 94 143 95 253 106 60 107 205 108 491 187 75 189 90 213 233 214 60 215 987 216 1000 217 166 943 benzoic acid m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 29 50 221 51 413 52 45 66 11 74 53 75 25 76 81 77 778 78 76 105 1000 122 868 564 benzyl alcohol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 17 59 16 50 155 51 319 52 78 53 84 61 11 62 31 63 70 64 12 65 75 74 35 75 13 76 18 77 565 78 116 79 1000 80 73 89 65 90 64 91 125 105 38 106 18 107 523 108 737 109 43 565 2-bromochlorobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 49 237 50 890 51 183 73 158 74 506 75 1000 76 202 111 961 113 287 190 638 192 809 194 193 56 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 566 3-bromochlorobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 49 201 50 834 51 174 73 169 74 509 75 914 76 197 111 1000 113 301 190 625 192 802 194 191 567 4-chloro-2-nitroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 49 119 50 174 51 260 52 531 61 205 62 394 63 1000 64 315 65 192 73 290 74 105 75 156 76 127 78 152 90 724 91 253 101 232 114 312 126 766 128 234 142 211 172 915 174 289 568 5-chloro-o -toluidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 115 51 261 52 257 53 137 77 420 78 134 79 140 89 152 106 1000 140 599 141 964 142 265 143 313 569 4-chloroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 60 62 55 63 147 64 135 65 329 73 51 91 63 92 186 99 67 100 115 127 1000 128 81 129 292 570 3-chloronitrobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 619 51 189 73 144 74 330 75 1000 76 169 85 101 99 258 111 851 113 266 157 424 159 137 571 o- cresol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 102 51 181 53 144 77 358 79 380 80 159 89 114 90 231 107 783 108 1000 944 p- -cresol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 136 51 224 52 106 53 196 77 420 79 308 80 145 90 122 107 822 108 1000 572 crotoxyphos m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 633 44 448 67 42 77 70 79 41 104 100 105 484 109 21 127 1000 166 180 193 401 194 20 September 1989 57 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 573 2,6-di-t-butyl-p-benzoquinone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 392 53 586 55 325 57 668 65 416 67 927 77 376 79 308 91 456 95 322 107 248 121 255 135 538 136 240 149 429 163 292 177 1000 205 203 220 410 574 2,4-diaminotoluene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 70 42 55 51 76 52 70 53 51 61 91 67 50 77 147 78 69 93 63 94 224 104 128 105 134 106 67 121 958 122 1000 123 79 575 l,2-dibromo-3-chloropropane m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 42 38 59 341 51 104 61 38 75 1000 76 75 77 331 81 43 93 117 95 106 97 12 105 67 106 17 119 74 121 66 155 635 157 784 158 20 159 204 187 10 945 3,5-dibromo-4-hydroxybenzonitrile m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 53 148 61 193 62 222 88 632 117 137 168 152 170 141 275 489 277 1000 279 451 576 2,6-dichloro-4-nitroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 206 52 1000 61 523 62 828 63 588 73 470 65 137 89 218 90 443 97 458 124 954 126 401 133 218 160 401 176 431 178 134 206 378 58 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 577 l,3-dichloro-2-propanol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 14 42 55 43 503 44 22 47 12 58 15 49 113 50 15 51 37 57 10 61 12 75 14 78 11 79 1000 80 25 81 310 578 2,3-dichloroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 52 138 61 151 62 265 63 455 64 142 65 105 73 130 90 460 99 202 125 108 126 149 161 1000 163 626 165 101 579 2,3-dichloronitrobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 49 220 50 257 61 150 62 120 63 173 73 336 74 976 75 743 84 351 85 166 86 125 109 1000 110 204 111 303 133 701 135 435 145 580 147 368 161 190 163 121 191 411 193 263 946 2,6-dichlorophenol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 49 111 62 160 63 714 73 132 98 293 99 117 126 260 162 1000 164 613 166 101 580 l,2:3,4-diepoxybutane m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 37 41 29 42 