**SW-846 Update V 8270D - 1 Revision 5 October 2012**  **METHOD 8270D**

**SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY** 

**SW-846 is not intended to be an analytical training manual. Therefore, method**  **procedures are written based on the assumption that they will be performed by analysts who are**  **formally trained in at least the basic principles o f chemical analysis and in the use of the subject**  **technology.**

**In addition, SW-846 methods, with the exception of required method use for the analysis**  **of method defined parameters (MDPs), are intended t o be guidance methods that contain**  **general information on how to perform an analytical procedure or technique, which a laboratory**  **can use as a basic starting point for generating it s own detailed standard operating procedure**  **(SOP), either for its own general use or for a spec ific project application. The performance data**  **included in this method are for guidance purposes o nly, and are not intended to be and must not**  **be used as absolute quality control (QC) acceptance criteria for purposes of laboratory**  **accreditation.**

**1.0 SCOPE AND APPLICATION**

**1.1 This method is used to determine the concentrat ion of semivolatile organic**  **compounds in extracts prepared from many types of s olid waste matrices, soils, air sampling**  **media and water samples. Direct injection of a sam ple may be used in limited applications.**  **The following Resource Conservation and Recovery Ac t (RCRA) analytes have been**  **determined by this method:**

**Compounds CAS No a**  **Appropriate Preparation Techniques b** 

**3510 3520 3540/** 

**3541 3550 3580 Acenaphthene 83-32-9**  **X X X X X Acenaphthylene 208-96-8**  **X X X X X Acetophenone 98-86-2**  **X ND ND ND X 2-Acetylaminofluorene 53-96-3**  **X ND ND ND X 1-Acetyl-2-thiourea 591-08-2**  **LR ND ND ND LR Aldrin 309-00-2**  **X X X X X 2-Aminoanthraquinone 117-79-3**  **X ND ND ND X Aminoazobenzene 60-09-3**  **X ND ND ND X 4-Aminobiphenyl 92-67-1**  **X ND ND ND X 3-Amino-9-ethylcarbazole 132-32-1**  **X X ND ND ND Anilazine 101-05-3**  **X ND ND ND X Aniline 62-53-3**  **X X ND X X o-Anisidine 90-04-0**  **X ND ND ND X Anthracene 120-12-7**  **X X X X X Aramite 140-57-8**  **HS ND ND ND X Aroclor 1016 12674-11-2**  **X X X X X Aroclor 1221 11104-28-2**  **X X X X X Aroclor 1232 11141-16-5**  **X X X X X Aroclor 1242 53469-21-9**  **X X X X X Aroclor 1248 12672-29-6**  **X X X X X Aroclor 1254 11097-69-1**  **X X X X X Aroclor 1260 11096-82-5**  **X X X X X SW-846 Update V 8270D - 2 Revision 5**  **October 2012 Compounds CAS No**  **a Appropriate Preparation Techniques**  **b**

**3510 3520 3540/** 

**3541 3550 3580 Azinphos-methyl 86-50-0**  **HS ND ND ND X Barban 101-27-9**  **LR ND ND ND LR Benzidine 92-87-5**  **CP CP CP CP CP Benzoic acid 65-85-0**  **X X ND X X Benzo(a)anthracene 56-55-3**  **X X X X X Benzo(b)fluoranthene 205-99-2**  **X X X X X Benzo(k)fluoranthene 207-08-9**  **X X X X X Benzo(g,h,i)perylene 191-24-2**  **X X X X X Benzo(a)pyrene 50-32-8**  **X X X X X p-Benzoquinone 106-51-4**  **OE ND ND ND X Benzyl alcohol 100-51-6**  **X X ND X X α-BHC 319-84-6**  **X X X X X β-BHC 319-85-7**  **X X X X X δ-BHC 319-86-8**  **X X X X X γ-BHC (Lindane) 58-89-9**  **X X X X X Bis(2-chloroethoxy)methane 111-91-1**  **X X X X X Bis(2-chloroethyl)ether 111-44-4**  **X X X X X Bis(2-chloro-1-methylethyl)ether**  **c 108-60-1**  **X X X X X Bis(2-ethylhexyl)phthalate 117-81-7**  **X X X X X 4-Bromophenyl phenyl ether 101-55-3**  **X X X X X Bromoxynil 1689-84-5**  **X ND ND ND X Butyl benzyl phthalate 85-68-7**  **X X X X X Captafol 2425-06-1**  **HS ND ND ND X Captan 133-06-2**  **HS ND ND ND X Carbaryl 63-25-2**  **X ND ND ND X Carbofuran 1563-66-2**  **X ND ND ND X Carbophenothion 786-19-6**  **X ND ND ND X Chlordane (NOS) 57-74-9**  **X X X X X Chlorfenvinphos 470-90-6**  **X ND ND ND X 4-Chloroaniline 106-47-8**  **X ND ND ND X Chlorobenzilate 510-15-6**  **X ND ND ND X 5-Chloro-2-methylaniline 95-79-4**  **X ND ND ND X 4-Chloro-3-methylphenol 59-50-7**  **X X X X X 3-(Chloromethyl)pyridine**  **hydrochloride 6959-48-4 X ND ND ND X 1-Chloronaphthalene 90-13-1**  **X X X X X 2-Chloronaphthalene 91-58-7**  **X X X X X 2-Chlorophenol 95-57-8**  **X X X X X 4-Chloro-1,2-phenylenediamine 95-83-0**  **X X ND ND ND 4-Chloro-1,3-phenylenediamine 5131-60-2**  **X X ND ND ND 4-Chlorophenyl phenyl ether 7005-72-3**  **X X X X X Chrysene 218-01-9**  **X X X X X Coumaphos 56-72-4**  **X ND ND ND X p-Cresidine 120-71-8**  **X ND ND ND X Crotoxyphos 7700-17-6**  **X ND ND ND X 2-Cyclohexyl-4,6-dinitro-phenol 131-89-5**  **X ND ND ND LR 4,4'-DDD 72-54-8**  **X X X X X 4,4'-DDE 72-55-9**  **X X X X X 4,4'-DDT 50-29-3**  **X X X X X Demeton-O 298-03-3**  **HS ND ND ND X Demeton-S 126-75-0**  **X ND ND ND X SW-846 Update V 8270D - 3 Revision 5**  **October 2012 Compounds CAS No**  **a Appropriate Preparation Techniques**  **b**

**3510 3520 3540/** 

**3541 3550 3580 Diallate (cis or trans) 2303-16-4**  **X ND ND ND X 2,4-Diaminotoluene 95-80-7**  **DC, OE ND ND ND X Dibenz(a,j)acridine 224-42-0**  **X ND ND ND X Dibenz(a,h)anthracene 53-70-3**  **X X X X X Dibenzofuran 132-64-9**  **X X ND X X Dibenzo(a,e)pyrene 192-65-4**  **ND ND ND ND X 1,2-Dibromo-3-chloropropane 96-12-8**  **X X ND ND ND Di-n-butyl phthalate 84-74-2**  **X X X X X Dichlone 117-80-6**  **OE ND ND ND X 1,2-Dichlorobenzene 95-50-1**  **X X X X X 1,3-Dichlorobenzene 541-73-1**  **X X X X X 1,4-Dichlorobenzene 106-46-7**  **X X X X X 3,3'-Dichlorobenzidine 91-94-1**  **X X X X X 2,4-Dichlorophenol 120-83-2**  **X X X X X 2,6-Dichlorophenol 87-65-0**  **X ND ND ND X Dichlorovos 62-73-7**  **X ND ND ND X Dicrotophos 141-66-2**  **X ND ND ND X Dieldrin 60-57-1**  **X X X X X Diethyl phthalate 84-66-2**  **X X X X X Diethylstilbestrol 56-53-1**  **AW, OS ND ND ND X Diethyl sulfate 64-67-5**  **LR ND ND ND LR Dimethoate 60-51-5**  **HE, HS ND ND ND X 3,3'-Dimethoxybenzidine 119-90-4**  **X ND ND ND LR Dimethylaminoazobenzene 60-11-7**  **X ND ND ND X 7,12-Dimethylbenz(a)-anthracene 57-97-6**  **CP ND ND ND CP 3,3'-Dimethylbenzidine 119-93-7**  **X ND ND ND X α,α-Dimethylphenethylamine 122-09-8**  **ND ND ND ND X 2,4-Dimethylphenol 105-67-9**  **X X X X X Dimethyl phthalate 131-11-3**  **X X X X X 1,2-Dinitrobenzene 528-29-0**  **X ND ND ND X 1,3-Dinitrobenzene 99-65-0**  **X ND ND ND X 1,4-Dinitrobenzene 100-25-4**  **HE ND ND ND X 4,6-Dinitro-2-methylphenol 534-52-1**  **X X X X X 2,4-Dinitrophenol 51-28-5**  **X X X X X 2,4-Dinitrotoluene 121-14-2**  **X X X X X 2,6-Dinitrotoluene 606-20-2**  **X X X X X Dinocap 39300-45-3**  **CP, HS ND ND ND CP Dinoseb 88-85-7**  **X ND ND ND X Diphenylamine 122-39-4**  **X X X X X 5,5-Diphenylhydantoin 57-41-0**  **X ND ND ND X 1,2-Diphenylhydrazine 122-66-7**  **X X X X X Di-n-octyl phthalate 117-84-0**  **X X X X X Disulfoton 298-04-4**  **X ND ND ND X Endosulfan I 959-98-8**  **X X X X X Endosulfan II 33213-65-9**  **X X X X X Endosulfan sulfate 1031-07-8**  **X X X X X Endrin 72-20-8**  **X X X X X Endrin aldehyde 7421-93-4**  **X X X X X Endrin ketone 53494-70-5**  **X X ND X X EPN 2104-64-5**  **X ND ND ND X Ethion 563-12-2**  **X ND ND ND X SW-846 Update V 8270D - 4 Revision 5**  **October 2012 Compounds CAS No**  **a Appropriate Preparation Techniques**  **b**

**3510 3520 3540/** 

**3541 3550 3580 Ethyl carbamate 51-79-6**  **DC ND ND ND X Ethyl methanesulfonate 62-50-0**  **X ND ND ND X Famphur 52-85-7**  **X ND ND ND X Fensulfothion 115-90-2**  **X ND ND ND X Fenthion 55-38-9**  **X ND ND ND X Fluchloralin 33245-39-5**  **X ND ND ND X Fluoranthene 206-44-0**  **X X X X X Fluorene 86-73-7**  **X X X X X 2-Fluorobiphenyl (surr) 321-60-8**  **X X X X X 2-Fluorophenol (surr) 367-12-4**  **X X X X X Heptachlor 76-44-8**  **X X X X X Heptachlor epoxide 1024-57-3**  **X X X X X Hexachlorobenzene 118-74-1**  **X X X X X Hexachlorobutadiene 87-68-3**  **X X X X X Hexachlorocyclopentadiene 77-47-4**  **X X X X X Hexachloroethane 67-72-1**  **X X X X X Hexachlorophene 70-30-4**  **AW, CP ND ND ND CP Hexachloropropene 1888-71-7**  **X ND ND ND X Hexamethylphosphoramide 680-31-9**  **X ND ND ND X Hydroquinone 123-31-9**  **ND ND ND ND X Indeno(1,2,3-cd)pyrene 193-39-5**  **X X X X X Isodrin 465-73-6**  **X ND ND ND X Isophorone 78-59-1**  **X X X X X Isosafrole 120-58-1**  **DC ND ND ND X Kepone 143-50-0**  **X ND ND ND X Leptophos 21609-90-5**  **X ND ND ND X Malathion 121-75-5**  **HS ND ND ND X Maleic anhydride 108-31-6**  **HE ND ND ND X Mestranol 72-33-3**  **X ND ND ND X Methapyrilene 91-80-5**  **X ND ND ND X Methoxychlor 72-43-5**  **X ND ND ND X 3-Methylcholanthrene 56-49-5**  **X ND ND ND X 4,4'-Methylenebis(2-chloroaniline) 101-14-4**  **OE, OS ND ND ND LR 4,4'-Methylenebis(N,N-dimethyl**  **aniline) 101-61-1 X X ND ND ND**  **Methyl methanesulfonate 66-27-3 X ND ND ND X**  **2-Methylnaphthalene 91-57-6 X X ND X X**  **Methyl parathion 298-00-0 X ND ND ND X**  **2-Methylphenol 95-48-7 X ND ND ND X**  **3-Methylphenol 108-39-4 X ND ND ND X**  **4-Methylphenol 106-44-5 X ND ND ND X**  **Mevinphos 7786-34-7 X ND ND ND X**  **Mexacarbate 315-18-4 HE, HS ND ND ND X**  **Mirex 2385-85-5 X ND ND ND X**  **Monocrotophos 6923-22-4 HE ND ND ND X**  **Naled 300-76-5 X ND ND ND X**  **Naphthalene 91-20-3 X X X X X**  **1,4-Naphthoquinone 130-15-4 X ND ND ND X**  **1-Naphthylamine 134-32-7 OS ND ND ND X**  **2-Naphthylamine 91-59-8 X ND ND ND X**  **Nicotine 54-11-5 DC ND ND ND X** **SW-846 Update V 8270D - 5 Revision 5 October 2012**  **Compounds CAS No a**  **Appropriate Preparation Techniques b** 

**3510 3520 3540/** 

**3541 3550 3580 5-Nitroacenaphthene 602-87-9**  **X ND ND ND X 2-Nitroaniline 88-74-4**  **X X ND X X 3-Nitroaniline 99-09-2**  **X X ND X X 4-Nitroaniline 100-01-6**  **X X ND X X 5-Nitro-o-anisidine 99-59-2**  **X ND ND ND X Nitrobenzene 98-95-3**  **X X X X X 4-Nitrobiphenyl 92-93-3**  **X ND ND ND X Nitrofen 1836-75-5**  **X ND ND ND X 2-Nitrophenol 88-75-5**  **X X X X X 4-Nitrophenol 100-02-7**  **X X X X X 5-Nitro-o-toluidine 99-55-8**  **X X ND ND X Nitroquinoline-1-oxide 56-57-5**  **X ND ND ND X N-Nitrosodi-n-butylamine 924-16-3**  **X ND ND ND X N-Nitrosodiethylamine 55-18-5**  **X ND ND ND X N-Nitrosodimethylamine 62-75-9**  **X X X X X N-Nitrosodiphenylamine 86-30-6**  **X X X X X N-Nitrosodi-n-propylamine 621-64-7**  **X X X X X N-Nitrosomethylethylamine 10595-95-6**  **X ND ND ND X N-Nitrosomorpholine 59-89-2**  **ND ND ND ND X N-Nitrosopiperidine 100-75-4**  **X ND ND ND X N-Nitrosopyrrolidine 930-55-2**  **X ND ND ND X Octamethyl pyrophosphoramide 152-16-9**  **LR ND ND ND LR 4,4'-Oxydianiline 101-80-4**  **X ND ND ND X Parathion 56-38-2**  **X X ND ND X Pentachlorobenzene 608-93-5**  **X ND ND ND X Pentachloronitrobenzene 82-68-8**  **X ND ND ND X Pentachlorophenol 87-86-5**  **X X X X X Phenacetin 62-44-2**  **X ND ND ND X Phenanthrene 85-01-8**  **X X X X X Phenobarbital 50-06-6**  **X ND ND ND X Phenol 108-95-2**  **DC X X X X 1,4-Phenylenediamine 106-50-3**  **X ND ND ND X Phorate 298-02-2**  **X ND ND ND X Phosalone 2310-17-0**  **HS ND ND ND X Phosmet 732-11-6**  **HS ND ND ND X Phosphamidon 13171-21-6**  **HE ND ND ND X Phthalic anhydride 85-44-9**  **CP, HE ND ND ND CP 2-Picoline (2-Methylpyridine) 109-06-8**  **X X ND ND ND Piperonyl sulfoxide 120-62-7**  **X ND ND ND X Pronamide 23950-58-5**  **X ND ND ND X Propylthiouracil 51-52-5**  **LR ND ND ND LR Pyrene 129-00-0**  **X X X X X Resorcinol 108-46-3**  **DC, OE ND ND ND X Safrole 94-59-7**  **X ND ND ND X Strychnine 57-24-9**  **AW, OS ND ND ND X Sulfallate 95-06-7**  **X ND ND ND X Terbufos 13071-79-9**  **X ND ND ND X 1,2,4,5-Tetrachlorobenzene 95-94-3**  **X ND ND ND X 2,3,4,6-Tetrachlorophenol 58-90-2**  **X ND ND ND X Tetrachlorvinphos 961-11-5**  **X ND ND ND X Tetraethyl dithiopyrophosphate 3689-24-5**  **X X ND ND ND SW-846 Update V 8270D - 6 Revision 5**  **October 2012 Compounds CAS No**  **a Appropriate Preparation Techniques**  **b**

**3510 3520 3540/** 

**3541 3550 3580 Tetraethyl pyrophosphate 107-49-3**  **X ND ND ND X Thionazine 297-97-2**  **X ND ND ND X Thiophenol (Benzenethiol) 108-98-5**  **X ND ND ND X Toluene diisocyanate 584-84-9**  **HE ND ND ND X o-Toluidine 95-53-4**  **X ND ND ND X Toxaphene 8001-35-2**  **X X X X X 1,2,4-Trichlorobenzene 120-82-1**  **X X X X X 2,4,5-Trichlorophenol 95-95-4**  **X X ND X X 2,4,6-Trichlorophenol 88-06-2**  **X X X X X Trifluralin 1582-09-8**  **X ND ND ND X 2,4,5-Trimethylaniline 137-17-7**  **X ND ND ND X Trimethyl phosphate 512-56-1**  **HE ND ND ND X 1,3,5-Trinitrobenzene 99-35-4**  **X ND ND ND X Tris(2,3-dibromopropyl)phosphate 126-72-7**  **X ND ND ND LR Tri-p-tolyl phosphate 78-32-0**  **X ND ND ND X O,O,O-Triethyl phosphorothioate 126-68-1**  **X ND ND ND X**

**a Chemical Abstract Service (CAS) Registry Number** 

**b See Sec. 1.2 for other acceptable preparation meth**  **ods.**

**c Chemical name was changed by the Integrated Risk In**  **formation System (IRIS) on November 30, 2007 from Bis(2-chloroisopropyl)ether to Bis(2-**  **chloro-1-methylethyl)ether (common name). This compound is also known as 2,2’-oxybis(1-chloro**  **propane) (CAS index name). See the link at**  **http://www.epa.gov/iris/subst/0407.htm , Section VII for the “Revision History” and Sectio**  **n VIII, for “Synonyms” of this chemical.** 

**KEY TO ANALYTE LIST**

**AW = Adsorption to walls of glassware during extra ction and storage**  **CP = Non-reproducible chromatographic performance DC = Unfavorable distribution coefficient**  **HE = Hydrolysis during extraction accelerated by a cidic or basic conditions**  **HS = Hydrolysis during storage potential LR = Low response**  **ND = Not determined OE = Oxidation during extraction accelerated by ba**  **sic conditions OS = Oxidation during storage potential**  **X = Historically, adequate recovery can be obtaine d by this technique. However, actual** 

**recoveries may vary depending on the extraction eff iciency, the number of**  **constituents being analyzed concurrently, and the a nalytical instrumentation.** 

**1.2 In addition to the sample preparation methods l isted in the above analyte list,**  **Method 3535 describes a solid-phase extraction (SPE ) procedure that may be applied to the**  **extraction of semivolatiles from toxicity character istic leaching procedure (TCLP) leachates (see**  **Tables 16 and 17 of this method for performance dat a). Method 3542 describes sample**  **preparation for semivolatile organic compounds in a ir sampled by Method 0010 (see Table 10 of**  **this method for surrogate performance data), Method 3545 describes an automated solvent**  **extraction (ASE) device for semivolatiles in solids (see Table 11 of this method for performance**  **data), Method 3561 describes a supercritical fluid extraction (SFE) device for the extraction of**  **polynuclear aromatic hydrocarbons (PAHs) from solid s (see Tables 12, 13, and 14 of this** **SW-846 Update V 8270D - 7 Revision 5 October 2012**  **method for performance data), and Method 3546 provi des an extraction procedure employing**  **commercially available microwave equipment to extra ct semivolatiles while using less solvent**  **and taking less time than procedures such as a Soxh let extraction (see Tables 18 through 22 of**  **this method for the applicable performance data). The tabulated data are provided for guidance**  **purposes only.**

**1.3 This method can be used to quantitate most neut ral, acidic, and basic organic**  **compounds that are soluble in methylene chloride (o r other suitable solvents provided that the**  **desired performance data can be generated) and are capable of being eluted, without**  **derivatization, as sharp peaks from a gas chromatog raphic fused-silica capillary column coated**  **with a slightly polar silicone. Such compounds inc lude PAHs, chlorinated hydrocarbons and**  **pesticides, phthalate esters, organophosphate ester s, nitrosamines, haloethers, aldehydes,**  **ethers, ketones, anilines, pyridines, quinolines, a romatic nitro compounds, and phenols,**  **including nitrophenols. See Table 1 for a list of compounds and their characteristic ions that**  **have been evaluated.**

**In most cases, this method is not appropriate for t he quantitation of multicomponent**  **analytes (e.g., Aroclors, toxaphene, chlordane, etc .) because of limited sensitivity for those**  **analytes. When these analytes have been identified by another technique, Method 8270 may**  **be appropriate for confirmation of the identificati on of these analytes when concentration in the**  **extract permits. Refer to Methods 8081 and 8082 fo r guidance on calibration and quantitation of**  **multicomponent analytes such as the Aroclors, Toxap hene, and Chlordane.** 

**1.4 The following compounds may require special tre atment when being determined by**  **this method:**

**1.4.1 Benzidine may be subject to oxidative losses during solvent concentration**  **and its chromatographic behavior is poor.**

**1.4.2 Under the alkaline conditions of the extracti on step from aqueous**  **matrices, α-BHC, γ-BHC, endosulfan I and II, and en drin are subject to decomposition.**  **Neutral extraction should be performed if these com pounds are expected to be present.** 

**1.4.3 Hexachlorocyclopentadiene is subject to therm al decomposition in the**  **inlet of the gas chromatograph, chemical reaction i n acetone solution, and photochemical**  **decomposition.**

**1.4.4 N-Nitrosodimethylamine is difficult to separa te from the solvent under the**  **chromatographic conditions described.**

**1.4.5 N-Nitrosodiphenylamine decomposes in the gas chromatographic inlet**  **and cannot be separated from diphenylamine. For th is reason, it is acceptable to report**  **the combined result for n-nitrosodiphenylamine and diphenylamine for either of these**  **compounds as a combined concentration.**

**1.4.6 1,2-Diphenylhydrazine is unstable even at roo m temperature and readily**  **converts to azobenzene. Given the stability proble ms, it would be acceptable to calibrate**  **for 1,2-diphenylhydrazine using azobenzene. Under these poor compound separation**  **circumstances the results for either of these compo unds should be reported as a**  **combined concentration.**

**1.4.7 Pentachlorophenol, 2,4-dinitrophenol, 4-nitro phenol, benzoic acid, 4,6-**  **dinitro-2-methylphenol, 4-chloro-3-methylphenol, 2- nitroaniline, 3-nitroaniline, 4-** **SW-846 Update V 8270D - 8 Revision 5 October 2012**  **nitroaniline, and benzyl alcohol are subject to err atic chromatographic behavior, especially**  **if the gas chromatograph (GC) system is contaminate d with high boiling material.** 

**1.4.8 Pyridine may perform poorly at the GC injecti on port temperatures listed**  **in this method. Lowering the injection port temper ature may reduce the amount of**  **degradation. However, the analyst must use caution in modifying the injection port**  **temperature, as the performance of other analytes m ay be adversely affected. Therefore,**  **if pyridine is to be determined in addition to othe r target analytes, it may be necessary to**  **perform separate analyses. In addition, pyridine m ay be lost during the evaporative**  **concentration of the sample extract. As a result, many of the extraction methods listed**  **above may yield low recoveries unless great care is exercised during the concentration**  **steps. For this reason, analysts may wish to consi der the use of extraction techniques**  **such as pressurized fluid extraction (Method 3545), microwave extraction (Method 3546),**  **or supercritical fluid extraction, which involve sm aller extract volumes, thereby reducing or**  **eliminating the need for evaporative concentration techniques for many applications.** 

**1.4.9 Toluene diisocyanate rapidly hydrolyzes in wa ter (it has a half-life of less**  **than 30 min). Therefore, recoveries of this compou nd from aqueous matrices should not**  **be expected. In addition, in solid matrices, tolue ne diisocyanate often reacts with alcohols**  **and amines to produce urethane and ureas and conseq uently cannot usually coexist in a**  **solution containing these materials.**

**1.4.10 In addition, analytes in the list provided a bove are flagged when there are**  **limitations caused by sample preparation and/or chr omatographic problems.** 

**1.5 The lower limits of quantitation (LLOQ) for thi s method when determining an**  **individual compound are approximately 660 μg/kg (we t weight) for soil/sediment samples, 1-200**  **mg/kg for wastes (dependent on matrix and method of preparation), and 10 μg/L for**  **groundwater samples (see Table 2). LLOQ will be pr oportionately higher for sample extracts**  **that require dilution to avoid saturation of the de tector. The lower limits of quantitation listed in**  **Table 2 are provided for guidance and may not alway s be achievable.** 

**1.6 Prior to employing this method, analysts are ad vised to consult the base method**  **for each type of procedure that may be employed in the overall analysis (e.g., Methods 3500,**  **3600, 5000, and 8000) for additional information on QC procedures, development of QC**  **acceptance criteria, calculations, and general guid ance. Analysts also should consult the**  **disclaimer statement at the front of the manual and the information in Chapter Two for guidance**  **on the intended flexibility in the choice of method s, apparatus, materials, reagents, and**  **supplies, and on the responsibilities of the analys t for demonstrating that the techniques**  **employed are appropriate for the analytes of intere st, in the matrix of interest, and at the levels**  **of concern.**

**In addition, analysts and data users are advised th at, except where explicitly specified in a**  **regulation, the use of SW-846 methods is** not **mandatory in response to Federal testing requirements. The information contained in this me**  **thod is provided by Environmental Protection Agency (EPA or the Agency) as guidance t**  **o be used by the analyst and the regulated community in making judgments necessary t**  **o generate results that meet the data quality objectives (DQOs) for the intended applicat**  **ion.**

**1.7 Use of this method is restricted to use by, or under supervision of, personnel**  **appropriately experienced and trained in the use of the GC/mass spectrometer (MS) and skilled**  **in the interpretation of mass spectra. Each analys t must demonstrate the ability to generate**  **acceptable results with this method. SW-846 Update V 8270D - 9 Revision 5**  **October 2012 2.0 SUMMARY OF METHOD** 

**2.1 The samples are prepared for analysis by GC/MS using the appropriate sample**  **preparation (refer to Method 3500) and, if necessar y, sample cleanup procedures (refer to**  **Method 3600).**

**2.2 The semivolatile compounds are introduced into the GC/MS by injecting the**  **sample extract into a GC equipped with a narrow-bor e fused-silica capillary column. The GC**  **column is temperature-programmed to separate the an alytes, which are then detected with an**  **MS connected to the GC.**

**2.3 Analytes eluted from the capillary column are i ntroduced into the MS via a jet**  **separator or a direct connection. Identification o f target analytes is accomplished by comparing**  **their mass spectra with the electron impact (or ele ctron impact like) spectra of authentic**  **standards. Quantitation is accomplished by compari ng the response of a major (quantitation)**  **ion relative to an internal standard using an appro priate calibration curve for the intended**  **application.**

**2.4 This method includes specific calibration and Q C steps that supersede the general**  **recommendations provided in Method 8000.**

**3.0 DEFINITIONS**

**Refer to Chapter One and the manufacturer's instruc tions for definitions that may be**  **relevant to this procedure.**

**4.0 INTERFERENCES**

**4.1 Solvents, reagents, glassware, and other sample processing hardware may yield**  **artifacts and/or interferences to sample analysis. All of these materials must be demonstrated**  **to be free from interferences under the conditions of the analysis by analyzing method blanks.**  **Specific selection of reagents and purification of solvents by distillation in all glass systems may**  **be necessary. Refer to each method to be used for specific guidance on QC procedures and to**  **Chapter Four for general guidance on the cleaning o f glassware. Also refer to Method 8000 for**  **a discussion of interferences.**

**4.2 Raw gas chromatography/mass spectrometry data f rom all blanks, samples, and**  **spikes must be evaluated for interferences. Determ ine if the source of interference is in the**  **preparation and/or cleanup of the samples and take corrective action to eliminate the problem.** 

**4.3 Contamination by carryover can occur whenever h igh concentration and low**  **concentration samples are sequentially analyzed. T o reduce carryover, the sample syringe**  **must be rinsed with solvent between sample injectio ns. Whenever an unusually concentrated**  **sample is encountered, it should be followed by the analysis of solvent to check for cross**  **contamination. SW-846 Update V 8270D - 10 Revision 5**  **October 2012 5.0 SAFETY** 

**This method does not address all safety issues asso ciated with its use. The laboratory is**  **responsible for maintaining a safe work environment and a current awareness file of**  **Occupational Safety and Health Administration (OSHA ) regulations regarding the safe handling**  **of the chemicals listed in this method. A referenc e file of material safety data sheets (MSDSs)**  **should be available to all personnel involved in th ese analyses.** 

**6.0 EQUIPMENT AND SUPPLIES**

**The mention of trade names or commercial products i n this manual is for illustrative**  **purposes only, and does not constitute an EPA endor sement or exclusive recommendation for**  **use. The products and instrument settings cited in SW-846 methods represent those products**  **and settings used during method development or subs equently evaluated by the Agency.**  **Glassware, reagents, supplies, equipment, and setti ngs other than those listed in this manual**  **may be employed provided that method performance ap propriate for the intended application**  **has been demonstrated and documented.**

**This section does not list common laboratory glassw are (e.g., beakers and flasks).** 

**6.1 Gas chromatograph/mass spectrometer system**

**6.1.1 GC - An analytical system equipped with a tem perature programmable**  **GC suitable for splitless injection and all require d accessories, including syringes,**  **analytical columns, and gases. The capillary colum n should be directly coupled to the** 

**source.**

**6.1.2 Column - 30 m x 0.25 mm ID (or 0.32 mm ID) 0. 25, 0.5, or 1 μm film**  **thickness silicone-coated fused-silica capillary co lumn (J&W Scientific DB-5 or equivalent).**  **The columns listed in this section were the columns used in developing the method. The**  **listing of these columns in this method is not inte nded to exclude the use of other columns**  **that may be developed. Laboratories may use these columns or other capillary columns**  **provided that the laboratories document method perf ormance data (e.g., chromatographic**  **resolution, analyte breakdown, and sensitivity) tha t are appropriate for the intended**  **application.**

**6.1.3 Mass spectrometer**

**6.1.3.1 Capable of scanning from 35 to 500 amu ever y 1 sec or less,**  **using 70 volts (nominal) electron energy in the ele ctron impact ionization mode.**  **The MS must be capable of producing a mass spectrum for**  **decafluorotriphenylphosphine (DFTPP) which meets th e criteria as outlined in Sec.**  **11.3.1.**

**6.1.3.2 An ion trap MS may be used if it is capable of axial modulation**  **to reduce ion-molecule reactions and can produce el ectron impact like spectra that**  **match those in the EPA/National Institute of Standa rds and Technology (NIST)**  **Library. The MS must be capable of producing a mas s spectrum for DFTPP which**  **meets the criteria as outlined in Sec. 11.3.1. SW-846 Update V 8270D - 11 Revision 5**  **October 2012 6.1.4 GC/MS interface - Any GC-to-MS interface may**  **be used that gives acceptable calibration points for each compound of**  **interest and achieves acceptable tuning performance criteria. For a narrow-bore cap**  **illary column, the interface is usually capillary direct into the MS source.** 

**6.1.5 Data system - A computer system should be int erfaced to the MS. The**  **system must allow the continuous acquisition and st orage on machine-readable media of**  **all mass spectra obtained throughout the duration o f the chromatographic program. The**  **computer should have software that can search any g as chromatography/mass**  **spectrometry data file for ions of a specific mass and that can plot such ion abundances**  **versus time or scan number. This type of plot is d efined as an Extracted Ion Current**  **Profile (EICP). Software should also be available that allows integrating the abundances**  **in any EICP between specified time or scan number l imits. The most recent version of the**  **EPA/National Institute of Standards and Technology (NIST) Mass Spectral Library should**  **also be available.**

**6.1.6 Guard column (optional) - (J&W deactivated fu sed-silica, 0.25 mm ID x 6**  **m, or equivalent) between the injection port and th e analytical column joined with column**  **connectors (Agilent Catalog No. 5062-3556, or equiv alent).** 

**6.2 Syringe - 10 μL**

**6.3 Volumetric flasks, Class A - Appropriate sizes equipped with ground-glass stoppers** 

**6.4 Balance - Analytical, capable of weighing 0.000 1 g** 

**6.5 Bottles - Glass equipped with polytetrafluoroet hylene (PTFE)-lined screw caps or**  **crimp tops**

**7.0 REAGENTS AND STANDARDS**

**7.1 Reagent-grade chemicals must be used in all tes ts. Unless otherwise indicated, it**  **is intended that all reagents conform to the specif ications of the Committee on Analytical**  **Reagents of the American Chemical Society (ACS), wh ere such specifications are available.**  **Other grades may be used, provided it is first asce rtained that the reagent is of sufficiently high**  **purity to permit its use without lessening the accu racy of the determination. Reagents should be**  **stored in glass to prevent the leaching of contamin ants from plastic containers.** 

**7.2 Organic-free reagent water - All references to water in this method refer to organic**  **free reagent water.**

**7.3 Standard solutions**

**The following sections describe the preparation of stock, intermediate, and working**  **standards for the compounds of interest. This disc ussion is provided as an example, and other**  **approaches and concentrations of the target compoun ds may be used, as appropriate for the**  **intended application. See Method 8000 for addition al information on the preparation of**  **calibration standards.**

**7.4 Stock standard solutions (1000 mg/L) - Standard solutions can be prepared from**  **pure standard materials or purchased as certified s olutions.** **SW-846 Update V 8270D - 12 Revision 5 October 2012**  **7.4.1 Prepare stock standard solutions by accuratel y weighing about 0.0100 g**  **of pure material. Dissolve the material in pestici de-quality acetone or other suitable**  **solvent and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at**  **the convenience of the analyst. When compound puri ty is assayed to be 96% or greater,**  **the weight may be used without correction to calcul ate the concentration of the stock**  **standard. Commercially prepared stock standards ma y be used at any concentration if**  **they are certified by the manufacturer or by an ind ependent source.** 

**7.4.2 Transfer the stock standard solutions into bo ttles equipped with PTFE**  **lined screw caps. Store, protected from light, at** ≤ **6** ° **C or as recommended by the standard manufacturer. Stock standard solutions sh**  **ould be checked frequently for signs of degradation or evaporation, especially just prio**  **r to preparing calibration standards from them.** 

**7.4.3 Stock standard solutions must be replaced aft er one year or sooner if**  **comparison with QC check samples indicates a proble m.** 

**7.4.4 It is recommended that nitrosamine compounds be placed together in a**  **separate calibration mix and not combined with othe r calibration mixes. When using a**  **premixed certified standard, consult the manufactur er's instructions for additional**  **guidance.**

**7.4.5 Mixes with hydrochloride salts may contain hy drochloric acid, which can**  **cause analytical difficulties. When using a premix ed certified standard, consult the**  **manufacturer's instructions for additional guidance**

**.**

**7.5 Internal standard solutions - The internal stan dards recommended are:**  **1,4-dichlorobenzene-d 4**  **, naphthalene-d 8**  **, acenaphthene-d 10**  **, phenanthrene-d 10**  **, chrysene-d 12**  **, and perylene-d**  **12 (see Table 5). Other compounds may be used as int**  **ernal standards as long as the criteria in Sec. 11.3.2 are met.** 

**7.5.1 Dissolve 0.200 g of each compound with a smal l volume of carbon**  **disulfide. Transfer to a 50-mL volumetric flask an d dilute to volume with methylene**  **chloride so that the final solvent is approximately 20% carbon disulfide. Most of the**  **compounds are also soluble in small volumes of meth anol, acetone, or toluene, except for**  **perylene-d 12**  **. The resulting solution will contain each standar d at a concentration of 4,000**  **ng/μL. Each 1-mL sample extract undergoing analysi s should be spiked with 10 μL of the**  **internal standard solution, resulting in a concentr ation of 40 ng/μL of each internal**  **standard. Store away from any light source at** ≤ **6** ° **C when not in use (−10** ° **C is recommended). When using premixed certified soluti**  **ons, store according to the manufacturer's documented holding time and storage**  **temperature recommendations.**

**7.5.2 If a more sensitive MS is employed to achieve lower quantitation levels, a**  **more dilute internal standard solution may be requi red. Area counts of the internal**  **standard peaks should be between 50-200% of the are a of the target analytes in the mid**  **point calibration analysis.**

**7.6 GC/MS tuning standard - A methylene chloride so lution containing 50 ng/μL of**  **DFTPP should be prepared. The standard should also contain 50 ng/μL each of 4,4'-DDT,**  **pentachlorophenol, and benzidine to verify injectio n port inertness and GC column performance.**  **Alternate concentrations may be used to compensate for different injection volumes if the total**  **amount injected is 50 ng or less. Store away from any light source at**  ≤ **6** ° **C when not in use (- 10**  ° **C is recommended). If a more sensitive MS is emplo yed to achieve lower quantitation**  **levels, a more dilute tuning solution may be necess ary. When using premixed certified** **SW-846 Update V 8270D - 13 Revision 5 October 2012**  **solutions, store according to the manufacturer's do cumented holding time and storage**  **temperature recommendations.**

**7.7 Calibration standards - A minimum of five calib ration standards should be prepared**  **at different concentrations. At least one of the c alibration standards should correspond to a**  **sample concentration at or below that necessary to meet the DQOs of the project. The**  **remaining standards should correspond to the range of concentrations found in actual samples**  **but should not exceed the working range of the GC/M S system. Each standard and/or series of**  **calibration standards prepared at a given concentra tion should contain all the desired project**  **specific target analytes for which quantitation and quantitative results are to be reported by this**  **method.**

**7.7.1 It is the intent of EPA that all target analy tes for a particular analysis be**  **included in the calibration standard(s). These tar get analytes may not include the entire**  **list of analytes (Sec. 1.1) for which the method ha s been demonstrated. However, the**  **laboratory shall not report a quantitative result f or a target analyte that was not included in**  **the calibration standard(s).**

**7.7.2 Each 1-mL aliquot of calibration standard sho uld be spiked with 10 μL of**  **the internal standard solution prior to analysis. All standards should be stored away from**  **any light source at** ≤ **6** ° **C when not in use (−10** ° **C is recommended), and should be freshly prepared once a year, or sooner if check standards**  **indicate a problem. The calibration verification standard should be prepared, as necess**  **ary, and stored at** ≤ **6** ° **C. When using premixed certified solutions, store according to th**  **e manufacturer's documented holding time and storage temperature recommendations.** 

**7.8 Surrogate standards - The recommended surrogate s are: phenol-d**  **6 , 2-**  **fluorophenol, 2,4,6-tribromophenol, nitrobenzene-d 5**  **, 2-fluorobiphenyl, and p-terphenyl-d 14**  **. See Method 3500 for instructions on preparing the surro**  **gate solutions.**

**NOTE : In the presence of samples containing residual ch**  **lorine, phenol-d 6**  **has been known to react to form chlorinated phenolic compounds that a**  **re not detected as the original spiked surrogate. Sample preservation precautions**  **outlined in Chapter Four should be used when residual chlorine is known to be present**  **in order to minimize degradation of deuterated phenols or any other susceptible target**  **analyte.**

**7.8.1 Surrogate standard check - Determine what the appropriate concentration**  **should be for the blank extracts after all extracti on, cleanup, and concentration steps.**  **Inject this concentration into the GC/MS to determi ne recovery of surrogate standards. It**  **is recommended that this check be done whenever a n ew surrogate spiking solution is**  **prepared.**

**NOTE : Method 3561 (SFE Extraction of PAHs) recommends t**  **he use of bromobenzene and p-quaterphenyl to better cover the range of PAH**  **s listed in the method.**

**7.8.2 If a more sensitive MS is employed to achieve lower quantitation levels, a**  **more dilute surrogate solution may be necessary.**

**7.9 Matrix spike and laboratory control standards ( LCSs) - See Method 3500 for**  **instructions on preparing the matrix spike standard . The same standard may be used as the**  **LCS and the spiking solution should be the same sou rce as used for the initial calibration**  **standards to restrict the influence of standard acc uracy on the determination of recovery**  **through preparation and analysis. SW-846 Update V 8270D - 14 Revision 5**  **October 2012 7.9.1 Matrix spike check - Determine what concentra**  **tion should be in the blank extracts after all extraction, cleanup, and concent**  **ration steps. Inject this concentration into the GC/MS to determine recovery. It is recomm**  **ended that this check be done whenever a new matrix spiking solution is prepared.** 