83 43 60 55 1000 56 67 57 155 58 16 85 13 581 3,3'-dimethoxybenzidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 65 44 79 222 85 69 93 84 107 46 115 110 122 115 158 154 186 144 201 552 229 162 244 1000 245 152 September 1989 59 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 582 dimethyl sulfone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 44 10 45 94 46 29 47 18 48 69 62 14 63 69 64 22 65 19 79 1000 81 36 94 528 96 23 583 p-dimethylaminoazobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 42 483 51 181 77 447 78 120 79 147 91 109 104 142 105 190 120 1000 148 160 225 676 584 7,12-dimethylbenzo(a)anthracene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 101 24 112 34 113 112 114 38 119 212 120 296 125 46 126 81 127 60 128 76 215 24 226 47 237 23 239 313 240 230 241 433 242 61 250 32 252 68 253 33 255 84 256 1000 257 180 585 N,N-dimethylformamide m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 58 41 79 42 497 43 115 44 1000 45 19 57 17 58 83 72 89 73 994 74 35 586 3,6-dimethylphenanthrene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 76 113 89 129 94 179 101 142 102 151 189 388 190 193 191 430 205 246 206 1000 207 159 587 1,4-dinitrobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 1000 51 131 63 228 64 218 74 311 75 623 76 664 92 240 122 166 168 399 588 diphenyldisulfide m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 153 51 293 65 671 59 282 77 141 109 1000 110 132 154 191 185 117 218 418 60 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 589 ethyl methanesulfonate m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 42 16 43 72 45 208 48 40 59 19 63 23 64 22 65 93 79 1000 80 127 81 42 96 16 97 206 109 579 111 18 123 15 124 33 590 ethylenethiourea m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 46 42 126 45 97 46 42 59 14 72 89 73 151 102 1000 591 ethynylestradiol 3-methyl ether m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 155 53 101 91 157 115 143 147 226 159 132 160 115 173 199 174 313 227 1000 228 149 242 153 310 516 592 hexachloropropene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 47 131 71 333 106 334 108 200 117 329 119 320 141 206 143 196 211 631 213 1000 215 623 217 186 947 hexanoic acid m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 627 42 535 43 214 45 186 46 19 55 128 56 90 57 102 60 1000 61 66 69 21 70 20 73 412 74 56 87 98 593 2-isopropylnaphthalene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 100 63 Ill 76 157 77 129 115 147 127 131 128 216 152 133 153 184 154 114 155 1000 156 139 170 368 594 isosafrole m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 110 51 222 63 127 77 277 78 208 103 355 104 441 131 371 132 107 135 129 161 250 162 1000 595 longifolene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 53 438 55 719 65 346 67 453 77 566 69 713 91 1000 93 611 94 546 95 404 105 614 107 475 119 394 133 338 161 568 204 172 September 1989 61 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 596 malachite green m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 118 113 126 313 165 369 208 135 209 233 210 181 237 158 253 1000 254 160 329 189 330 775 331 170 597 methapyriline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 42 72 45 47 53 40 58 1000 71 188 72 225 78 54 79 48 97 516 190 40 191 67 598 methyl methanesulfonate m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 178 56 15 48 108 50 26 63 35 64 48 65 285 78 27 79 821 80 1000 81 44 82 33 95 137 109 59 110 60 599 2-methylbenzothiozole m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 152 50 133 58 153 62 106 63 309 69 513 82 204 108 392 109 102 148 279 149 1000 150 110 900 3-methylcholanthrene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 113 58 119 55 125 83 126 305 132 99 133 122 134 160 250 56 252 322 253 271 263 59 265 106 266 50 267 192 268 1000 269 185 901 4,4'-methylenebis(2-chloroaniline) m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 77 190 84 107 98 299 104 133 115 226 140 316 195 352 229 228 231 