**7.9.2 If a more sensitive MS is employed to achieve lower quantitation levels, a**  **more dilute matrix and LCS spiking solution may be necessary.** 

**7.9.3 Some projects may require the spiking of the specific compounds of**  **interest, since the spiking compounds listed in Met hod 3500 would not be representative**  **of the compounds of interest required for the proje ct. When this occurs, the matrix and**  **LCS spiking standards should be prepared in methano l, with each compound present at a**  **concentration appropriate for the project.**

**7.10 Solvents - Acetone, hexane, methylene chloride , isooctane, carbon disulfide,**  **toluene, and other appropriate solvents may be used . All solvents should be pesticide quality or**  **equivalent. Solvents may be degassed prior to use, if necessary.** 

**8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE**

**8.1 See the introductory material to Chapter Four, "Organic Analytes."** 

**8.2 Store the sample extracts at** ≤ **6** ° **C, protected from light, in sealed vials (e.g., screw-cap vials or crimp-capped vials) equipped wit**  **h unpierced PTFE-lined septa.**

**9.0 QUALITY CONTROL**

**9.1 Refer to Chapter One for guidance on quality as surance (QA) and QC protocols.**  **When inconsistencies exist between QC guidelines, m ethod-specific QC criteria take**  **precedence over both technique-specific criteria an d those criteria given in Chapter One, and**  **technique-specific QC criteria take precedence over the criteria in Chapter One. Any effort**  **involving the collection of analytical data should include development of a structured and**  **systematic planning document, such as a quality ass urance project plan (QAPP) or a sampling**  **and analysis plan (SAP), which translates project o bjectives and specifications into directions for**  **those that will implement the project and assess th e results. Each laboratory should maintain a**  **formal QA program. The laboratory should also main tain records to document the quality of the**  **data generated. All data sheets and QC data should be maintained for reference or inspection.** 

**9.2 Refer to Method 8000 for specific determinative method QC procedures. Refer to**  **Method 3500 or 5000 for QC procedures to ensure the proper operation of the various sample**  **preparation techniques. If an extract cleanup proc edure is performed, refer to Method 3600 for**  **the appropriate QC procedures. Any more specific Q C procedures provided in this method will**  **supersede those noted in Methods 8000, 5000, 3500, or 3600.** 

**9.3 QC procedures necessary to evaluate the GC syst em operation are found in**  **Method 8000 and include evaluation of retention tim e windows, calibration verification and**  **chromatographic analysis of samples. In addition, discussions regarding the instrument QC**  **requirements listed below can be found in the refer enced sections of this method:** 

**9.3.1 The GC/MS must be tuned to meet the recomme nded DFTPP criteria**  **prior to the initial calibration and for each twelv e-hour period during which analyses are**  **performed. See Secs. 11.3.1 and 11.4.1 for further details.** **SW-846 Update V 8270D - 15 Revision 5 October 2012**  **9.3.2 There must be an initial calibration of the G C/MS system as described in**  **Sec. 11.3. In addition, the initial calibration cu rve should be verified immediately after**  **performing the standard analyses using a second sou rce standard (prepared using**  **standards different from the calibration standards) . The suggested acceptance limits for**  **this initial calibration verification analysis are 70-130%. Alternative acceptance limits**  **may be appropriate based on the desired project-spe cific DQOs. Quantitative sample**  **analyses should not proceed for those analytes that fail the second source standard**  **initial calibration verification. However, analyse s may continue for those analytes that**  **fail the criteria with an understanding these resul ts could be used for screening purposes**  **and would be considered estimated values.**

**9.3.3 The GC/MS system must meet the calibration ve rification acceptance**  **criteria in Sec. 11.4.**

**9.3.4 The relative retention time (RRT) of the samp le component must fall**  **within the RRT window of the standard component pro vided in Sec. 11.6.1** 

. **9.4 Initial demonstration of proficiency (IDP)**

**Prior to implementation of a method, each laborator y must perform an IDP consisting of at**  **least four replicate reference samples spiked into a clean matrix taken through the entire**  **sample preparation and analysis. Whenever a signif icant change to instrumentation or**  **procedure occurs, the laboratory must demonstrate t hat acceptable precision and bias can still**  **be obtained by the changed conditions. Whenever ne w staff members are trained, an analyst**  **IDP must be performed. See Method 8000 for more in formation on how to accomplish an IDP.** 

**9.4.1 Demonstration of proficiency for new analysts - Each laboratory should**  **have a training program which documents that a new analyst is capable of performing the**  **method, or portion of the method, for which the ana lyst is responsible. This demonstration**  **should document that the new analyst is capable of successfully following the SOP**  **established by the laboratory.**

**9.5 Initially, before processing any samples, the a nalyst should demonstrate that all**  **parts of the equipment in contact with the sample a nd reagents are interference-free. This is**  **accomplished through the analysis of a method blank . As a continuing check, each time**  **samples are extracted, cleaned up, and analyzed, a method blank must be prepared and**  **analyzed for the compounds of interest as a safegua rd against chronic laboratory**  **contamination. If a peak is observed within the re tention time window of any analyte that would**  **prevent the determination of that analyte, determin e the source and eliminate it, if possible,**  **before processing the samples. The blanks should b e carried through all stages of sample**  **preparation and analysis. When new reagents or che micals are received, the lab should**  **monitor the preparation and/or analysis blanks asso ciated with samples for any signs of**  **contamination. It is not necessary to test every n ew batch of reagents or chemicals prior to**  **sample preparation if the source shows no prior pro blems. However, if reagents are changed**  **during a preparation batch, separate blanks need to be prepared for each set of reagents.** **SW-846 Update V 8270D - 16 Revision 5 October 2012**  **9.6 Sample QC for preparation and analysis**

**The laboratory must also have procedures for docume nting the effect of the matrix on**  **method performance (precision, accuracy, method sen sitivity). At a minimum, this should**  **include the analysis of QC samples including a meth od blank, a matrix spike, a duplicate, and a**  **LCS in each analytical batch and the addition of su rrogates to each field sample and QC sample**  **when surrogates are used. Any method blanks, matri x spike samples, and replicate samples**  **should be subjected to the same analytical procedur es (Sec. 11.0) as those used on actual**  **samples.**

**9.6.1 Documenting the effect of the matrix should i nclude the analysis of at**  **least one matrix spike and one duplicate unspiked s ample or one matrix spike/matrix spike**  **duplicate pair. The decision on whether to prepare and analyze duplicate samples or a**  **matrix spike/matrix spike duplicate must be based o n knowledge of the samples in the**  **sample batch. If samples are expected to contain t arget analytes, laboratories may use a**  **matrix spike and a duplicate analysis of an unspike d field sample. If samples are not**  **expected to contain target analytes, then laborator ies should use a matrix spike and matrix**  **spike duplicate pair. Consult Method 8000 for info rmation on developing acceptance**  **criteria for the matrix spike and matrix spike dupl icate.** 

**9.6.2 An LCS should be included with each analytica l batch. The LCS consists**  **of an aliquot of a clean (control) matrix similar t o the sample matrix and of the same weight**  **or volume. The LCS is spiked with the same analyte s at the same concentrations as the**  **matrix spike, when appropriate. When the results o f the matrix spike analysis indicate a**  **potential problem due to the sample matrix itself, the LCS results are used to verify that**  **the laboratory can perform the analysis in a clean matrix. Consult Method 8000 for**  **information on developing acceptance criteria for t he LCS.** 

**9.6.3 Also see Method 8000 for the details on carry ing out sample QC**  **procedures for preparation and analysis. In-house method performance criteria for**  **evaluating method performance should be developed u sing the guidance found in Method**  **8000.**

**9.7 Surrogate recoveries**

**If surrogates are used, the laboratory should evalu ate surrogate recovery data from**  **individual samples versus the surrogate control lim its developed by the laboratory. See Method**  **8000 for information on evaluating surrogate data a nd developing and updating surrogate limits.**  **Procedures for evaluating the recoveries of multipl e surrogates and the associated corrective**  **actions should be defined in an approved project pl an.** 

**9.8 The experience of the analyst performing gas ch romatography/mass spectrometry**  **analyses is invaluable to the success of the method s. Each day that analysis is performed, the**  **calibration verification standard should be evaluat ed to determine if the chromatographic system**  **is operating properly. Questions that should be as ked are: Do the peaks look normal? Is the**  **response obtained comparable to the response from p revious calibrations? Careful**  **examination of the standard chromatogram can indica te whether the column is still performing**  **acceptably, the injector is leaking, the injector s eptum needs replacing, etc. When any changes**  **are made to the system (e.g., the column is changed , a septum is changed), see the guidance**  **in Method 8000 regarding whether recalibration of t he system must take place.** 

**9.9 It is recommended that the laboratory adopt add itional QA practices for use with**  **this method. The specific practices that are most productive depend upon the needs of the** **SW-846 Update V 8270D - 17 Revision 5 October 2012**  **laboratory and the nature of the samples. Whenever possible, the laboratory should analyze**  **standard reference materials and participate in rel evant performance evaluation studies.** 

**9.10 Lower limit of quantitation**

**The laboratory shall establish the LLOQ as the low est point of quantitation, which**  **in most cases is the lowest concentration in the ca libration curve. LLOQ verification is**  **recommended for each project application to validat e quantitation capability at low analyte**  **concentration levels. This verification may be acc omplished with either clean control material**  **(e.g., reagent water, solvent blank, Ottawa sand, d iatomaceous earth, etc.) or a representative**  **sample matrix, free of target compounds. Optimally , the LLOQ should be less than the desired**  **regulatory action levels based on the stated DQOs.**

**10.0 CALIBRATION AND STANDARDIZATION**

**See Sec 11.3 for information on calibration and sta ndardization.** 

**11.0 PROCEDURE**

**11.1 Sample preparation**

**11.1.1 Samples are normally prepared by one of the following methods prior to**  **gas chromatography/mass spectrometry analysis.**

**Matrix Methods** 

**Air (particulates and sorbent resin) 3542 Water (including TCLP leachates) 3510, 3520, 3535**  **Soil/sediment 3540, 3541, 3545, 3546, 3550, 3560, 3 561**  **Waste 3540, 3541, 3545, 3546, 3550, 3560, 3561, 3580** 

**11.1.2 In very limited applications, direct injecti on of the sample into the GC/MS**  **system with a 10-μL syringe may be appropriate. Th e quantitation limit is very high**  **(approximately 10,000 μg/L) when this procedure is used. Therefore, it is only appropriate**  **where concentrations in excess of 10,000 μg/L are e xpected.** 

**11.2 Extract cleanup - Cleanup procedures may not b e necessary for a relatively clean**  **sample matrix, but most extracts from environmental and waste samples will require additional**  **preparation before analysis. The specific cleanup procedure used will depend on the nature of**  **the sample to be analyzed and the DQOs for the meas urements. General guidance for sample**  **extract cleanup is provided in this section and in Method 3600.** 

**Extracts may be cleaned up by any of the following methods prior to gas**  **chromatography/mass spectrometry analysis.**

**Analytes of Interest Methods** 

**Aniline and aniline derivatives 3620 Phenols 3630, 3640, 8041**  **a Phthalate esters 3610, 3620, 3640**  **Nitrosamines 3610, 3620, 3640 SW-846 Update V 8270D - 18 Revision 5**  **October 2012 Organochlorine pesticides 3610, 3620, 3630, 3640,**  **3660 PCBs**  **3620, 3630, 3660, 3665 Nitroaromatics and cyclic ketones 3620, 3640**  **PAHs 3611, 3630, 3640**  **Haloethers 3620, 3640 Chlorinated hydrocarbons 3620, 3640**  **Organophosphorus pesticides 3620 Petroleum waste 3611, 3650**  **All base, neutral, and acid Priority pollutants 3640** 

**a Method 8041 includes a derivatization technique an**  **d a GC/electron capture detector (ECD) analysis, if interferences are encountered on**  **GC/flame ionization detector (FID).**

**11.3 Initial calibration**

**Establish the GC/MS operating conditions, using the following recommendations as**  **guidance.**

**Mass range: 35-500 amu Scan time:**  ≤ **1 sec/scan Initial temperature: 40**  ° **C, hold for 4 min Temperature program: 40-320**  ° **C at 10** ° **C/min Final temperature: 320**  ° **C, hold until 2 min after benzo[g,h,i]perylene elut es**  **Injector temperature: 250-300** ° **C Transfer line temperature: 250-300**  ° **C Source temperature: According to manufacturer's spe**  **cifications Injector: Grob-type, splitless**  **Injection volume: 1-2 μL Carrier gas: Hydrogen at 50 cm/sec or helium at 30**  **cm/sec Ion trap only: Set axial modulation, manifold tempe**  **rature, and emission current to manufacturer's recommendations** 

**Split injection is allowed if the sensitivity of th e MS is sufficient.** 

**11.3.1 The GC/MS system must be hardware-tuned such that injecting 50 ng or**  **less of DFTPP meets the manufacturer's specified ac ceptance criteria or as listed in Table**  **3. The tuning criteria as outlined in Table 3 were developed using quadrupole MS**  **instrumentation and it is recognized that other tun ing criteria may be more effective**  **depending on the type of instrumentation (e.g., Tim e-of-Flight, Ion Trap, etc.). In these**  **cases it would be appropriate to follow the manufac turer's tuning instructions or some**  **other consistent tuning criteria. However, no matt er which tuning criteria is selected, the**  **system calibration must not begin until the tuning acceptance criteria are met with the**  **sample analyses performed under the same conditions as the calibration standards.** 

**11.3.1.1 In the absence of specific recommendations on how to acquire**  **the mass spectrum of DFTPP from the instrument manu facturer, the following**  **approach should be used: Three scans (the peak ape x scan and the scans**  **immediately preceding and following the apex) are a cquired and averaged.**  **Background subtraction is required, and must be acc omplished using a single scan**  **acquired within 20 scans of the elution of DFTPP. The background subtraction**  **should be designed only to eliminate column bleed o r instrument background ions.**  **Do not subtract part of the DFTPP peak or any other discrete peak that does not**  **coelute with DFTPP. SW-846 Update V 8270D - 19 Revision 5**  **October 2012 11.3.1.2 Use the DFTPP mass intensity criteria in t**  **he manufacturer's instructions as primary tuning acceptance criteria**  **or those in Table 3 as default tuning acceptance criteria if the primary tuning cr**  **iteria are not available. Alternatively, other documented tuning criteria may**  **be used (e.g., Contract Laboratory Program (CLP) or Method 625), provided t**  **hat method performance is not adversely affected. The analyst is always free**  **to choose criteria that are tighter than those included in this method or to use other**  **documented criteria provided they are used consistently throughout the initial c**  **alibration, calibration verification, and sample analyses.** 

**NOTE : All subsequent standards, samples, matrix spikes/**  **matrix spike duplicates, and blanks associated with a DFTPP analysis must us**  **e identical MS instrument conditions.** 

**11.3.1.3 The GC/MS tuning standard solution should also be used to**  **assess the GC column performance and injection port inertness. Degradation of**  **dichlorodiphenyltrichloroethane** 

### ( **DDT) to dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD) should not**  **exceed 20%. (See Method 8081 for the percent breakdown calculation.) Benzi**  **dine and pentachlorophenol should be present at their normal responses, and sh**  **ould not exceed a tailing factor of 2 given by the following equation:** 

**where the peak is defined as follows: AC is the wi dth at 10% height; DE is the**  **height of peak and B is the height at 10% of DE. T his equation compares the width**  **of the back half of the peak to the width of the fr ont half of the peak at 10% of the**  **height. (See Figure 1 for an example tailing facto r calculation.)** 

**11.3.1.4 If degradation is excessive and/or poor c hromatography is**  **noted, the injection port may require cleaning. It may also be necessary to cut off**  **the first 6 to 12 in. of the capillary column to re move high boiling contaminants in**  **the column. The use of a guard column (Sec. 6.1.6) between the injection port and**  **the analytical column may help prolong analytical c olumn performance life.** 

**11.3.2 The internal standards selected in Sec. 7.5 should permit most of the**  **components of interest in a chromatogram to have re tention times of 0.80-1.20 relative**  **to one of the internal standards. Use the base pea k ion from the specific internal**  **standard as the primary ion for quantitation (see T able 1). If interferences are noted,**  **use the next most intense ion as the quantitation i on (e.g., for 1,4-dichlorobenzen-d**  **4 , use**  **m/z 150 for quantitation).**

**11.3.3 Analyze a consistent volume (typically 1-2 μL) of each calibration**  **standard (i.e., containing the compounds for quanti tation and the appropriate surrogates**  **and internal standards) and tabulate the area of th e primary ion against concentration for**  **each target analyte (as indicated in Table 1). A s et of at least five calibration standards**  **is necessary (see Sec. 7.7 and Method 8000). Alter nate injection volumes may be used**  **if the applicable QC requirements for using this me thod are met. The injection volume**  **must be the same for all standards and sample extra cts. Figure 2 shows a**  **chromatogram of a calibration standard containing b ase/neutral and acid analytes.**  AB BC Factor Tailing =**SW-846 Update V 8270D - 20 Revision 5 October 2012**  **11.3.4 Initial calibration calculations**

**Calculate response factors (RFs) for each target a nalyte relative to one of the**  **internal standards (see Table 4) as follows:**

**where: A**  **s = Peak area (or height) of the analyte or surrogat**  **e A**  **is = Peak area (or height) of the internal standard**  **C s**  **= Concentration of the analyte or surrogate, in μg /L**  **C is**  **= Concentration of the internal standard, in μg/L**

**11.3.4.1 Calculate the mean RF and the relative s tandard deviation**  **(RSD) of the RFs for each target analyte using the following equations. The RSD**  **should be less than or equal to 20% for each target analyte. It is also**  **recommended that a minimum RF for the most common t arget analytes, as noted**  **in Table 4, be demonstrated for each individual cal ibration level as a means to**  **ensure that these compounds are behaving as expecte d. In addition, meeting the**  **minimum RF criteria for the lowest calibration stan dard is critical in establishing**  **and demonstrating the desired sensitivity. Due to the large number of compounds**  **that may be analyzed by this method, some compounds will fail to meet these**  **criteria. For these occasions, it is acknowledged that the failing compounds may**  **not be critical to the specific project and therefo re they may be used as qualified**  **data or estimated values for screening purposes. T he analyst should also strive to**  **place more emphasis on meeting the calibration crit eria for those compounds that**  **are critical project compounds, rather than meeting the criteria for those less**  **important compounds.**

**where: RF**  **i = RF for each of the calibration standards** 

**RF = mean RF for each compound from the initial calib**  **ration n = Number of calibration standards, e.g., 5**  **SD = Standard deviation**

**11.3.4.2 If more than 10% of the compounds includ ed with the initial**  **calibration exceed the 20% RSD limit and do not mee t the minimum correlation**  **coefficient (0.99) for alternative curve fits, then the chromatographic system is**  **considered too reactive for analysis to begin. Cle an or replace the injector liner**  **and/or capillary column, then repeat the calibratio n procedure beginning with Sec.**  **11.3.**

**11.3.5 Evaluation of retention times - The RRT of each target analyte in each**  **calibration standard should agree within 0.06 RRT u nits. Late-eluting target analytes**  **usually have much better agreement.** s is is s 

### C A C A RF

× ×

=

1

- n RF (RF

SD n

1

i i 

# ∑

= 

### −

= 2



### )

n RF

RF RF mean n

1 i i 

# ∑

= = =



### 100 × = RF SD RSD**SW-846 Update V 8270D - 21 Revision 5 October 2012**  **11.3.6 Linearity of target analytes - If the RSD of any target analyte is 20% or**  **less, then the relative RF is assumed to be constan t over the calibration range, and the**  **average relative RF may be used for quantitation (S ec. 11.7.2).** 

**11.3.6.1 If the RSD of any target analyte is gre ater than 20%, refer to** 

**Method 8000 for additional calibration options. On e of the options must be applied**  **to GC/MS calibration in this situation, or a new in itial calibration must be**  **performed. The RF**  **should not be used for compounds that have an RSD g reater**  **than 20% unless the concentration is reported as es timated.** 

**11.3.6.2 When the RSD exceeds 20%, the plotting and visual** 

**inspection of a calibration curve can be a useful d iagnostic tool. The inspection**  **may indicate analytical problems, including errors in standard preparation, the**  **presence of active sites in the chromatographic sys tem, analytes that exhibit poor**  **chromatographic behavior, etc.**

**11.3.6.3 Due to the large number of compounds th at may be analyzed** 

**by this method, some compounds may fail to meet eit her the 20% RSD, minimum**  **correlation coefficient criteria (0.99), or the acc eptance criteria for alternative**  **calibration procedures in Method 8000. Any calibra tion method described in**  **Method 8000 may be used, but it should be used cons istently. It is considered**  **inappropriate once the calibration analyses are com pleted to select an alternative**  **calibration procedure in order to pass the recommen ded criteria on a case-by-case**  **basis. If compounds fail to meet these criteria, t he associate concentrations may**  **still be determined but they must be reported as es timated. In order to report non**  **detects, it must be demonstrated that there is adeq uate sensitivity to detect the**  **failed compounds at the applicable lower quantitati on limit.** 

**11.4 GC/MS calibration verification - Calibration verification consists of three steps that**  **are performed at the beginning of each twelve hour analytical shift.** 

**11.4.1 Prior to the analysis of samples or calib ration standards, inject 50 ng or**  **less of the DFTPP standard into the GC/MS system. The resultant mass spectrum for**  **DFTPP must meet the criteria as outlined in Sec. 11 .3.1 before sample analysis begins.**  **These criteria must be demonstrated each twelve hou r shift during which samples are**  **analyzed.**

**11.4.2 The initial calibration function for each target analyte should be checked**  **immediately after the first occurrence in the regio n of the middle of the calibration range**  **with a standard from a source different from that u sed for the initial calibration. The value**  **determined from the second source check should be w ithin 30% of the expected**  **concentration. An alternative recovery limit may b e appropriate based on the desired**  **project-specific DQOs. Quantitative sample analyse s should not proceed for those**  **analytes that fail the second source standard initi al calibration verification. However,**  **analyses may continue for those analytes that fail the criteria with an understanding that**  **these results could be used for screening purposes and would be considered estimated**  **values.** standard internal the of time Retention analyte

the of time Retention RRT =**SW-846 Update V 8270D - 22 Revision 5 October 2012**  **11.4.3 The initial calibration (Sec. 11.3) for e ach compound of interest should be**  **verified once every twelve hours prior to sample an alysis, using the introduction technique**  **and conditions used for samples. This is accomplis hed by analyzing a calibration**  **standard (containing all the compounds for quantita tion) at a concentration either near the**  **midpoint concentration for the calibrating range of the GC/MS or near the action level for**  **the project. The results must be compared against t he most recent initial calibration curve**  **and should meet the verification acceptance criteri a provided in Secs. 11.4.5 through**  **11.4.7.**

**NOTE : The DFTPP and calibration verification standard m**  **ay be combined into a single standard as long as both tuning and calibration ve**  **rification acceptance criteria for the project can be met without interferences.** 

**11.4.4 A method blank should be analyzed prior to sample analyses in order to**  **ensure that the total system (i.e., introduction de vice, transfer lines and GC/MS system) is**  **free of contaminants. If the method blank indicate s contamination, then it may be**  **appropriate to analyze a solvent blank to demonstra te that the contamination is not a**  **result of carryover from standards or samples. See Method 8000 for information regarding**  **method blank performance criteria.**

**11.4.5 Calibration verification standard criteria**

**11.4.5.1 Each of the most common target analytes in the calibration** 

**verification standard should meet the minimum RFs a s noted in Table 4. This**  **criterion is particularly important when the common target analytes are also critical**  **project-required compounds. This is the same check that is applied during the**  **initial calibration.**

**11.4.5.2 If the minimum RFs are not met, the sys tem should be** 

**evaluated, and corrective action should be taken be fore sample analysis begins.**  **Possible problems include standard mixture degradat ion, injection port inlet**  **contamination, contamination at the front end of th e analytical column, and active**  **sites in the column or chromatographic system.**

**11.4.5.3 All target compounds of interest must b e evaluated using a** 

**20% criterion. Use percent difference when perform ing the**  **RF model calibration.**  **Use percent drift when calibrating using a regressi on fit model. Refer to Method**  **8000 for guidance on calculating percent difference and drift.** 

**11.4.5.4 If the percent difference or percent dr ift for a compound is less** 

**than or equal to 20%, then the initial calibration for that compound is assumed to**  **be valid. Due to the large numbers of compounds th at may be analyzed by this**  **method, it is expected that some compounds will fai l to meet the criterion. If the**  **criterion is not met (i.e., greater than 20% differ ence or drift) for more than 20% of**  **the compounds included in the initial calibration, then corrective action must be**  **taken prior to the analysis of samples. In cases w here compounds fail, they may**  **still be reported as non-detects if it can be demon strated that there was adequate**  **sensitivity to detect the compound at the applicabl e quantitation limit. For**  **situations when the failed compound is present, the concentrations must be**  **reported as estimated values.**

**11.4.5.5 Problems similar to those listed under initial calibration could** 

**affect the ability to pass the calibration verifica tion standard analysis. If the**  **problem cannot be corrected by other measures, a ne w initial calibration must be** **SW-846 Update V 8270D - 23 Revision 5 October 2012**  **generated. The calibration verification criteria m ust be met before sample analysis**  **begins.**

**11.4.5.6 The method of linear regression analysi s has the potential for** 

**a significant bias to the lower portion of a calibr ation curve, while the relative**  **percent difference and quadratic methods of calibra tion do not have this potential**  **bias. When calculating the calibration curves usin g the linear regression model, a**  **minimum quantitation check on the viability of the lowest calibration point should be**  **performed by re-fitting the response from the low c oncentration calibration**  **standard back into the curve (see Method 8000 for a dditional details). It is not**  **necessary to re-analyze a low concentration standar d; rather the data system can**  **recalculate the concentrations as if it were an unk nown sample. The recalculated**  **concentration of the low calibration point should b e within ± 30% of the standard's**  **true concentration. Other recovery criteria may be applicable depending on the**  **project's DQOs and for those situations the minimum quantitation check criteria**  **should be outlined in a laboratory SOP, or a projec t-specific QAPP. Analytes**  **which do not meet the minimum quantitation calibrat ion re-fitting criteria should be**  **considered "out of control" and corrective action s uch as redefining the LLOQ**  **and/or reporting those "out of control" target anal ytes as estimated when the**  **concentration is at or near the lowest calibration point may be appropriate.** 

**11.4.6 Internal standard retention time - The re tention times of the internal** 

**standards in the calibration verification standard must be evaluated immediately after or**  **during data acquisition. If the absolute retention time for any internal standard changes by**  **more than 30 sec from that in the mid-point standar d level of the most recent initial**  **calibration sequence, then the chromatographic syst em must be inspected for**  **malfunctions and corrections must be made, as requi red. When corrections are made,**  **reanalysis of samples analyzed while the system was malfunctioning is required.** 

**11.4.7 Internal standard response - If the EICP area for any of the internal** 

**standards in the calibration verification standard changes by a factor of two (−50% to**  **+100%) from that in the mid-point standard level of the most recent initial calibration**  **sequence, the MS must be inspected for malfunctions and corrections must be made, as**  **appropriate. When corrections are made, reanalysis of samples analyzed while the**  **system was malfunctioning is required.**

**11.5 Gas chromatography/mass spectrometry analysis of samples** 

**11.5.1 It is highly recommended that sample extra cts be screened on a GC/FID**  **or GC/PID using the same type of capillary column u sed in the GC/MS system. This will**  **minimize contamination of the GC/MS system from une xpectedly high concentrations of**  **organic compounds.**

**11.5.2 Allow the sample extract to warm to room t emperature. Just prior to**  **analysis, add 10 μL of the internal standard soluti on to the 1 mL of concentrated sample**  **extract obtained from sample preparation.**

**11.5.3 Inject an aliquot of the sample extract in to the GC/MS system, using the**  **same operating conditions that were used for the ca libration (Sec. 11.3). The volume to**  **be injected should include an appropriate concentra tion that is within the calibration range**  **of base/neutral and acid surrogates using the surro gate solution as noted in Sec. 7.8. The**  **injection volume must be the same volume that was u sed for the calibration standards.** **SW-846 Update V 8270D - 24 Revision 5 October 2012**  **11.5.4 If the response for any quantitation ion e xceeds the initial calibration**  **range of the GC/MS system, the sample extract must be diluted and reanalyzed.**  **Additional internal standard solution must be added to the diluted extract to maintain the**  **same concentration as in the calibration standards (usually 40 ng/μL, or other**  **concentrations as appropriate, if a more sensitive GC/MS system is being used).**  **Secondary ion quantitation should be used only when there are sample interferences with**  **the primary ion.**

**NOTE : It may be a useful diagnostic tool to monitor int**  **ernal standard retention times in all samples, spikes, blanks, and standards to effectiv**  **ely check drifting, method performance, poor injection execution, and anticipa**  **te the need for system inspection and/or maintenance. Internal standard r**  **esponses (area counts) should be monitored in all samples, spikes and blanks for**  **similar reasons. If the EICP area for any of the internal standards in samples,**  **spikes, and blanks changes by a factor of two (−50% to +100%) from the areas determ**  **ined in the continuing calibration analyzed that day, corrective action sh**  **ould be taken. The samples, spikes, or blanks should be reanalyzed or the data**  **should be qualified.**

**11.5.4.1 When ions from a compound in the sample saturate the** 

**detector, this analysis should be followed by the a nalysis of an instrument blank**  **consisting of clean solvent. If the blank analysis is not free of interferences, then**  **the system must be decontaminated. Sample analysis may not resume until the**  **blank analysis is demonstrated to be free of interf erences. Contamination from**  **one sample to the next on the instrument usually ta kes place in the syringe. If**  **adequate syringe washers are employed, then carryov er from high concentration**  **samples can usually be avoided.**

**11.5.4.2 All dilutions should keep the response of the major** 

**constituents (previously saturated peaks) in the up per half of the linear range of the** 

**curve.**

**11.5.5 The use of a selected ion monitoring (SIM ) technique is acceptable for** 

**applications requiring quantitation limits below th e normal range of electron impact mass**  **spectrometry. However, SIM may provide a lesser deg ree of confidence in the compound**  **identification, since less mass spectral informatio n is available. Using the primary ion for**  **quantitation and the secondary ions for confirmatio n, set up the collection groups based on**  **their retention times. The selected ions are nomin al ions and most compounds have small**  **mass defect, usually less than 0.2 amu, in their sp ectra. These mass defects should be**  **used in the acquisition table. The dwell time may be automatically calculated by the**  **laboratory's GC/MS software or manually calculated using the following formula. The total**  **scan time should be less than 1,000 msec and produc e at least 5 to 10 scans per**  **chromatographic peak. The start and stop times for the SIM groups are determined from**  **the full scan analysis using the formula below:**

**Additional guidance for performing SIM analyses, in particular for PAHs and phenol target**  **analyte compounds, can be found in the most recent CLP semivolatile organic methods**  **statement of work (SOW). See the SIM sections from the following CLP SOW for further**  **details: EPA CLP Organics SOW (Reference 14).** Group the in Ions Total (msec) Time Scan Group the for Time Dwell =**SW-846 Update V 8270D - 25 Revision 5 October 2012**  **11.6 Analyte identification**

**11.6.1 The qualitative identification of compound s determined by this method is**  **based on retention time and on comparison of the sa mple mass spectrum, after**  **background correction, with characteristic ions in a reference mass spectrum. The**  **reference mass spectrum must be generated by the la boratory using the conditions of this**  **method. The characteristic ions from the reference mass spectrum are defined as the**  **three ions of greatest relative intensity, or any i ons over 30% relative intensity, if less than**  **three such ions occur in the reference spectrum. C ompounds are identified when the**  **following criteria are met.**

**11.6.1.1 The intensities of the characteristic i ons of a compound must** 

**maximize in the same scan or within one scan of eac h other. Selection of a peak**  **by a data system target compound search routine whe re the search is based on**  **the presence of a target chromatographic peak conta ining ions specific for the**  **target compound at a compound-specific retention ti me will be accepted as**  **meeting this criterion.**

**11.6.1.2 The RRT of the sample component is with in ± 0.06 RRT units** 

**of the RRT of the standard component.**

**11.6.1.3 The relative intensities of the charact eristic ions agree within** 

**30% of the relative intensities of these ions in th e reference spectrum. For**  **example, an ion with an abundance of 50% in the ref erence spectrum, the**  **corresponding abundance in a sample spectrum can ra nge between 20% and**  **80%. Use professional judgment in interpretation w here interferences are**  **observed.**

**11.6.1.4 Structural isomers that produce very si milar mass spectra** 

**should be identified as individual isomers if they have sufficiently different gas**  **chromatographic retention times. Sufficient gas ch romatographic resolution is**  **achieved if the height of the valley between two is omer peaks is less than 50% of**  **the average of the two peak heights. Otherwise, str uctural isomers are identified as**  **isomeric pairs. The resolution should be verified on the mid-point concentration of**  **the initial calibration as well as the laboratory d esignated continuing calibration**  **verification level if closely eluting isomers are t o be reported (e.g.,**  **benzo(b)fluoranthene and benzo(k)fluoranthene).**

**11.6.1.5 Identification is hampered when sample components are not** 

**resolved chromatographically and produce mass spect ra containing ions**  **contributed by more than one analyte. When gas chr omatographic peaks**  **obviously represent more than one sample component (i.e., a broadened peak with**  **shoulder(s) or a valley between two or more maxima) , appropriate selection of**  **analyte spectra and background spectra is important**

**. 11.6.1.6 Examination of extracted ion current pr**  **ofiles of appropriate**

**ions can aid in the selection of spectra and in qua litative identification of**  **compounds. When analytes co-elute (i.e., only one chromatographic peak is**  **apparent), the identification criteria may be met, but each analyte spectrum will**  **contain extraneous ions contributed by the co-eluti ng compound.** 

**11.6.2 For samples containing components not ass ociated with the calibration** 

**standards, a library search may be made for the pur pose of tentative identification. The**  **necessity to perform this type of identification wi ll be determined by the purpose of the** **SW-846 Update V 8270D - 26 Revision 5 October 2012**  **analyses being conducted. Data system library sear ch routines should not use**  **normalization routines that would misrepresent the library or unknown spectra when**  **compared to each other.**

**For example, the RCRA permit or waste delisting r equirements may require the**  **reporting of non-target analytes. Only after visua l comparison of sample spectra with the**  **nearest library searches may the analyst assign a t entative identification. Guidelines for**  **tentative identification are:**

**(1) Relative intensities of major ions in the ref erence spectrum (i.e., ions > 10%**  **of the most abundant ion) should be present in the sample spectrum.** 

**(2) The relative intensities of the major ions sh ould agree within ± 30%. For**  **example, an ion with an abundance of 50% in the sta ndard spectrum must**  **have a corresponding sample ion abundance between 2 0 and 80%.** 

**(3) Molecular ions present in the reference spect rum should be present in the**  **sample spectrum.**

**(4) Ions present in the sample spectrum but not i n the reference spectrum**  **should be reviewed for possible background contamin ation or presence of**  **co-eluting compounds.**

**(5) Ions present in the reference spectrum but no t in the sample spectrum**  **should be reviewed for possible subtraction from th e sample spectrum**  **because of background contamination or co-eluting p eaks. Data system**  **library reduction programs can sometimes create the se discrepancies.** 

**11.7 Quantitation**

**11.7.1 Once a target compound has been identified , the quantitation of that**  **compound will be based on the integrated abundance of the primary characteristic ion**  **from the EICP.**

**11.7.1.1 It is highly recommended to use the int egration produced by** 

**the software if the integration is correct because the software should produce more**  **consistent integrations than an analyst will manual ly. However, manual**  **integrations may be necessary when the software doe s not produce proper**  **integrations because baseline selection is improper ; the correct peak is missed; a**  **coelution is integrated; the peak is partially inte grated; etc. The analyst is**  **responsible for ensuring that the integration is co rrect whether performed by the**  **software or done manually.**

**11.7.1.2 Manual integrations should not be subst ituted for proper** 

**maintenance of the instrument or setup of the metho d (e.g., retention time updates,**  **integration parameter files, etc.). The analyst sh ould seek to minimize manual**  **integration by properly maintaining the instrument, updating retention times, and**  **configuring peak integration parameters.**

**11.7.2 If the RSD of a compound's RF is 20% or le ss, then the concentration in**  **the extract may be determined using the** RF **from initial calibration data (Sec. 11.3.4). See Method 8000 for the equations describing internal s**  **tandard calibration and either linear or non-linear calibrations.** **SW-846 Update V 8270D - 27 Revision 5 October 2012**  **11.7.3 Where applicable, the concentration of any non-target analytes identified**  **in the sample (Sec. 11.6.2) should be estimated. T he same formula as in Sec. 11.3.4**  **should be used with the following modifications: T he areas A**  **x and A**  **is should be from the**  **total ion chromatograms, and the RF for the compoun d should be assumed to be 1.** 

**11.7.4 The resulting concentration should be repo rted indicating that the value is**  **an estimate. Use the nearest internal standard fre e of interferences.** 

**11.7.5 Quantitation of multicomponent compounds ( e.g., toxaphene, Aroclors,**  **etc.) is beyond the scope of Method 8270. Normally , quantitation is performed using a**  **GC/ECD, for example by Methods 8081 or 8082. Howev er, this method (8270) may be**  **used to confirm the identification of these compoun ds, when the concentrations are at**  **least 10 ng/μL in the concentrated sample extract.**

**11.7.6 Quantitation of multicomponent parameters such as diesel range organics**  **(DROs) and total petroleum hydrocarbons (TPH) using the Method 8270 recommended**  **internal standard quantitation technique is beyond the scope of this method. Typically,**  **analyses for these parameters are performed using G C/FID or GC with a MS detector**  **capability that is available with Method 8015.**

**11.7.7 Structural isomers that produce very simil ar mass spectra should be**  **quantitated as individual isomers if they have suff iciently different gas chromatographic**  **retention times. Sufficient gas chromatographic re solution is achieved if the height of the**  **valley between two isomer peaks is less than 50% of the average of the two peak heights.**  **Otherwise, structural isomers are identified as iso meric pairs. The resolution should be**  **verified on the mid-point concentration of the init ial calibration as well as the laboratory**  **designated continuing calibration verification leve l if closely eluting isomers are to be**  **reported (e.g., benzo(b)fluoranthene and benzo(k)fl uoranthene).** 

**12.0 DATA ANALYSIS AND CALCULATIONS**

**See Sec. 11.7 and Method 8000 for information on d ata analysis and calculations.** 

**13.0 METHOD PERFORMANCE**

**13.1 Performance data and related information are provided in SW-846 methods only as**  **examples and guidance. The data do not represent r equired performance criteria for users of**  **the methods. Instead, performance criteria should be developed on a project-specific basis,**  **and the laboratory should establish in-house QC per formance criteria for the application of this**  **method. These performance data are not intended to be and must not be used as absolute QC**  **acceptance criteria for purposes of laboratory accr editation.** 

**13.2 Single laboratory initial demonstration of ca pability data were generated from five**  **replicate measurements using a modified continuous liquid-liquid extractor (Method 3520) with**  **hydrophobic membrane. In this case only a single a cid pH extraction was performed using the**  **CLP calibration criteria and the applicable CLP tar get analytes. These data are presented in**  **Table 6. Laboratories should generate their own ac ceptance criteria depending on the**  **extraction and instrument conditions. See Method 8 000 for more detailed guidance.** 

**13.3 Chromatograms from calibration standards anal yzed with Day 0 and Day 7**  **samples were compared to detect possible deteriorat ion of gas chromatographic performance.** **SW-846 Update V 8270D - 28 Revision 5 October 2012**  **These recoveries (using Method 3510 extraction) are presented in Table 7. These data are**  **provided for guidance purposes only.**

**13.4 Method performance data using Method 3541 (i. e., automated Soxhlet extraction)**  **are presented in Tables 8 and 9. Single laboratory accuracy and precision data were obtained**  **for semivolatile organics in a clay soil by spiking at a concentration of 6 mg/kg for each**  **compound. The spiking solution was mixed into the soil during addition and then allowed to**  **equilibrate for approximately one hour prior to ext raction. The spiked samples were then**  **extracted by Method 3541 (Automated Soxhlet). Thre e extractions were performed and each**  **extract was analyzed by GC/MS following Method 8270 . The low recovery of the more volatile**  **compounds is probably due to volatilization losses during equilibration. These data as listed**  **were taken from Reference 7 and are provided for gu idance purposes only.** 

**13.5 Surrogate precision and accuracy data are pre sented in Table 10 from a field**  **dynamic spiking study based on air sampling by Meth od 0010. The trapping media were**  **prepared for analysis by Method 3542 and subsequent ly analyzed by this method (i.e., 8270).**  **These data are provided for guidance purposes only.**