1000 233 227 265 171 266 631 267 144 268 358 902 4,5-methylenephenanthrene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 50 62 55 63 95 74 69 81 145 86 53 87 60 94 255 95 659 163 80 187 213 188 137 189 900 190 1000 62 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 903 1-methylfluorene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 66 51 87 62 57 63 137 74 64 75 85 76 196 83 135 87 53 88 78 89 203 90 58 139 54 151 73 152 124 163 57 164 58 165 1000 166 136 176 96 177 52 178 202 179 182 180 686 181 99 904 2-methylnaphthalene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 29 51 39 57 28 58 47 62 26 63 65 65 19 69 56 70 25 71 126 74 25 75 23 76 14 77 15 86 13 87 18 89 42 113 19 114 13 115 303 116 25 126 13 139 98 140 24 141 748 142 1000 143 105 905 1-methylphenanthrene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 54 63 86 70 62 74 51 81 52 83 164 96 132 163 55 165 217 189 165 191 532 192 1000 193 152 906 2-(methylthio)benzothiazole m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 790 50 212 63 383 69 578 82 233 108 627 136 239 148 938 180 250 181 1000 907 1,5-naphthalenediamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 48 65 83 77 75 79 111 103 86 118 52 130 262 131 40 141 43 157 89 158 1000 159 117 908 1,4-naphthoquinone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 445 51 62 52 52 66 69 74 189 75 205 76 590 101 51 102 613 103 52 104 550 130 433 158 1000 159 100 909 alpha-naphthylamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 25 51 31 57 36 59 46 62 28 63 59 65 27 71 58 72 104 89 62 113 22 114 34 115 401 116 212 142 53 143 1000 144 101 September 1989 63 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 910 5-nitro-o-toluidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 194 52 159 53 121 77 766 78 176 79 619 94 168 104 120 106 691 152 1000 911 2-nitroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 64 50 51 51 89 52 207 53 74 62 58 63 181 64 155 65 960 66 96 80 212 91 86 92 566 108 170 138 1000 139 63 912 3-nitroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 101 52 120 53 59 62 58 63 143 64 121 65 1000 66 114 80 169 91 62 92 764 93 62 108 87 138 717 139 51 913 4-nitroaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 52 228 53 160 62 110 63 216 64 164 65 1000 66 124 80 266 92 300 108 636 138 520 914 4-nitrobiphenyl m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 131 63 104 76 179 115 134 141 277 151 259 152 902 153 284 169 374 199 1000 200 125 915 N-nitroso-di-n-butylamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 1000 42 536 43 570 44 313 55 129 56 167 57 994 84 985 86 103 99 197 115 158 116 237 158 161 916 N-nitrosodiethylamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 170 42 079 43 69 44 1000 45 20 54 18 56 525 57 492 70 24 71 28 85 25 87 31 102 807 103 35 917 N-nitrosomethylethylamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 117 42 1000 43 667 44 26 54 17 56 189 57 99 59 13 71 60 73 57 88 772 89 20 64 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 918 N-nitrosomethylphenylamine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 181 51 434 52 104 63 110 77 1000 78 194 79 331 104 147 106 673 107 220 212 137 919 N-nitrosomorpholine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 181 42 192 43 52 44 17 54 85 55 95 56 1000 57 49 85 13 86 333 87 14 116 337 920 N-nitrosopiperidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 320 42 1000 43 43 51 14 52 12 53 32 54 58 55 444 56 224 57 17 67 21 82 26 83 28 84 47 114 491 115 26 921 pentachlorobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 73 160 108 239 125 102 178 102 213 179 215 218 217 106 248 648 250 1000 252 642 254 199 922 pentachloroethane m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 47 203 60 398 62 119 83 378 85 218 94 114 95 165 117 1000 119 979 121 306 130 293 132 272 165 716 167 901 169 422 923 pentamethylbenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 126 53 84 63 61 65 99 77 145 79 64 91 218 105 128 115 120 