**13.6 Single laboratory precision and bias data usi ng Method 3545 (i.e., pressurized fluid**  **extraction) for semivolatile organic compounds are presented in Table 11. The samples were**  **conditioned spiked samples prepared and certified b y a commercial supplier that contained 57**  **semivolatile organics at three concentrations (i.e. , 250, 2500, and 12,500 μg/kg) on three types**  **of soil (i.e, clay, loam, and sand). Spiked sample s were extracted both by the Dionex ASE**  **system and by the Perstorp Environmental Soxtec TM**  **(i.e., automated Soxhlet). The data in Table 11 represent seven replicate extractions and**  **analyses for each individual sample and were taken from Reference 9. The average recoverie**  **s from the three matrices for all analytes and all replicates relative to the automated Soxhle**  **t data are as follows: clay 96.8%, loam 98.7% and sand 102.1%. The average recoveries from**  **the three concentrations also relative to the automated Soxhlet data are as follows: low – 1**  **01.2%, mid – 97.2% and high – 99.2%. These data are provided for guidance purposes only.** 

**13.7 Single laboratory precision and bias data usi ng Method 3561 (i.e., SFE extraction**  **of PAHs with a variable restrictor and solid trappi ng material) were obtained for the method**  **analytes by the extraction of two certified referen ce materials (i.e., EC-1, a lake sediment from**  **Environment Canada and HS-3, a marine sediment from the National Science and Engineering**  **Research Council of Canada, both naturally contamin ated with PAHs). The SFE instrument**  **used for these extractions was a Hewlett-Packard Mo del 7680. Analysis was by GC/MS.**  **Average recoveries from six replicate extractions r anged from 85 to 148%, with an overall**  **average of 100%, based on the certified value (or a Soxhlet value if a certified value was**  **unavailable for a specific analyte) for the lake se diment. Average recoveries from three**  **replicate extractions ranged from 73 to 133%, with an overall average of 92%, based on the**  **certified value for the marine sediment. The data are found in Tables 12 and 13 and were taken**  **from Reference 10. These data are provided for gui dance purposes only.** 

**13.8 Single laboratory precision and accuracy usin g Method 3561 (i.e., SFE extraction**  **of PAHs with a fixed restrictor and liquid trapping ) were obtained for twelve of the method**  **analytes by the extraction of a certified reference material (i.e., a soil naturally contaminated**  **with PAHs). The SFE instrument used for these extr actions was a Dionex Model 703-M.**  **Analysis was by GC/MS. Average recoveries from fou r replicate extractions ranged from 60 to**  **122%, with an overall average of 89%, based on the certified value. The instrument conditions**  **that were utilized to extract a 3.4 g sample were a s follows: Pressure - 300 atm; time - 60 min;**  **extraction fluid - CO 2**  **; modifier - 10% 1:1 (v/v) methanol/methylene chlor ide; Oven temperature -**  **80 °C; Restrictor temperature - 120 °C; and, trappi ng fluid - chloroform (methylene chloride has** **SW-846 Update V 8270D - 29 Revision 5 October 2012**  **also been used). The data are found in Table 14 an d were taken from Reference 11. These**  **data are provided for guidance purposes only.**

**13.9 Tables 15 and 16 contain single-laboratory pr ecision and accuracy data for solid**  **phase extraction of TCLP buffer solutions spiked at two levels and extracted using Method**  **3535. These data are provided for guidance purpose s only.** 

**13.10 Table 17 contains multiple-laboratory data f or solid-phase extraction of spiked**  **TCLP soil leachates extracted using Method 3535. T hese data are provided for guidance**  **purposes only.**

**13.11 Tables 18 through 22 contain single-laborato ry PAH recovery data for microwave**  **extraction of contaminated soils and standard refer ence materials using Method 3546. These**  **data are provided for guidance purposes only.**

**14.0 POLLUTION PREVENTION**

**14.1 Pollution prevention encompasses any techniqu e that reduces or eliminates the**  **quantity and/or toxicity of waste at the point of g eneration. Numerous opportunities for pollution**  **prevention exist in laboratory operations. The EPA has established a preferred hierarchy of**  **environmental management techniques that places pol lution prevention as the management**  **option of first choice. Whenever feasible, laborat ory personnel should use pollution prevention**  **techniques to address their waste generation. When wastes cannot be feasibly reduced at the**  **source, the Agency recommends recycling as the next best option.** 

**14.2 For information about pollution prevention tha t may be applicable to laboratories**  **and research institutions consult** Less is Better: Laboratory Chemical Management for Waste Reduction **, a free publication available from the ACS, Commit tee on Chemical Safety,**  **http://portal.acs.org/portal/fileFetch/C/WPCP_01229 0/pdf/WPCP_012290.pdf** 

**.**

**15.0 WASTE MANAGEMENT**

**The EPA requires that laboratory waste management practices be conducted consistent**  **with all applicable rules and regulations. The Age ncy urges laboratories to protect the air,**  **water, and land by minimizing and controlling all r eleases from hoods and bench operations,**  **complying with the letter and spirit of any sewer d ischarge permits and regulations, and by**  **complying with all solid and hazardous waste regula tions, particularly the hazardous waste**  **identification rules and land disposal restrictions . For further information on waste**  **management, consult** The Waste Management Manual for Laboratory Personne l **available from the ACS at the web address listed in Sec. 14.2.** 

**16.0 REFERENCES**

**1. J. W. Eichelberger, L. E. Harris, and W. L. Budd e, "Reference Compound to Calibrate Ion**  **Abundance Measurement in Gas Chromatography-Mass Sp ectrometry Systems,"**  Analytical Chemistry **, 47, 995-1000, 1975.**

**2. P. Olynk, W. L. Budde, and J. W. Eichelberger, " Method Detection Limit for Methods 624**  **and 625," unpublished report, October 1980.**

**3. "Interlaboratory Method Study for EPA Method 625 - Base/Neutrals, Acids, and**  **Pesticides," Final Report for EPA Contract 68-03-31 02.** **SW-846 Update V 8270D - 30 Revision 5 October 2012**  **4. J. A. Burke, "Gas Chromatography for Pesticide R esidue Analysis: Some Practical**  **Aspects,"** Journal of the Association of Official Analytical C hemists **(AOAC), 48, 1037, 1965.** 

**5. S. V. Lucas, R. A. Kornfeld, "GC-MS Suitability Testing of RCRA Appendix VIII and**  **Michigan List Analytes," U.S. Environmental Protect ion Agency, Environmental Monitoring**  **and Support Laboratory, Cincinnati, OH 45268, Contr act No. 68-03-3224, February 20,**  **1987.**

**6. T. M. Engel, R. A. Kornfeld, J. S. Warner, and K . D. Andrews, "Screening of Semivolatile**  **Organic Compounds for Extractability and Aqueous St ability by SW-846, Method 3510,"**  **U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory,**  **Cincinnati, OH 45268, Contract 68-03-3224, June 5, 1987.** 

**7. V. Lopez-Avila (W. Beckert, Project Officer), "D evelopment of a Soxtec Extraction**  **Procedure for Extraction of Organic Compounds from Soils and Sediments," U.S.**  **Environmental Protection Agency, Environmental Moni toring and Support Laboratory, Las**  **Vegas, NV, EPA 600/X-91/140, October 1991.**

**8. J. Bursey, R. Merrill, R. McAllister, and J. McG aughey, "Laboratory Validation of VOST**  **and SemiVOST for Halogenated Hydrocarbons from the Clean Air Act Amendments List,"**  **Vol. 1 and 2, U.S. Environmental Protection Agency, EPA 600/R-93/123a and b, (NTIS PB**  **93-227163 and 93-27171), Research Triangle Park, NC , July 1993.** 

**9. B. Richter, J. Ezzell, and D. Felix, "Single Lab oratory Method Validation Report:**  **Extraction of Target Compound List/Priority Polluta nt List BNAs and Pesticides using**  **Accelerated Solvent Extraction (ASE) with Analytica l Validation by GC/MS and GC/ECD,"**  **Document 101124, Dionex Corporation, Salt Lake City , UT, June 16, 1994.** 

**10. H. B. Lee, T. E. Peart, R. L. Hong-You, and D. R. Gere, "Supercritical Carbon Diozide**  **Extraction of Polycyclic Aromatic Hydrocarbons from Sediments,"**  J. Chromatography **, A, 653, 83-91 (1993).** 

**11. S. Warner, "SFE Extraction of PNAs from Solid M atrices Using the Dionex 703M SFE**  **Extractor and a Liquid Trap," EPA Region III, Centr al Regional Laboratory, 839 Bestgate**  **Road, Annapolis, MD 21401, December 12, 1994.**

**12. C. Markell, "3M Data Submission to EPA," letter to B. Lesnik, June 27, 1995.** 

**13. U.S. EPA Method 525.2, "Determination of Organi c Compounds in Drinking Water by**  **Liquid-Solid Extraction and Capillary Column Gas Ch romatography/Mass Spectrometry,"**  **Environmental Monitoring Systems Laboratory, Office of Research and Development, US**  **EPA, Cincinnati, OH, Revision 2.0, March 1995.**

**14. USEPA, Superfund Analytical Services/Contract L aboratory Program (CLP), Multi-Media,**  **Multi-Concentration Organics Analysis, SOM01.X, Exh ibit D - Analytical Methods,**  **"Analytical Method for the Analysis of Semivolatile Organic Compounds," November,**  **2003.**

**17.0 TABLES, DIAGRAMS, FLOW CHARTS, AND VALIDATION DATA** 

**The following pages contain the tables and figures referenced by this method.** **SW-846 Update V 8270D - 31 Revision 5 October 2012**  **TABLE 1**

**CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS IN A PPROXIMATE**  **RETENTION TIME ORDER a** 

**Compound Primary Ion Secondary Ion(s)**  **2-Picoline 93 66,92**  **Aniline 93 66,65**  **Phenol 94 65,66**  **Bis(2-chloroethyl) ether 93 63,95 2-Chlorophenol**  **128 64,130 1,3-Dichlorobenzene 146 148,111**  **1,4-Dichlorobenzene-d 4**  **(IS) 152 150,115 1,4-Dichlorobenzene 146 148,111**  **Benzyl alcohol 108 79,77**  **1,2-Dichlorobenzene 146 148,111 N-Nitrosomethylethylamine 88 42,43,56**  **Bis(2-chloro-1-methylethyl)ether 45 77,121 Ethyl carbamate**  **62 44,45,74 Thiophenol (Benzenethiol) 110 66,109,84**  **Methyl methanesulfonate 80 79,65,95 N-Nitrosodi-n-propylamine 70 42,101,130**  **Hexachloroethane 117 201,199**  **Maleic anhydride 54 98,53,44**  **Nitrobenzene 77 123,65**  **Isophorone 82 95,138**  **N-Nitrosodiethylamine 102 42,57,44,56 2-Nitrophenol**  **139 109,65 2,4-Dimethylphenol**  **122 107,121 p-Benzoquinone**  **108 54,82,80 Bis(2-chloroethoxy)methane 93 95,123**  **Benzoic acid 122 105,77**  **2,4-Dichlorophenol 162 164,98**  **Trimethyl phosphate 110 79,95,109,140**  **Ethyl methanesulfonate 79 109,9745,65 1,2,4-Trichlorobenzene 180 182,145**  **Naphthalene-d 8**  **(IS) 136 68**  **Naphthalene 128 129,127**  **Hexachlorobutadiene 225 223,227 Tetraethyl pyrophosphate 99 155,127,81,109**  **Diethyl sulfate 139 45,59,99,111,125**  **4-Chloro-3-methylphenol 107 144,142 2-Methylnaphthalene 142 141**  **2-Methylphenol 107 108,77,79,90**  **Hexachloropropene 213 211,215,117,106,141**  **Hexachlorocyclopentadiene 237 235,272 N-Nitrosopyrrolidine**  **100 41,42,68,69 Acetophenone**  **105 71,51,120 3/4-Methylphenol**  **b 107 108,77,79,90**  **2,4,6-Trichlorophenol 196 198,200 o-Toluidine**  **106 107,77,51,79 2-Chloronaphthalene 162 127,164**  **N-Nitrosopiperidine 114 42,55,56,41** **SW-846 Update V 8270D - 32 Revision 5 October 2012**  **Compound Primary Ion Secondary Ion(s)**  **1,4-Phenylenediamine 108 80,53,54,52 1-Chloronaphthalene 162 127,164**  **2-Nitroaniline 65 92,138**  **5-Chloro-2-methylaniline 106 141,140,77,89 Dimethyl phthalate**  **163 194,164 Acenaphthylene**  **152 151,153 2,6-Dinitrotoluene**  **165 63,89 Phthalic anhydride**  **104 76,50,148 o-Anisidine**  **108 80,123,52 3-Nitroaniline**  **138 108,92 Acenanaphthene-d**  **10 (IS) 164 162,160**  **Acenaphthene 154 153,152**  **2,4-Dinitrophenol 184 63,154**  **2,6-Dinitrophenol 162 164,126,98,63**  **4-Chloroaniline 127 129,65,92**  **Isosafrole 162 131,104,77,51**  **Dibenzofuran 168 139**  **2,4-Diaminotoluene 121 122,94,77,104**  **2,4-Dinitrotoluene 165 63,89**  **4-Nitrophenol 139 109,65**  **2-Naphthylamine 143 115,116**  **1,4-Naphthoquinone 158 104,102,76,50,130**  **p-Cresidine 122 94,137,77,93**  **Dichlorovos 109 185,79,145**  **Diethyl phthalate 149 177,150**  **Fluorene 166 165,167**  **2,4,5-Trimethylaniline 120 135,134,91,77 N-Nitrosodi-n-butylamine 84 57,41,116,158**  **4-Chlorophenyl phenyl ether 204 206,141 Hydroquinone**  **110 81,53,55 4,6-Dinitro-2-methylphenol 198 51,105**  **Resorcinol 110 81,82,53,69**  **N-Nitrosodiphenylamine 169 168,167 Safrole**  **162 104,77,103,135 Hexamethyl phosphoramide 135 44,179,92,42**  **3-(Chloromethyl)pyridine hydrochloride 92 127,129,6 5,39**  **Diphenylamine 169 168,167**  **1,2,4,5-Tetrachlorobenzene 216 214,179,108,143,218 1-Naphthylamine**  **143 115,89,63 1-Acetyl-2-thiourea**  **118 43,42,76 4-Bromophenyl phenyl ether 248 250,141**  **Toluene diisocyanate 174 145,173,146,132,91 2,4,5-Trichlorophenol 196 198,97,132,99**  **Hexachlorobenzene 284 142,249**  **Nicotine 84 133,161,162**  **Pentachlorophenol 266 264,268**  **5-Nitro-o-toluidine 152 77,79,106,94**  **Thionazine 107 96,97,143,79,68**  **4-Nitroaniline 138 65,108,92,80,39**  **Phenanthrene-d 10**  **(IS) 188 94,80 Phenanthrene**  **178 179,176 Anthracene**  **178 176,179 SW-846 Update V 8270D - 33 Revision 5**  **October 2012 Compound**  **Primary Ion Secondary Ion(s) 1,4-Dinitrobenzene**  **168 75,50,76,92,122 Mevinphos**  **127 192,109,67,164 Naled**  **109 145,147,301,79,189 1,3-Dinitrobenzene**  **168 76,50,75,92,122 Diallate (cis or trans)**  **86 234,43,70 1,2-Dinitrobenzene**  **168 50,63,74 Diallate (trans or cis)**  **86 234,43,70 Pentachlorobenzene**  **250 252,108,248,215,254 5-Nitro-o-anisidine**  **168 79,52,138,153,77 Pentachloronitrobenzene 237 142,214,249,295,265**  **4-Nitroquinoline-1-oxide 174 101,128,75,116 Di-n-butyl phthalate**  **149 150,104 2,3,4,6-Tetrachlorophenol 232 131,230,166,234,168**  **Dihydrosaffrole 135 64,77**  **Demeton-O 88 89,60,61,115,171**  **Fluoranthene 202 101,203**  **1,3,5-Trinitrobenzene 75 74,213,120,91,63 Dicrotophos**  **127 67,72,109,193,237 Benzidine**  **184 92,185 Trifluralin**  **306 43,264,41,290 Bromoxynil**  **277 279,88,275,168 Pyrene**  **202 200,203 Monocrotophos**  **127 192,67,97,109 Phorate**  **75 121,97,93,260 Sulfallate**  **188 88,72,60,44 Demeton-S**  **88 60,81,89,114,115 Phenacetin**  **108 180,179,109,137,80 Dimethoate**  **87 93,125,143,229 Phenobarbital**  **204 117,232,146,161 Carbofuran**  **164 149,131,122 Octamethyl pyrophosphoramide 135 44,199,286,153,243**  **4-Aminobiphenyl 169 168,170,115**  **Dioxathion 97 125,270,153**  **Terbufos 231 57,97,153,103**  **α,α-Dimethylphenylamine 58 91,65,134,42 Pronamide**  **173 175,145,109,147 Aminoazobenzene**  **197 92,120,65,77 Dichlone**  **191 163,226,228,135,193 Dinoseb**  **211 163,147,117,240 Disulfoton**  **88 97,89,142,186 Fluchloralin**  **306 63,326,328,264,65 Mexacarbate**  **165 150,134,164,222 4,4'-Oxydianiline**  **200 108,171,80,65 Butyl benzyl phthalate 149 91,206**  **4-Nitrobiphenyl 199 152,141,169,151**  **Phosphamidon 127 264,72,109,138**  **2-Cyclohexyl-4,6-Dinitrophenol 231 185,41,193,266 Methyl parathion**  **109 125,263,79,93 Carbaryl**  **144 115,116,201 Dimethylaminoazobenzene 225 120,77,105,148,42**  **Propylthiouracil 170 142,114,83**  **Benz(a)anthracene 228 229,226** **SW-846 Update V 8270D - 34 Revision 5 October 2012**  **Compound Primary Ion Secondary Ion(s)**  **Chrysene-d 12**  **(IS) 240 120,236**  **3,3'-Dichlorobenzidine 252 254,126 Chrysene**  **228 226,229 Malathion**  **173 125,127,93,158 Kepone**  **272 274,237,178,143,270 Fenthion**  **278 125,109,169,153 Parathion**  **109 97,291,139,155 Anilazine**  **239 241,143,178,89 Bis(2-ethylhexyl)phthalate 149 167,279**  **3,3'-Dimethylbenzidine 212 106,196,180 Carbophenothion**  **157 97,121,342,159,199 5-Nitroacenaphthene 199 152,169,141,115**  **Methapyrilene 97 50,191,71**  **Isodrin 193 66,195,263,265,147**  **Captan 79 149,77,119,117**  **Chlorfenvinphos 267 269,323,325,295**  **Crotoxyphos 127 105,193,166**  **Phosmet 160 77,93,317,76**  **EPN 157 169,185,141,323**  **Tetrachlorvinphos 329 109,331,79,333**  **Di-n-octyl phthalate 149 167,43**  **2-Aminoanthraquinone 223 167,195 Barban**  **222 51,87,224,257,153 Aramite**  **185 191,319,334,197,321 Benzo(b)fluoranthene 252 253,125**  **Nitrofen 283 285,202,139,253**  **Benzo(k)fluoranthene 252 253,125 Chlorobenzilate**  **251 139,253,111,141 Fensulfothion**  **293 97,308,125,292 Ethion**  **231 97,153,125,121 Diethylstilbestrol**  **268 145,107,239,121,159 Famphur**  **218 125,93,109,217 Tri-p-tolyl phosphate**  **c 368 367,107,165,198**  **Benzo(a)pyrene 252 253,125**  **Perylene-d 12**  **(IS) 264 260,265**  **7,12-Dimethylbenz(a)anthracene 256 241,239,120 5,5-Diphenylhydantoin 180 104,252,223,209**  **Captafol 79 77,80,107**  **Dinocap 69 41,39**  **Methoxychlor 227 228,152,114,274,212**  **2-Acetylaminofluorene 181 180,223,152 4,4'-Methylenebis(2-chloroaniline) 231 266,268,140,**  **195 3,3'-Dimethoxybenzidine 244 201,229**  **3-Methylcholanthrene 268 252,253,126,134,113 Phosalone**  **182 184,367,121,379 Azinphos-methyl**  **160 132,93,104,105 Leptophos**  **171 377,375,77,155,379 Mirex**  **272 237,274,270,239,235 Tris(2,3-dibromopropyl)phosphate 201 137,119,217,21**  **9,199 Dibenz(a,j)acridine**  **279 280,277,250 Mestranol**  **277 310,174,147,242 Coumaphos**  **362 226,210,364,97,109 SW-846 Update V 8270D - 35 Revision 5**  **October 2012 Compound**  **Primary Ion Secondary Ion(s) Indeno(1,2,3-cd)pyrene 276 138,277**  **Dibenz(a,h)anthracene 278 139,279 Benzo(g,h,i)perylene 276 138,277**  **1,2:4,5-Dibenzopyrene 302 151,150,300 Strychnine**  **334 334,335,333 Piperonyl sulfoxide**  **162 135,105,77 Hexachlorophene**  **196 198,209,211,406,408 Aldrin**  **66 263,220 Aroclor 1016**  **222 260,292 Aroclor 1221**  **190 224,260 Aroclor 1232**  **190 224,260 Aroclor 1242**  **222 256,292 Aroclor 1248**  **292 362,326 Aroclor 1254**  **292 362,326 Aroclor 1260**  **360 362,394 α-BHC**  **183 181,109 β-BHC**  **181 183,109 δ-BHC**  **183 181,109 γ-BHC (Lindane)**  **183 181,109 4,4'-DDD**  **235 237,165 4,4'-DDE**  **246 248,176 4,4'-DDT**  **235 237,165 Dieldrin**  **79 263,279 1,2-Diphenylhydrazine 77 105,182**  **Endosulfan I 195 339,341**  **Endosulfan II 337 339,341**  **Endosulfan sulfate 272 387,422**  **Endrin 263 82,81**  **Endrin aldehyde 67 345,250**  **Endrin ketone 317 67,319**  **2-Fluorobiphenyl (surr) 172 171 2-Fluorophenol (surr) 112 64**  **Heptachlor 100 272,274**  **Heptachlor epoxide 353 355,351**  **Nitrobenzene-d 5**  **(surr) 82 128,54 N-Nitrosodimethylamine 42 74,44**  **Phenol-d 6**  **(surr) 99 42,71**  **Terphenyl-d 14**  **(surr) 244 122,212**  **2,4,6-Tribromophenol (surr) 330 332,141 Toxaphene**  **159 231,233**