117 91 133 1000 134 105 147 60 148 420 924 perylene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 74 33 111 43 112 70 113 Ill 124 132 125 251 126 243 224 49 248 75 249 52 250 284 251 86 252 1000 253 219 925 phenacetin m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 43 443 51 33 52 112 53 164 63 39 64 30 65 47 79 31 80 179 31 154 108 1000 109 196 110 50 137 461 138 40 179 672 180 64 September 1989 65 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 926 phenothiazine^ m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 145 51 120 63 134 69 190 100 128 154 149 166 240 167 607 198 186 199 1000 200 143 927 1-phenylnaphthalene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 132 51 156 63 148 74 124 75 142 76 136 87 101 88 183 89 162 100 155 101 527 102 111 200 144 201 136 202 643 203 1000 204 999 205 159 928 2-phenylnaphthalene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 51 108 63 101 76 136 88 133 89 158 101 333 102 188 202 398 203 270 204 1000 205 157 929 pronamide m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 270 66 109 74 112 75 137 84 194 109 186 145 334 147 198 173 1000 175 615 254 133 255 211 256 102 257 122 930 pyridine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 45 48 11 49 62 50 324 51 414 52 879 53 112 54 12 55 16 75 21 76 19 77 22 78 151 79 1000 80 101 81 58 931 safrole m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 132 51 369 63 108 77 391 78 228 103 348 104 477 105 130 131 437 132 166 161 298 162 1000 163 109 932 squalene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 53 62 55 94 67 105 68 119 69 1000 70 57 79 43 81 465 82 52 93 70 95 104 107 43 109 47 121 46 137 41 933 1,2,4,5-tetrachlorobenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 47 125 49 176 61 127 72 183 73 332 74 448 84 197 108 284 109 231 143 194 145 117 179 237 181 224 214 791 216 1000 218 482 220 101 66 September 1989 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 948 2,3,4,6-tetrachlorophenol m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 61 234 65 167 66 105 83 134 84 178 96 202 97 107 131 463 133 270 166 298 168 273 194 168 196 164 230 793 232 1000 234 471 934 thianaphthene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 80 50 91 51 65 62 82 63 162 67 78 69 139 74 55 89 191 90 136 108 82 134 1000 135 104 136 52 935 thioacetamide m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 225 42 485 43 44 46 18 57 36 58 93 59 165 60 437 75 1000 76 25 77 43 936 thioxanthone m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 262 63 180 69 320 74 116 69 176 82 121 92 188 108 129 139 385 152 227 183 112 184 951 185 137 212 1000 213 145 937 o- toluidine m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 40 51 41 38 42 35 49 10 50 88 51 169 52 164 53 192 53 86 62 26 63 68 64 30 65 59 66 24 74 19 65 14 76 21 77 313 78 113 79 243 80 80 89 107 90 76 91 52 104 45 106 1000 107 90 938 1,2,3-trimethoxybenzene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 50 257 51 459 52 139 53 276 63 112 65 341 67 114 77 246 79 132 82 117 93 483 95 801 107 190 108 144 110 898 125 578 153 759 168 1000 939 2,4,5-trimethylaniline m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 41 80 52 58 51 63 53 66 65 150 67 74 79 62 91 167 93 51 117 54 118 65 119 93 120 1000 121 87 134 670 135 978 136 99 September 1989 67 ------- Method 1625C Appendix A Mass Spectra in the Form of Mass/Intensity Lists 940 triphenylene m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 74 52 87 55 100 107 101 108 112 131 113 244 114 181 200 67 202 56 224 84 225 56 226 313 227 132 228 1000 229 184 941 tripropylene glycol methyl ether m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 45 492 46 15 47 19 55 17 57 68 58 43 59 1000 60 34 71 16 72 44 73 363 74 232 103 57 117 92 161 21 942 1,3,5-trithiane m/z int. m/z int. m/z int. m/z int. m/z int. m/z int. 46 1000 47 150 48 98 59 93 60 76 64 136 73 102 91 92 92 111 110 58 138 259 68 September 1989 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