**IS = internal standard surr = surrogate** 

**a The data presented are representative of DB-5 type**  **analytical columns.**

**b Compounds cannot be separated for quantitation** 

**c Substitute for the non-specific mixture, tricresyl**  **phosphate SW-846 Update V 8270D - 36 Revision 5**  **October 2012 TABLE 2** 

**EXAMPLE LOWER LIMITS OF QUANTITATION FOR SEMIVOLATI LE ORGANICS** 

**Compound Lower Limits of Quantitation**  **a Ground water**  **(μg/L) Low Soil/Sediment**  **b**

**(μg/kg) Acenaphthene**  **10 660 Acenaphthylene**  **10 660 Acetophenone**  **10 ND 2-Acetylaminofluorene 20 ND**  **1-Acetyl-2-thiourea 1000 ND 2-Aminoanthraquinone 20 ND**  **Aminoazobenzene 10 ND**  **4-Aminobiphenyl 20 ND**  **Anilazine 100 ND**  **o-Anisidine 10 ND**  **Anthracene 10 660**  **Aramite 20 ND**  **Azinphos-methyl 100 ND**  **Barban 200 ND**  **Benz(a)anthracene 10 660**  **Benzo(b)fluoranthene 10 660 Benzo(k)fluoranthene 10 660**  **Benzoic acid 50 3300**  **Benzo(g,h,i)perylene 10 660 Benzo(a)pyrene**  **10 660 p-Benzoquinone**  **10 ND Benzyl alcohol**  **20 1300 Bis(2-chloroethoxy)methane 10 660**  **Bis(2-chloroethyl) ether 10 660 Bis(2-chloro-1-methylethyl)ether 10 660**  **4-Bromophenyl phenyl ether 10 660 Bromoxynil**  **10 ND Butyl benzyl phthalate 10 660**  **Captafol 20 ND**  **Captan 50 ND**  **Carbaryl 10 ND**  **Carbofuran 10 ND**  **Carbophenothion 10 ND**  **Chlorfenvinphos 20 ND**  **4-Chloroaniline 20 1300**  **Chlorobenzilate 10 ND**  **5-Chloro-2-methylaniline 10 ND 4-Chloro-3-methylphenol 20 1300**  **3-(Chloromethyl)pyridine hydrochloride 100 ND 2-Chloronaphthalene 10 660**  **2-Chlorophenol 10 660**  **4-Chlorophenyl phenyl ether 10 660 Chrysene**  **10 660 Coumaphos**  **40 ND p-Cresidine**  **10 ND Crotoxyphos**  **20 ND 2-Cyclohexyl-4,6-dinitrophenol 100 ND** **SW-846 Update V 8270D - 37 Revision 5 October 2012**  **Compound Lower Limits of Quantitation**  **a Ground water**  **(μg/L) Low Soil/Sediment**  **b**

**(μg/kg) Demeton-O**  **10 ND Demeton-S**  **10 ND Diallate (cis or trans) 10 ND**  **Diallate (trans or cis) 10 ND 2,4-Diaminotoluene 20 ND**  **Dibenz(a,j)acridine 10 ND**  **Dibenz(a,h)anthracene 10 660 Dibenzofuran**  **10 660 Dibenzo(a,e)pyrene 10 ND**  **Di-n-butyl phthalate 10 ND Dichlone**  **NA ND 1,2-Dichlorobenzene 10 660**  **1,3-Dichlorobenzene 10 660 1,4-Dichlorobenzene 10 660**  **3,3'-Dichlorobenzidine 20 1300 2,4-Dichlorophenol**  **10 660 2,6-Dichlorophenol**  **10 ND Dichlorovos**  **10 ND Dicrotophos**  **10 ND Diethyl phthalate**  **10 660 Diethylstilbestrol**  **20 ND Diethyl sulfate**  **100 ND Dimethoate**  **20 ND 3,3'-Dimethoxybenzidine 100 ND**  **Dimethylaminoazobenzene 10 ND 7,12-Dimethylbenz(a)anthracene 10 ND**  **3,3'-Dimethylbenzidine 10 ND 2,4-Dimethylphenol**  **10 660 Dimethyl phthalate**  **10 660 1,2-Dinitrobenzene**  **40 ND 1,3-Dinitrobenzene**  **20 ND 1,4-Dinitrobenzene**  **40 ND 4,6-Dinitro-2-methylphenol 50 3300**  **2,4-Dinitrophenol 50 3300**  **2,4-Dinitrotoluene 10 660**  **2,6-Dinitrotoluene 10 660**  **Dinocap 100 ND**  **Dinoseb 20 ND**  **5,5-Diphenylhydantoin 20 ND Di-n-octyl phthalate**  **10 660 Disulfoton**  **10 ND EPN**  **10 ND Ethion**  **10 ND Ethyl carbamate**  **50 ND Bis(2-ethylhexyl)phthalate 10 660**  **Ethyl methanesulfonate 20 ND Famphur**  **20 ND Fensulfothion**  **40 ND Fenthion**  **10 ND Fluchloralin**  **20 ND Fluoranthene**  **10 660 SW-846 Update V 8270D - 38 Revision 5**  **October 2012 Compound**  **Lower Limits of Quantitation a**  **Ground water (μg/L)**  **Low Soil/Sediment b** 

**(μg/kg) Fluorene**  **10 660 Hexachlorobenzene 10 660**  **Hexachlorobutadiene 10 660 Hexachlorocyclopentadiene 10 660**  **Hexachloroethane 10 660**  **Hexachlorophene 50 ND**  **Hexachloropropene 10 ND Hexamethylphosphoramide 20 ND**  **Indeno(1,2,3-cd)pyrene 10 660 Isodrin**  **20 ND Isophorone**  **10 660 Isosafrole**  **10 ND Kepone**  **20 ND Leptophos**  **10 ND Malathion**  **50 ND Mestranol**  **20 ND Methapyrilene**  **100 ND Methoxychlor**  **10 ND 3-Methylcholanthrene 10 ND**  **Methyl methanesulfonate 10 ND 2-Methylnaphthalene 10 660**  **Methyl parathion 10 ND**  **2-Methylphenol 10 660**  **3-Methylphenol 10 ND**  **4-Methylphenol 10 660**  **Mevinphos 10 ND**  **Mexacarbate 20 ND**  **Mirex 10 ND**  **Monocrotophos 40 ND**  **Naled 20 ND**  **Naphthalene 10 660**  **1,4-Naphthoquinone 10 ND 1-Naphthylamine**  **10 ND 2-Naphthylamine**  **10 ND Nicotine**  **20 ND 5-Nitroacenaphthene 10 ND**  **2-Nitroaniline 50 3300**  **3-Nitroaniline 50 3300**  **4-Nitroaniline 20 ND**  **5-Nitro-o-anisidine 10 ND**  **Nitrobenzene 10 660**  **4-Nitrobiphenyl 10 ND**  **Nitrofen 20 ND**  **2-Nitrophenol 10 660**  **4-Nitrophenol 50 3300**  **5-Nitro-o-toluidine 10 ND**  **4-Nitroquinoline-1-oxide 40 ND N-Nitrosodi-n-butylamine 10 ND**  **N-Nitrosodiethylamine 20 ND N-Nitrosodiphenylamine 10 660**  **N-Nitroso-di-n-propylamine 10 660 SW-846 Update V 8270D - 39 Revision 5**  **October 2012 Compound**  **Lower Limits of Quantitation a**  **Ground water (μg/L)**  **Low Soil/Sediment b** 

**(μg/kg) N-Nitrosopiperidine**  **20 ND N-Nitrosopyrrolidine 40 ND**  **Octamethyl pyrophosphoramide 200 ND 4,4'-Oxydianiline**  **20 ND Parathion**  **10 ND Pentachlorobenzene 10 ND**  **Pentachloronitrobenzene 20 ND Pentachlorophenol**  **50 3300 Phenacetin**  **20 ND Phenanthrene**  **10 660 Phenobarbital**  **10 ND Phenol**  **10 660 1,4-Phenylenediamine 10 ND**  **Phorate 10 ND**  **Phosalone 100 ND**  **Phosmet 40 ND**  **Phosphamidon 100 ND**  **Phthalic anhydride 100 ND**  **2-Picoline ND ND**  **Piperonyl sulfoxide 100 ND Pronamide**  **10 ND Propylthiouracil**  **100 ND Pyrene**  **10 660 Resorcinol**  **100 ND Safrole**  **10 ND Strychnine**  **40 ND Sulfallate**  **10 ND Terbufos**  **20 ND 1,2,4,5-Tetrachlorobenzene 10 ND**  **2,3,4,6-Tetrachlorophenol 10 ND Tetrachlorvinphos**  **20 ND Tetraethyl pyrophosphate 40 ND**  **Thionazine 20 ND**  **Thiophenol (Benzenethiol) 20 ND o-Toluidine**  **10 ND 1,2,4-Trichlorobenzene 10 660**  **2,4,5-Trichlorophenol 10 660 2,4,6-Trichlorophenol 10 660**  **Trifluralin 10 ND**  **2,4,5-Trimethylaniline 10 ND Trimethyl phosphate 10 ND**  **1,3,5-Trinitrobenzene 10 ND Tris(2,3-dibromopropyl)phosphate 200 ND**  **Tri-p-tolyl phosphate(h) 10 ND SW-846 Update V 8270D - 40 Revision 5**  **October 2012 a**  **Sample LLOQs are highly matrix-dependent and those listed here are provided for guidance**  **and may not always be achievable.**

**b LLOQs listed for soil/sediment are based on wet wei**  **ght. When data are reported on a dry weight basis, the lower limits will be higher based**  **on the % dry weight of each sample. These lower limits are based on a 30-g sample and gel per**  **meation chromatography cleanup.**

**ND = Not Determined**

**NA = Not Applicable**

**Other Matrices Factor**  **c**

**High-concentration soil and sludges by ultrasonic e xtraction 7.5**  **Non-water miscible waste 75**

**c LLOQ=(LLOQ for low soil/sediment given above in Ta**  **ble 2) x (Factor) SW-846 Update V 8270D - 41 Revision 5**  **October 2012 TABLE 3** 

**DFTPP KEY IONS AND ION ABUNDANCE CRITERIA a,b** 

**Mass Ion Abundance Criteria**

**51 10-80% of Base Peak**

**68 < 2% of mass 69**

**70 < 2% of mass 69**

**127 10-80% of Base Peak**

**197 < 2% of mass 198 198 Base peak, or > 50% of Mass 442** 

**199 5-9% of mass 198**

**275 10-60% of Base Peak**

**365 > 1% of mass 198 441 present but < 24% of mass 442** 
**442 Base Peak, or > 50% of mass 198**

**443 15-24% of mass 442**

**a The majority of the data are taken from Reference**  **13 (Method 525.2).**

**b The criteria in this table are intended to be used**  **as default criteria for quadrupole instrumentation if optimized manufacturer's operati**  **ng conditions are not available. Alternate tuning criteria may be employed (e.g., CL**  **P or Method 625), provided that method performance is not adversely affected. See**  **Sec. 11.3.1. SW-846 Update V 8270D - 42 Revision 5**  **October 2012 TABLE 4** 

**RECOMMENDED MINIMUM RESPONSE FACTOR CRITERIA FOR IN ITIAL AND**  **CONTINUING CALIBRATION VERIFICATION USING THE SUGGE STED IONS**  **FROM TABLE 1**

**Semivolatile Compounds Minimum Response**  **Factor (RF) Benzaldehyde**  **0.010 Phenol**  **0.800 Bis(2-chloroethyl)ether 0.700**  **2-Chlorophenol 0.800**  **2-Methylphenol 0.700**  **2,2'-Oxybis-(1-chloropropane) 0.010 Acetophenone**  **0.010 4-Methylphenol**  **0.600 N-Nitroso-di-n-propylamine 0.500**  **Hexachloroethane 0.300 Nitrobenzene**  **0.200 Isophorone**  **0.400 2-Nitrophenol**  **0.100 2,4-Dimethylphenol 0.200**  **Bis(2-chloroethoxy)methane 0.300 2,4-Dichlorophenol 0.200**  **Naphthalene 0.700**  **4-Chloroaniline 0.010**  **Hexachlorobutadiene 0.010 Caprolactam**  **0.010 4-Chloro-3-methylphenol 0.200**  **2-Methylnaphthalene 0.400 Hexachlorocyclopentadiene 0.050**  **2,4,6-Trichlorophenol 0.200 2,4,5-Trichlorophenol 0.200**  **1,1'-Biphenyl 0.010**  **2-Chloronaphthalene 0.800 2-Nitroaniline**  **0.010 Dimethyl phthalate 0.010**  **2,6-Dinitrotoluene 0.200**  **Acenaphthylene 0.900**  **3-Nitroaniline 0.010**  **Acenaphthene 0.900**  **2,4-Dinitrophenol 0.010**  **4-Nitrophenol 0.010**  **Dibenzofuran 0.800**  **2,4-Dinitrotoluene 0.200**  **Diethyl phthalate 0.010**  **1,2,4,5-Tetrachlorobenzene 0.010 4-Chlorophenyl-phenyl ether 0.400**  **Fluorene 0.900**  **4-Nitroaniline 0.010**  **4,6-Dinitro-2-methylphenol 0.010 4-Bromophenyl-phenyl ether 0.100**  **N-Nitrosodiphenylamine 0.010 Hexachlorobenzene 0.100** **SW-846 Update V 8270D - 43 Revision 5 October 2012**  **Semivolatile Compounds Minimum Response**  **Factor (RF) Atrazine**  **0.010 Pentachlorophenol 0.050**  **Phenanthrene 0.700**  **Anthracene 0.700**  **Carbazole 0.010**  **Di-n-butyl phthalate 0.010 Fluoranthene**  **0.600 Pyrene**  **0.600 Butyl benzyl phthalate 0.010**  **3,3'-Dichlorobenzidine 0.010 Benzo(a)anthracene 0.800**  **Chrysene 0.700**  **Bis-(2-ethylhexyl)phthalate 0.010 Di-n-octyl phthalate 0.010**  **Benzo(b)fluoranthene 0.700 Benzo(k)fluoranthene 0.700**  **Benzo(a)pyrene 0.700**  **Indeno(1,2,3-cd)pyrene 0.500 Dibenz(a,h)anthracene 0.400**  **Benzo(g,h,i)perylene 0.500 2,3,4,6-Tetrachlorophenol 0.010** **SW-846 Update V 8270D - 44 Revision 5 October 2012**  **TABLE 5**

**SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES**  **ASSIGNED FOR QUANTITATION**

**1,4-Dichlorobenzene-d 4**  **Naphthalene-d 8**  **Acenaphthene-d 10**  **Aniline Acetophenone Acenaphthene Benzyl alcohol Benzoic acid Acenaphthylene**  **Bis(2-chloroethyl)ether Bis(2-chloroethoxy)methane 1-Chloronaphthalene**  **Bis(2-chloro-1-methylethyl) ether**  **4-Chloroaniline 2-Chloronaphthalene**

**2-Chlorophenol 4-Chloro-3-methylphenol 4-Chlorophen yl phenyl ether**  **1,3-Dichlorobenzene 2,4-Dichlorophenol Dibenzofuran 1,4-Dichlorobenzene 2,6-Dichlorophenol Diethyl phth**  **alate 1,2-Dichlorobenzene α,α-Dimethylphenethylamine Dime**  **thyl phthalate Ethyl methanesulfonate 2,4-Dimethylphenol 2,4-Dinit**  **rophenol 2-Fluorophenol (surr) Hexachlorobutadiene 2,4-Dinit**  **rotoluene Hexachloroethane Isophorone 2,6-Dinitrotoluene**  **Methyl methanesulfonate 2-Methylnaphthalene Fluoren e**  **2-Methylphenol Naphthalene 2-Fluorobiphenyl (surr) 4-Methylphenol Nitrobenzene Hexachlorocyclopentadie**  **ne N-Nitrosodimethylamine Nitrobenzene-d**  **8 (surr) 1-Naphthylamine**  **N-Nitroso-di-n-propylamine 2-Nitrophenol 2-Naphthyl amine**  **Phenol N-Nitrosodi-n-butylamine 2-Nitroaniline**

**Phenol-d 6**  **(surr) N-Nitrosopiperidine 3-Nitroaniline**
**2-Picoline 1,2,4-Trichlorobenzene 4-Nitroaniline 4-Nitrophenol** 

**Pentachlorobenzene**
**1,2,4,5-Tetrachlorobenzene 2,3,4,6-Tetrachlorophenol**  **2,4,6-Tribromophenol (surr) 2,4,6-Trichlorophenol**  **2,4,5-Trichlorophenol**

**(surr) = surrogate SW-846 Update V 8270D - 45 Revision 5**  **October 2012 TABLE 5**  **(continued)**

**Phenanthrene-d 10**  **Chrysene-d 12**  **Perylene-d 12**  **4-Aminobiphenyl Benzidine Benzo(b)fluoranthene Anthracene Benzo(a)anthracene Benzo(k)fluoranthene**  **4-Bromophenyl phenyl ether Bis(2-ethylhexyl)phthalate Benzo(g,h,i)perylene**  **Di-n-butyl phthalate Butyl benzyl phthalate Benzo(a )pyrene**  **4,6-Dinitro-2-methylphenol Chrysene Dibenz(a,j)acri dine**  **Diphenylamine 3,3'-Dichlorobenzidine Dibenz(a,h)ant hracene**  **Fluoranthene p-Dimethyl aminoazobenzene 7,12-Dimeth ylbenz(a)anthracene**  **Hexachlorobenzene Pyrene Di-n-octyl phthalate N-Nitrosodiphenylamine Terphenyl-d**  **14 (surr) Indeno(1,2,3-cd)pyrene**  **Pentachlorophenol 3-Methylcholanthrene**

**Pentachloronitrobenzene**

**Phenacetin**

**Phenanthrene**

**Pronamide**

**(surr) = surrogate SW-846 Update V 8270D - 46 Revision 5**  **October 2012 TABLE 6** 

**EXAMPLE SINGLE LABORATORY PERFORMANCE DATA a** 

**Compound Test conc.**  **(μg/L)** x **of 5**

**replicates (μg/L)**  **% Recovery**

**of Avg.**

**Acenaphthene 50 46.7 93.4**  **Acenaphthylene 50 46.1 92.2 Aniline**  **50 8.3 16.7 Anthracene**  **50 48.4 96.8 Benzoic acid**  **50 43.7 87.4 Benzo(a)anthracene 50 49.6 99.2**  **Benzo(b)fluoranthene 50 49.8 99.6 Benzo(k)fluoranthene 50 50.6 101**  **Benzo(a)pyrene 50 47.7 95.5 Benzo(g,h,i)perylene 50 52.6 105**  **Benzyl alcohol 50 44.4 88.8**  **Bis(2-chloroethyl)ether 50 44.2 88.4 Bis(2-chloroethoxy)methane 50 46.6 93.1**  **Bis(2-chloro-1-methylethyl)ether 50 43.4 86.8 Bis(2-ethylhexyl)phthalate 50 50.2 100**  **4-Bromophenyl phenyl ether 50 48.6 97.2 Butyl benzyl phthalate 50 49.6 99.3**  **Carbazole 50 52.1 104**  **2-Chloroaniline 50 38.9 77.7 4-Chloro-3-methylphenol 50 47.3 94.6**  **2-Chloronaphthalene 50 45.3 90.8 2-Chlorophenol 50 43.1 86.2**  **4-Chlorophenyl phenyl ether 50 47.3 94.6 Chrysene**  **50 50.3 101 Dibenzofuran**  **50 47.4 94.7 Dibenz(a,h)anthracene 50 51.6 103**  **Di-n-butyl phthalate 50 50.5 101 1,2-Dichlorobenzene 50 35.8 71.6**  **1,3-Dichlorobenzene 50 33.3 66.7 1,4-Dichlorobenzene 50 34.4 68.7**  **3,3'-Dichlorobenzidine 50 32.0 64.0 2,4-Dichlorophenol 50 47.4 94.8**  **Diethyl phthalate 50 50.0 99.9 Dimethyl phthalate 50 48.5 97.0**  **2,4-Dimethylphenol 50 31.2 62.3 4,6-Dinitro-2-methylphenol 50 57.6 115**  **2,4-Dinitrophenol 50 58.7 117 2,4-Dinitrotoluene 50 51.3 103**  **2,6-Dinitrotoluene 50 50.2 100 Di-n-octyl phthalate 50 51.1 102**  **Fluoranthene 50 51.0 102** **SW-846 Update V 8270D - 47 Revision 5 October 2012**  **Compound Test conc.**  **(μg/L)** x **of 5**

**replicates (μg/L)**  **% Recovery**

**of Avg.**

**Fluorene 50 48.5 97.0**  **Hexachlorobenzene 50 49.0 97.9 Hexachlorobutadiene 50 34.7 69.5**  **Hexachlorocyclopentadiene 50 1.9 3.8 Hexachloroethane 50 29.9 58.8**  **Indeno(1,2,3-cd)pyrene 50 51.7 103 Isophorone**  **50 47.1 94.3 2-Methylnaphthalene 50 44.7 89.4**  **2-Methylphenol 50 41.7 83.4 4-Methylphenol 50 42.6 85.2**  **Naphthalene 50 43.4 86.8**  **2-Nitroaniline 50 48.4 96.7**  **3-Nitroaniline 50 46.8 93.6**  **4-Nitroaniline 50 56.1 112**  **Nitrobenzene 50 47.1 94.1**  **2-Nitrophenol 50 47.3 94.6**  **4-Nitrophenol 50 55.4 111**  **N-Nitrosodiphenylamine 50 46.7 93.4 N-Nitroso-di-propylamine 50 44.6 89.3**  **Pentachlorophenol 50 56.9 114 Phenanthrene**  **50 49.7 99.4 Phenol**  **50 40.9 81.8 Pyrene**  **50 49.2 98.4 1,2,4-Trichlorobenzene 50 39.1 78.2**  **2,4,5-Trichlorophenol 50 47.7 95.4 2,4,6-Trichlorophenol 50 49.2 98.4** 

x **=Average recovery for five initial demonstrations o f capability measurements, in μg/L** 

**a Extraction using acidic pH only with a modified co**  **ntinuous liquid-liquid extractor with hydrophobic membrane according to Method 3520. The**  **se values are for guidance only. Appropriate derivation of acceptance criteria for s**  **imilar extraction conditions may result in much different recovery ranges. See Method 8000 for inf**  **ormation on developing and updating acceptance criteria for method performance.** **SW-846 Update V 8270D - 48 Revision 5 October 2012**  **TABLE 7**

**EXTRACTION EFFICIENCY AND AQUEOUS STABILITY RESULTS**

**Compound Percent Recovery, Day 0 Percent Recovery, Day 7** 

**Mean RSD Mean RSD**

**3-Amino-9-ethylcarbazole 80 8 73 3**

**4-Chloro-1,2-phenylenediamine 91 1 108 4**

**4-Chloro-1,3-phenylenediamine 84 3 70 3**

**1,2-Dibromo-3-chloropropane 97 2 98 5**

**Dinoseb 99 3 97 6** 

**Parathion 100 2 103 4**

**4,4'-Methylenebis(N,N dimethylaniline) 108 4 90 4** 

**5-Nitro-o-toluidine 99 10 93 4**

**2-Picoline 80 4 83 4**

**Tetraethyl dithiopyrophosphate 92 7 70 1**

**Data taken from Reference 6. SW-846 Update V 8270D - 49 Revision 5**  **October 2012 TABLE 8** 

**MEAN PERCENT RECOVERIES AND PERCENT RSD VALUES FOR SEMIVOLATILE**  **ORGANIC FROM SPIKED CLAY SOIL AND TOPSOIL BY AUTOMA TED SOXHLET**  **(SOXTEC) EXTRACTION (METHOD 3541) WITH HEXANE-ACETO NE (1:1)**  **a**

**Compound Clay Soil Top Soil** 

**Mean Recovery**  **RSD Mean**  **Recovery RSD** 

**1,3-Dichlorobenzene 0 -- 0 -- 1,2-Dichlorobenzene 0 -- 0 --**  **Nitrobenzene 0 -- 0 --**  **Benzal chloride 0 -- 0 -- Benzotrichloride 0 -- 0 --**  **4-Chloro-2-nitrotoluene 0 -- 0 -- Hexachlorocyclopentadiene 4.1 15 7.8 23**  **2,4-Dichloronitrobenzene 35.2 7.6 21.2 15 3,4-Dichloronitrobenzene 34.9 15 20.4 11**  **Pentachlorobenzene 13.7 7.3 14.8 13 2,3,4,5-Tetrachloronitrobenzene 55.9 6.7 50.4 6.0**  **Benefin 62.6 4.8 62.7 2.9**  **alpha-BHC 58.2 7.3 54.8 4.8**  **Hexachlorobenzene 26.9 13 25.1 5.7 delta-BHC**  **95.8 4.6 99.2 1.3 Heptachlor**  **46.9 9.2 49.1 6.3 Aldrin**  **97.7 12 102 7.4 Isopropalin**  **102 4.3 105 2.3 Heptachlor epoxide 90.4 4.4 93.6 2.4**  **trans-Chlordane 90.1 4.5 95.0 2.3 Endosulfan I**  **96.3 4.4 101 2.2 Dieldrin**  **129 4.7 104 1.9 2,5-Dichlorophenyl-4-nitrophenyl ether 110 4.1 112**  **2.1 Endrin**  **102 4.5 106 3.7 Endosulfan II**  **104 4.1 105 0.4 p,p'-DDT**  **134 2.1 111 2.0 2,3,6-Trichlorophenyl-4'-nitrophenyl ether 110 4.8**  **110 2.8 2,3,4-Trichlorophenyl-4'-nitrophenyl ether 112 4.4**  **112 3.3 Mirex**  **104 5.3 108 2.2**

**a The operating conditions for the Soxtec apparatus**  **were as follows: immersion time 45 min; the sample size was 10 g; the spiking concentration**  **was 500 ng/g, except for the surrogate compounds at 1000 ng/g, 2,5-Dichlorophenyl-4-nitrop**  **henyl ether, 2,3,6-Trichlorophenyl-4- nitrophenyl ether, and 2,3,4-Trichlorophenyl-4-nitr**  **ophenyl ether at 1500 ng/g, Nitrobenzene at 2000 ng/g, and 1,3-Dichlorobenzene and 1,2-Dichloro**  **benzene at 5000 ng/g. SW-846 Update V 8270D - 50 Revision 5**  **October 2012 TABLE 9** 

**SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR T HE EXTRACTION** 

**OF SEMIVOLATILE ORGANICS FROM SPIKED CLAY BY AUTOMATED SOXHLET (SOXTEC) (METHOD 3541)**  **a**

**Compound Mean Recovery RSD** 

**Phenol 47.8 5.6**  **Bis(2-chloroethyl) ether 25.4 13 2-Chlorophenol**  **42.7 4.3 Benzyl alcohol**  **55.9 7.2 2-Methylphenol**  **17.6 6.6 Bis(2-chloro-1-methylethyl)ether 15.0 15**  **4-Methylphenol 23.4 6.7**  **N-Nitroso-di-n-propylamine 41.4 6.2 Nitrobenzene**  **28.2 7.7 Isophorone**  **56.1 4.2 2-Nitrophenol**  **36.0 6.5 2,4-Dimethylphenol 50.1 5.7**  **Benzoic acid 40.6 7.7**  **Bis(2-chloroethoxy)methane 44.1 3.0 2,4-Dichlorophenol 55.6 4.6**  **1,2,4-Trichlorobenzene 18.1 31 Naphthalene**  **26.2 15 4-Chloroaniline**  **55.7 12 4-Chloro-3-methylphenol 65.1 5.1**  **2-Methylnaphthalene 47.0 8.6 Hexachlorocyclopentadiene 19.3 19**  **2,4,6-Trichlorophenol 70.2 6.3 2,4,5-Trichlorophenol 26.8 2.9**  **2-Chloronaphthalene 61.2 6.0 2-Nitroaniline**  **73.8 6.0 Dimethyl phthalate**  **74.6 5.2 Acenaphthylene**  **71.6 5.7 3-Nitroaniline**  **77.6 5.3 Acenaphthene**  **79.2 4.0 2,4-Dinitrophenol**  **91.9 8.9 4-Nitrophenol**  **62.9 16 Dibenzofuran**  **82.1 5.9 2,4-Dinotrotoluene**  **84.2 5.4 2,6-Dinitrotoluene**  **68.3 5.8 Diethyl phthalate**  **74.9 5.4 4-Chlorophenyl-phenyl ether 67.2 3.2** 
**Fluorene 82.1 3.4**  **4-Nitroaniline 79.0 7.9**  **4,6-Dinitro-2-methylphenol 63.4 6.8 N-Nitrosodiphenylamine 77.0 3.4**  **4-Bromophenyl-phenyl ether 62.4 3.0 SW-846 Update V 8270D - 51 Revision 5**  **October 2012 Compound**  **Mean Recovery RSD**

**Hexachlorobenzene 72.6 3.7 Pentachlorophenol**  **62.7 6.1 Phenanthrene**  **83.9 5.4 Anthracene**  **96.3 3.9 Di-n-butyl phthalate 78.3 40**  **Fluoranthene 87.7 6.9**  **Pyrene 102 0.8**  **Butyl benzyl phthalate 66.3 5.2 3,3'-Dichlorobenzidine 25.2 11**  **Benzo(a)anthracene 73.4 3.8 Bis(2-ethylhexyl)phthalate 77.2 4.8**  **Chrysene 76.2 4.4**  **Di-n-octyl phthalate 83.1 4.8 Benzo(b)fluoranthene 82.7 5.0**  **Benzo(k)fluoranthene 71.7 4.1 Benzo(a)pyrene**  **71.7 4.1 Indeno(1,2,3-cd)pyrene 72.2 4.3**  **Dibenz(a,h)anthracene 66.7 6.3 Benzo(g,h,i)perylene 63.9 8.0**  **1,2-Dichlorobenzene 0 -- 1,3-Dichlorobenzene 0 --**  **1,4-Dichlorobenzene 0 -- Hexachloroethane**  **0 -- Hexachlorobutadiene 0 --** 

**a Number of determinations was three. The operating**  **conditions for the Soxtec apparatus were as follows: immersion time 45 min; the sample size**  **was 10 g clay soil; the spike concentration was 6 mg/kg per compound. The sample was allowed t**  **o equilibrate 1 hour after spiking.**

**Data taken from Reference 7. SW-846 Update V 8270D - 52 Revision 5**  **October 2012 TABLE 10** 

**PRECISION AND BIAS VALUES FOR METHOD 3542 a** 

**Compound Mean Recovery Standard Deviation % RSD**
**2-Fluorophenol 74.6 28.6 38.3**

**Phenol-d 5**  **77.8 27.7 35.6**

**Nitrobenzene-d 5**  **65.6 32.5 49.6 2-Fluorobiphenyl 75.9 30.3 39.9**  **2,4,6-Tribromophenol 67.0 34.0 50.7 Terphenyl-d**  **14 78.6 32.4 41.3** 

**a The surrogate values shown in Table 10 represent me**  **an recoveries for surrogates in all Method 0010 matrices in a field dynamic spiking stu**  **dy. SW-846 Update V 8270D - 53 Revision 5**  **October 2012 TABLE 11** 

**PRESSURIZED FLUID EXTRACTION (METHOD 3545) RECOVERY VALUES**  **AS PERCENT OF SOXTEC TM** 

**Compound Clay Loam Sand**  **Mean Rec.**  **Low Mid High Low Mid High Low Mid High**

**Phenol 93.3 78.7 135.9 73.9 82.8 124.6 108.8 130.6 89.7 102.0**  **Bis(2-chloroethyl)ether 102.1 85.1 109.1 96.0 88.0 103.6 122.3 119.9 90.8 101.9**  **2-Chlorophenol 100.8 82.6 115.0 93.8 88.9 111.1 115 .0 115.3 91.9 101.6** 
**1,3-Dichlorobenzene 127.7 129.7 110.0 *364.2 129.9** **119.0 *241.3 *163.7 107.1 120.6**
**1,4-Dichlorobenzene 127.9 127.0 110.5 *365.9 127.8** **116.4 *309.6 *164.1 105.8 119.2**
**1,2-Dichlorobenzene 116.8 115.8 101.3 *159.2 113.4** **105.5 *189.3 134.0 100.4 112.5** **2-Methylphenol 98.9 82.1 119.7 87.6 89.4 111.0 133. 2 128.0 92.1 104.7**  **Bis(2-chloro-1-methylethyl) ether**  **109.4 71.5 108.0 81.8 81.0 88.6 118.1 148.3 94.8 10 0.2** 

**o-Toluidine 100.0 89.7 117.2 100.0 *152.5 120.3 100** **.0 *199.5 102.7 110.3** **N-Nitroso-di-n-propylamine 103.0 79.1 107.7 83.9 88 .1 96.2 109.9 123.3 91.4 98.1** 

**Hexachloroethane 97.1 125.1 111.0 *245.4 117.1 128.** **1 *566.7 147.9 103.7 118.6**

**Nitrobenzene 104.8 82.4 106.6 86.8 84.6 101.7 119.7 122.1 93.3 100.2**  **Isophorone 100.0 86.4 98.2 87.1 87.5 109.7 135.5 11 8.4 92.7 101.7**  **2,4-Dimethylphenol 100.0 104.5 140.0 100.0 114.4 12** **3.1 100.0 *180.6 96.3 109.8** **2-Nitrophenol 80.7 80.5 107.9 91.4 86.7 103.2 122.1 107.1 87.0 96.3**  **Bis(chloroethoxy)methane 94.4 80.6 94.7 86.5 84.4 9 9.6 130.6 110.7 93.2 97.2**  **2,4-Dichlorophenol 88.9 87.8 111.4 85.9 87.6 103.5 123.3 107.0 92.1 98.6** 
**1,2,4-Trichlorobenzene 98.0 97.8 98.8 123.0 93.7 94 .5 137.0 99.4 95.3 104.2**  **Naphthalene 101.7 97.2 123.6 113.2 102.9 129.5 *174** **.5 114.0 89.8 106.1**

**4-Chloroaniline 100.0 *150.2 *162.4 100.0 125.5 *26** **3.6 100.0 *250.8 114.9 108.1**

**Hexachlorobutadiene 101.1 98.7 102.2 124.1 90.3 98. 0 134.9 96.1 96.8 104.7**  **4-Chloro-3-methylphenol 90.4 80.2 114.7 79.0 85.2 1 09.8 131.6 116.2 90.1 99.7**  **2-Methylnaphthalene 93.2 89.9 94.6 104.1 92.2 105.9 146.2 99.1 93.3 102.1**  **Hexachlorocyclopentadiene 100.0 100.0 0.0 100.0 100** **.0 6.8 100.0 100.0 *238.3 75.8** **2,4,6-Trichlorophenol 94.6 90.0 112.0 84.2 91.2 103 .6 101.6 95.9 89.8 95.9**  **2,4,5-Trichlorophenol 84.4 91.9 109.6 96.1 80.7 103 .6 108.9 83.9 87.9 94.1**  **2-Chloronaphthalene 100.0 91.3 93.6 97.6 93.4 98.3 106.8 93.0 92.0 96.2** 

**2-Nitroaniline 90.0 83.4 97.4 71.3 88.4 89.9 112.1 113.3 87.7 92.6** 
**2,6-Dinitrotoluene 83.1 90.6 91.6 86.4 90.6 90.3 10 4.3 84.7 90.9 90.3**  **Acenaphthylene 104.9 95.9 100.5 99.0 97.9 108.8 118 .5 97.8 92.0 101.7** 

**3-Nitroaniline *224.0 115.6 97.6 100.0 111.8 107.8** **0.0 111.7 99.0 92.9 Acenaphthene 102.1 92.6 97.6 97.2 96.9 104.4 114.2**  **92.0 89.0 98.4 4-Nitrophenol 0.0 93.2 121.5 18.1 87.1 116.6 69.1 9**  **0.5 84.5 75.6**
**2,4-Dinitrotoluene 73.9 91.9 100.2 84.7 93.8 98.9 1 00.9 84.3 87.3 90.7** 

**Dibenzofuran 89.5 91.7 109.3 98.5 92.2 111.4 113.8 92.7 90.4 98.8**  **4-Chlorophenyl phenyl ether 83.0 94.5 98.7 95.7 94. 3 94.2 111.4 87.7 90.3 94.4** 

**Fluorene 85.2 94.9 89.2 102.0 95.5 93.8 121.3 85.7 90.9 95.4** 

**4-Nitroaniline 77.8 114.8 94.5 129.6 103.6 95.4 *15** **4.1 89.3 87.5 99.1 N-Nitrosodiphenylamine 82.6 96.7 93.8 92.9 93.4 116**  **.4 97.5 110.9 86.7 96.8 4-Bromophenyl phenyl ether 85.6 92.9 92.8 91.1 107.**  **6 89.4 118.0 97.5 87.1 95.8**

**Hexachlorobenzene 95.4 91.7 92.3 95.4 93.6 83.7 106 .8 94.3 90.0 93.7** **SW-846 Update V 8270D - 54 Revision 5 October 2012**  **Compound Clay Loam Sand**  **Mean Rec.**  **Low Mid High Low Mid High Low Mid High Pentachlorophenol 68.2 85.9 107.7 53.2 89.8 88.1 96**  **.6 59.8 81.3 81.2**

**Phenanthrene 92.1 93.7 93.3 100.0 97.8 113.3 124.4 101.0 89.9 100.6** 

**Anthracene 101.6 95.0 93.5 92.5 101.8 118.4 123.0 9 4.5 90.6 101.2** 

**Carbazole 94.4 99.3 96.6 105.5 96.7 111.4 115.7 83. 2 88.9 99.1** 

**Fluoranthene 109.9 101.4 94.3 111.6 96.6 109.6 123. 2 85.4 92.7 102.7**  **Pyrene 106.5 105.8 107.6 116.7 90.7 127.5 103.4 95. 5 93.2 105.2** 
**3,3 '**  **-Dichlorobenzidine** **100.0 *492.3 131.4 100.0 *217.6 *167.6 100.0 *748.8** **100.0 116.5 Benzo(a)anthracene 98.1 107.0 98.4 119.3 98.6 104.0**  **105.0 93.4 89.3 101.5 Chrysene 100.0 108.5 100.2 116.8 93.0 117.0 106.7 9**  **3.6 90.2 102.9 Benzo(b)fluoranthene 106.6 109.9 75.6 121.7 100.7 9**  **3.9 106.9 81.9 93.6 99.0 Benzo(k)fluoranthene 102.4 105.2 88.4 125.5 99.4 95**  **.1 144.7 89.2 78.1 103.1 Benzo(a)pyrene 107.9 105.5 80.8 122.3 97.7 104.6 10**  **1.7 86.2 92.0 99.9 Indeno(1,2,3-cd)pyrene 95.1 105.7 93.8 126.0 105.2**  **90.4 133.6 82.6 91.9 102.7 Dibenz(a,h)anthracene 85.0 102.6 82.0 118.8 100.7 9**  **1.9 142.3 71.0 93.1 98.6 Benzo(g,h,i)perylene 98.0 0.0 81.2 0.0 33.6 78.6 12**  **8.7 83.0 94.2 66.4**

**Mean 95.1 94.3 101.0 95.5 96.5 104.1 113.0 100.9 92 .5** 

***Values greater than 150% were not used to determin e the averages, but the 0% values were used.** **SW-846 Update V 8270D - 55 Revision 5 October 2012**  **TABLE 12**

**SINGLE LABORATORY ACCURACY AND PRECISION FOR THE EX TRACTION OF PAHs**  **FROM A CERTIFIED REFERENCE SEDIMENT EC-1, USING MET HOD 3561**  **(SFE - SOLID TRAP)**

**Compound Certified Value**  **(mg/kg) SFE Value**  **a**

**(mg/kg) Percent of** 

**Certified Value SFE** 

**RSD**
**Naphthalene (27.9) b**  **41.3 ± 3.6 (148) 8.7 Acenaphthylene (0.8) 0.9 ± 0.1 (112) 11.1**  **Acenaphthene (0.2) 0.2 ± 0.01 (100) 0.05 Fluorene (15.3) 15.6 ± 1.8 (102) 11.5** 

**Phenanthrene 15.8 ± 1.2 16.1 ± 1.8 102 11.2 Anthracene (1.3) 1.1 ± 0.2 (88) 18.2** 

**Fluoranthene 23.2 ± 2.0 24.1 ± 2.1 104 8.7 Pyrene 16.7 ± 2.0 17.2 ± 1.9 103 11.0**  **Benz(a)anthracene 8.7 ± 0.8 8.8 ± 1.0 101 11.4 Chrysene (9.2) 7.9 ± 0.9 (86) 11.4**  **Benzo(b)fluoranthene 7.9 ± 0.9 8.5 ± 1.1 108 12.9 Benzo(k)fluoranthene 4.4 ± 0.5 4.1 ± 0.5 91 12.2**  **Benzo(a)pyrene 5.3 ± 0.7 5.1 ± 0.6 96 11.8 Indeno(1,2,3-cd)pyrene 5.7 ± 0.6 5.2 ± 0.6 91 11.5**  **Benzo(g,h,i)perylene 4.9 ± 0.7 4.3 ± 0.5 88 11.6 Dibenz(a,h)anthracene (1.3) 1.1 ± 0.2 (85) 18.2** 

**a RSDs for the SFE values are based on six replicate**  **extractions.**

**b Values in parentheses were obtained from, or compar**  **ed to, Soxhlet extraction results which were not certified.** 

**Data are taken from Reference 10. SW-846 Update V 8270D - 56 Revision 5**  **October 2012 TABLE 13** 

**SINGLE LABORATORY ACCURACY AND PRECISION FOR THE EX TRACTION OF PAHs**  **FROM A CERTIFIED REFERENCE SEDIMENT HS-3, USING MET HOD 3561**  **(SFE - SOLID TRAP)**

**Compound Certified Value**  **(mg/kg) SFE Value**  **a**

**(mg/kg) Percent of** 

**Certified Value SFE** 

**RSD**
**Naphthalene 9.0 ± 0.7 7.4 ± 0.6 82 8.1 Acenaphthylene 0.3 ± 0.1 0.4 ± 0.1 133 25.0**  **Acenaphthene 4.5 ± 1.5 3.3 ± 0.3 73 9.0**

**Fluorene 13.6 ± 3.1 10.4 ± 1.3 77 12.5**

**Phenanthrene 85.0 ± 20.0 86.2 ± 9.5 101 11.0**

**Anthracene 13.4 ± 0.5 12.1 ± 1.5 90 12.4**

**Fluoranthene 60.0 ± 9.0 54.0 ± 6.1 90 11.3 Pyrene 39.0 ± 9.0 32.7 ± 3.7 84 11.3**  **Benz(a)anthracene 14.6 ± 2.0 12.1 ± 1.3 83 10.7 Chrysene 14.1 ± 2.0 12.0 ± 1.3 85 10.8**  **Benzo(b)fluoranthene 7.7 ± 1.2 8.4 ± 0.9 109 10.7 Benzo(k)fluoranthene 2.8 ± 2.0 3.2 ± 0.5 114 15.6**  **Benzo(a)pyrene 7.4 ± 3.6 6.6 ± 0.8 89 12.1 Indeno(1,2,3-cd)pyrene 5.0 ± 2.0 4.5 ± 0.6 90 13.3**  **Benzo(g,h,i)perylene 5.4 ± 1.3 4.4 ± 0.6 82 13.6 Dibenz(a,h)anthracene 1.3 ± 0.5 1.1 ± 0.3 85 27.3** 

**a RSDs for the SFE values are based on three replicat**  **e extractions.**

**Data are taken from Reference 10. SW-846 Update V 8270D - 57 Revision 5**  **October 2012 TABLE 14** 

**SINGLE LABORATORY ACCURACY AND PRECISION FOR THE EX TRACTION OF PAHs**  **FROM A CERTIFIED REFERENCE SOIL SRS103-100, USING M ETHOD 3561**  **(SFE – LIQUID TRAP)**

**Compound Certified Value**  **(mg/kg) SFE Value**  **a**

**(mg/kg) Percent of** 

**Certified Value SFE** 

**RSD**
**Naphthalene 32.4 ± 8.2 29.55 91 10.5 2-Methylnaphthalene 62.1 ± 11.5 76.13 122 2.0**  **Acenaphthene 632 ± 105 577.28 91 2.9**

**Dibenzofuran 307 ± 49 302.25 98 4.1**

**Fluorene 492 ± 78 427.15 87 3.0**

**Phenanthrene 1618 ± 340 1278.03 79 3.4**

**Anthracene 422 ± 49 400.80 95 2.6**

**Fluoranthene 1280 ± 220 1019.13 80 4.5 Pyrene 1033 ± 285 911.82 88 3.1**  **Benz(a)anthracene 252 ± 8 225.50 89 4.8 Chrysene 297 ± 26 283.00 95 3.8**  **Benzo(a)pyrene 97.2 ± 17.1 58.28 60 6.5**

**Benzo(b)fluoranthene + Benzo(k)fluoranthene**  **153 ± 22 130.88 86 10.7**

**a Relative standard deviationsRSDs for the SFE values**  **are based on four replicate extractions.**

**Data are taken from Reference 11. SW-846 Update V 8270D - 58 Revision 5**  **October 2012 TABLE 15** 

**SINGLE LABORATORY RECOVERY DATA FOR SPE (METHOD 353 5) OF**  **BASE/NEUTRAL/ACID EXTRACTABLES FROM SPIKED TCLP BUF FERS**  **LOW SPIKE LEVEL**

**Analyte Spike**  **Level (μg/L)**  **Buffer 1 (pH=2.886) Buffer 2 (pH=4.937)**

**Recovery (%) RSD Recovery (%) RSD**

**1,4-Dichlorobenzene 3,750 63 10 63 9**
**Hexachloroethane 1,500 55 6 77 4**
**Nitrobenzene 1,000 82 10 100 5**

**Hexachlorobutadiene 250 65 3 56 4**
**2,4-Dinitrotoluene 65 89 4 101 5**

**Hexachlorobenzene 65 98 5 95 6**
**o-Cresol 100,000 83 10 85 5**
**m-Cresol* 100,000 86 8 85 3** **p-Cresol* 100,000 * * * *** **2,4,6-Trichlorophenol 1,000 84 12 95 12 2,4,5-Trichlorophenol 200,000 83 11 88 3**  **Pentachlorophenol 50,000 82 9 78 9**

**Results from seven replicate spiked buffer samples.**

***In this study, m-cresol and p-cresol co-eluted and were quantified as a mixture of both isomers.** 

**Data from Reference 12. SW-846 Update V 8270D - 59 Revision 5**  **October 2012 TABLE 16** 

**SINGLE LABORATORY RECOVERY DATA FOR SPE (METHOD 353 5) OF**  **BASE/NEUTRAL/ACID EXTRACTABLES FROM SPIKED TCLP BUF FERS**  **HIGH SPIKE LEVEL**

**Analyte Spike**  **Level (μg/L)**  **Buffer 1 (pH=2.886) Buffer 2 (pH=4.937)**

**Recovery (%) RSD Recovery (%) RSD**

**1,4-Dichlorobenzene 15,000 63 10 63 9**
**Hexachloroethane 6,000 54 7 46 7**
**Nitrobenzene 4,000 81 4 81 13**
**Hexachlorobutadiene 1,000 81 5 70 11**
**2,4-Dinitrotoluene 260 99 8 98 3**

**Hexachlorobenzene 260 89 8 91 9**
**o-Cresol* 400,000 92 15 90 4**
**m-Cresol* 400,000 95 8 82 6** **p-Cresol* 400,000 82 14 84 7** **2,4,6-Trichlorophenol 4,000 93 12 104 12 2,4,5-Trichlorophenol 800,000 93 14 97 23**  **Pentachlorophenol 200,000 84 9 73 8**

**Results from seven replicate spiked buffer samples.**

***In this study, recoveries of these compounds were determined from triplicate spikes of the**  **individual compounds into separate buffer solutions**

**.**

**Data from Reference 12. SW-846 Update V 8270D - 60 Revision 5**  **October 2012 TABLE 17** 

**RECOVERY DATA FROM THREE LABORATORIES FOR SPE (METH OD 3535)**  **OF BASE/NEUTRAL/ACID/EXTRACTABLES FROM SPIKED TCLP LEACHATES FROM SOIL**  **SAMPLES**

**Buffer 1 pH=2.886 Lab 1 Lab 2 Lab 3** 

**Analyte Spike**  **Level** **(μg/L)* %R RSD n %R RSD n %R RSD n**

**o-Cresol 200,000 86 8 7 35.3 0.7 3 7.6 6 3**

**m-Cresol** -- 77 8 7 -- -- -- -- -- --**

**p-Cresol** -- -- -- -- -- -- -- 7.7 11 3**

**2,4,6-Trichlorophenol 2,000 106 6 7 96.3 3.9 3 44.8 5 3** 

**2,4,5-Trichlorophenol 400,000 93 3 7 80.5 4.5 3 63. 3 11 3** 

**Pentachlorophenol 100,000 79 2 7 33.8 12.2 3 29.2 1 3 3** 

**1,4-Dichlorobenzene 7,500 51 5 7 81.3 5.3 3 19.2 7 3** 

**Hexachloroethane 3,000 50 5 7 66.2 2.1 3 12.6 11 3**

**Nitrobenzene 2,000 80 8 7 76.3 5.3 3 63.9 12 3**

**Hexachlorobutadiene 500 53 8 7 63.3 4.8 3 9.6 9 3**

**2,4-Dinitrotoluene 130 89 8 7 35.7 2.6 3 58.2 17 3**

**Hexachlorobenzene 130 84 21 7 92.3 1.6 3 71.7 9 3**

**(continued) SW-846 Update V 8270D - 61 Revision 5**  **October 2012 TABLE 17**  **(continued)**

**Buffer 2 pH=4.937 Lab 1 Lab 2 Lab 3** 

**Analyte Spike**  **Level** **(μg/L)* %R RSD n %R RSD n %R RSD n**

**o-Cresol 200,000 97 13 7 37.8 4.5 3 6.1 24 3**

**m-Cresol** -- 83 4 7 -- -- -- 6.0 25 3**

**p-Cresol** -- -- -- -- -- -- -- -- -- --**

**2,4,6-Trichlorophenol 2,000 104 4 7 91.7 8.0 3 37.7 25 3** 

**2,4,5-Trichlorophenol 400,000 94 4 7 85.2 0.4 3 64. 4 10 3** 

**Pentachlorophenol 100,000 109 11 7 41.9 28.2 3 36.6 32 3** 

**1,4-Dichlorobenzene 7,500 50 5 7 79.7 1.0 3 26.5 68 3** 

**Hexachloroethane 3,000 51 3 7 64.9 2.0 3 20.3 90 3**

**Nitrobenzene 2,000 80 4 7 79.0 2.3 3 59.4 6 3**

**Hexachlorobutadiene 500 57 5 7 60 3.3 3 16.6 107 3**

**2,4-Dinitrotoluene 130 86 6 7 38.5 5.2 3 62.2 6 3**

**Hexachlorobenzene 130 86 7 7 91.3 0.9 3 75.5 5 3**

*** 250-mL aliquots of leachate were spiked. Lab 1 s piked at one-half these levels.** 

**** m-Cresol and p-Cresol co-elute. Lab 1 and Lab 3 reported o-Cresol and the sum of m- and p**  **Cresol. Lab 2 reported the sum of all three isomer s of Cresol.** 

**Data from Reference 12. SW-846 Update V 8270D - 62 Revision 5**  **October 2012 TABLE 18** 

**SINGLE LABORATORY PAH ANALYSIS DATA FROM: A REAL SOIL CONTAMINATED WITH CREOSOTE, USING METH**  **OD 3546 (MICROWAVE EXTRACTION)** 

**Compound Concentration (μg/kg) RSD (%)**  **REAC values (μg/kg)**

**Naphthalene 2,170 12.4 710,000 2-Methylnaphthalene 28,710 3.1 N/R**  **1-Methylnaphthalene 33,180 2.4 N/R Biphenyl 13,440 6.0 N/R**  **2,6-Dimethylnaphthalene 52,990 3.8 N/R Acenaphthylene 16,320 3.1 21,000**  **Acenaphthene 801,210 6.0 1,700,000**
**Fluorene 789,980 3.4 990,000**
**Phenanthrene 1,627,480 0.7 3,300,00**
**Anthracene 346,010 4.0 360,000 Benzo(a)anthracene 300,380 2.7 310,000** 
**Fluoranthene 1,331,690 1.6 1,600,000 Pyrene 1,037,710 3.0 1,100,000**  **Chrysene 293,200 3.4 320,000 Benzo(b)fluoranthene 152,000 3.8 140,000**  **Benzo(k)fluoranthene 127,740 3.6 130,000 Benzo(e)pyrene 87,610 3.9 N/R**  **Benzo(a)pyrene 128,330 3.9 110,000 Perylene 35,260 4.3 N/R**  **Indeno(1,2,3-cd)pyrene 63,900 5.0 25,000 Dibenz(a,h)anthracene 17,290 6.9 N/R**  **Benzo(g,h,i)perylene 42,270 6.9 20,000**

**n = 4**

**Soil samples obtained from U.S. EPA Emergency Respo nse Center archive bank through their**  **Response Engineering and Analytical Contract (REAC) laboratory (Edison, NJ). The standard**  **Soxhlet extraction procedures were performed by REA C three years earlier; this long storage**  **period is believed to account for the low naphthale ne recovery data in the present study.** 

**REAC data labeled N/R = not reported SW-846 Update V 8270D - 63 Revision 5**  **October 2012 TABLE 19** 

**SINGLE LABORATORY PAH RECOVERY DATA FROM: HS-5 MARINE SEDIMENT MATERIALS, USING METHOD 3546** 

**(MICROWAVE EXTRACTION)**

**Compound Certified Value**  **(μg/kg) Confidence** 

**Interval (μg/kg)**  **Recovery**

**(%)**

**Naphthalene 250 180 - 320 76** **Acenaphthylene 150 * 107** **Acenaphthene 230 130 - 330 61**

**Fluorene 400 300 - 500 63**
**Phenanthrene 5,200 4,200 - 6,200 72**

**Anthracene 380 230 - 530 84**
**Fluoranthene 8,400 5,800 - 10,000 81 Pyrene 5,800 4,000 - 7,600 69**  **Benzo(a)anthracene 2,900 1,700 - 4,100 53 Chrysene 2,800 1,900 - 3,700 76**  **Benzo(b)fluoranthene 2,000 1,000 - 3,000 84 Benzo(k)fluoranthene 1,000 600 - 1,400 137**  **Benzo(a)pyrene 1,700 900 - 2,500 52 Indeno(1,2,3-cd)pyrene 1,300 600 - 2,000 63**  **Dibenz(a,h)anthracene 200 100 - 300 125 Benzo(g,h,i)perylene 1,300 1000 - 1600 64** 

**n = 3**

*** values not certified**

**The uncertainties represent 90% confidence interval s.** **SW-846 Update V 8270D - 64 Revision 5 October 2012**  **TABLE 20**

**SINGLE LABORATORY PAH RECOVERY DATA FROM: HS-4 MARINE SEDIMENT MATERIALS, USING METHOD 3546** 

**(MICROWAVE EXTRACTION)**

**Compound Certified**  **Value (μg/kg)**  **Confidence**

**Interval (μg/kg)**  **Recovery**

**(%)**

**Naphthalene 150 * 54** **Acenaphthylene 150 * 82** **Acenaphthene 150 * 63**

**Fluorene 150 * 81**

**Phenanthrene 680 600 - 760 81**

**Anthracene 140 70 - 210 108**
**Fluoranthene 1250 1,150 - 1,350 84 Pyrene 940 820 - 1,060 85**  **Benzo(a)anthracene 530 470 - 580 78 Chrysene 650 570 - 730 84**  **Benzo(b)fluoranthene 700 550 - 850 84 Benzo(k)fluoranthene 360 310 - 410 156**  **Benzo(a)pyrene 650 570 - 730 73 Indeno(1,2,3-cd)pyrene 510 360 - 660 88**  **Dibenz(a,h)anthracene 120 70 - 170 117 Benzo(g,h,i)perylene 580 360 - 800 91** 

**n = 3**

*** values not certified**

**The uncertainties represent 90% confidence interval s.** **SW-846 Update V 8270D - 65 Revision 5 October 2012**  **TABLE 21**

**SINGLE LABORATORY PAH RECOVERY DATA FROM: HS-3 MARINE SEDIMENT MATERIALS, USING METHOD 3546** 

**(MICROWAVE EXTRACTION)**

**Compound Certified**  **Value (μg/kg)**  **Confidence**

**Interval (μg/kg)**  **Recovery**

**(%)**

**Naphthalene 9,000 8300 - 9,700 61 Acenaphthylene 300 200 - 400 199**  **Acenaphthene 4,500 3,000 - 6,000 80**
**Fluorene 13,300 10,200 - 16,400 58**
**Phenanthrene 85,000 65000 - 105,000 87**
**Anthracene 13,400 12,900 - 13,900 47**
**Fluoranthene 60,000 51,000 - 69,000 91 Pyrene 39,000 30,000 - 48,000 86**  **Benzo(a)anthracene 14,600 12,600 - 16,600 78 Chrysene 14,100 12,100 - 16,100 91**  **Benzo(b)fluoranthene 7,700 6,500 - 8,900 101 Benzo(k)fluoranthene 2,800 800 - 4,800 275**  **Benzo(a)pyrene 7,400 3,000 - 7,000 74 Indeno(1,2,3-cd)pyrene 5,400 4,100 - 6,700 100**  **Dibenz(a,h)anthracene 1,300 800 - 1,800 118 Benzo(g,h,i)perylene 5,000 3,000 - 7,000 99** 

**n = 3**

*** values not certified**

**The uncertainties represent 90% confidence interval s.** **SW-846 Update V 8270D - 66 Revision 5 October 2012**  **TABLE 22**

**SINGLE LABORATORY PAH RECOVERY DATA FROM: SRM 1941 MARINE SEDIMENT MATERIALS, USING METHOD 35**  **46**

**(MICROWAVE EXTRACTION)**

**Compound Certified Value**  **(μg/kg) Recovery** 

**(%)**

**Naphthalene 1010 97.4**

**Fluorene 100 100.0**

**Phenanthrene 490 102.0**

**Fluoranthene 980 116.7 Pyrene 810 97.3**  **Benzo(a)anthracene 430 89.8 Chrysene 380 130.3**  **Benzo(b)fluoranthene 740 95.8 Benzo(k)fluoranthene 360 130.2**  **Benzo(e)pyrene 550 81.0 Benzo(a)pyrene 630 76.0**  **Perylene 450 72.4 Indeno(1,2,3-cd)pyrene 500 126.0**  **Dibenz(a,h)anthracene 110 78.7 Benzo(g,h,i)perylene 530 85.2** 

**n = 3**

**All RSDs < 10%. SW-846 Update V 8270D - 67 Revision 5**  **October 2012 FIGURE 1**  **TAILING FACTOR CALCULATION SW-846 Update V 8270D - 68 Revision 5**  **October 2012 FIGURE 2**  **GAS CHROMATOGRAM OF BASE/NEUTRAL AND ACID CALIBRATI ON STANDARD** **SW-846 Update V 8270D - 69 Revision 5 October 2012**  **Appendix A:**

**Summary of Revisions to Method 8270D (From Revision 4 Feb 2007)** 

**1. Improved overall method formatting for consisten cy with new SW-846 methods style**  **guidance. The format was updated to Microsoft Word 2007.docx.** 

**2. Many minor editorial and technical revisions wer e made throughout to improve method**  **clarity.**

**3. The revision number was changed to 5 and the dat e published was changed to October**  **2012.**

**4. This appendix was added showing changes from the previous revision.** 

**5. Chemical name was changed by the Integrated Risk Information System (IRIS) on**  **November 30, 2007 from Bis(2-chloroisopropyl)ether to Bis(2-chloro-1-methylethyl)ether**  **(common name). This compound is also known as 2,2’ -oxybis(1-chloropropane) (CAS**  **index name). See the link at http://www.epa.gov/iris/subst/0407.htm**  **, Section VII for the “Revision History” and Section VIII, for “Synonyms”**  **of this chemical.**