**SW-846 Update V 8021B - 1 Revision 3**

**October 2012 METHOD 8021B** 

**AROMATIC AND HALOGENATED VOLATILES BY GAS CHROMATOG RAPHY USING** 

**PHOTOIONIZATION AND/OR ELECTROLYTIC CONDUCTIVITY DE TECTORS** 

**1.0 SCOPE AND APPLICATION**

**1.1 Method 8021 is used to determine volatile organ ic compounds in a variety of solid**  **waste matrices. This method is applicable to nearl y all types of samples, regardless of water**  **content, including ground water, aqueous sludges, c austic liquors, acid liquors, waste solvents,**  **oily wastes, mousses, tars, fibrous wastes, polymer ic emulsions, filter cakes, spent carbons,**  **spent catalysts, soils, and sediments. The followi ng compounds can be determined by this** 

**method:**

**Appropriate Technique**

**Analyte CAS No.**  **a Purge and**  **Trap Direct** 

**Injection Vacuum** 

**Distillation Head** 

**space Allyl chloride**  **107-05-1 b**  **b nd**  **nd**

**Benzene 71-43-2**  **b b**  **b b** 
**Benzyl chloride 100-44-7**  **pp b**  **nd nd**  **Bis(2-chloro-1- methylethyl)ether** * **108-60-1 b**  **b nd**  **nd**

**Bromoacetone 598-31-2**  **pp b**  **nd nd** 

**Bromobenzene 108-86-1**  **b nd**  **nd nd** 

**Bromochloromethane 74-97-5**  **b b**  **nd b** 

**Bromodichloromethane 75-27-4**  **b b**  **b b** 

**Bromoform 75-25-2**  **b b**  **b b** 

**Bromomethane 74-83-9**  **b b**  **b b** 

**Carbon tetrachloride 56-23-5**  **b b**  **b b** 

**Chlorobenzene 108-90-7**  **b b**  **b b** 

**Chlorodibromomethane 124-48-1**  **b b**  **b b** 

**Chloroethane 75-00-3**  **b b**  **b b** 

**2-Chloroethanol 107-07-03**  **pp b**  **nd nd**  **2-Chloroethyl vinyl ether 110-75-8**  **b b**  **b nd** 

**Chloroform 67-66-3**  **b b**  **b b** 

**Chloromethane 74-87-3**  **b b**  **b b**  **Chloromethyl methyl ether 107-30-2**  **pp pc**  **nd nd** 
**Chloroprene 126-99-8**  **b nd**  **nd nd** 

**4-Chlorotoluene 106-43-4**  **b b**  **nd nd** 
**1,2-Dibromo-3-chloropropane 96-12-8**  **pp b**  **nd b** 

**1,2-Dibromoethane 106-93-4**  **b nd**  **nd b** 

**Dibromomethane 74-95-3**  **b b**  **b b** 

**1,2-Dichlorobenzene 95-50-1**  **b nd**  **nd b** 

**1,3-Dichlorobenzene 541-73-1**  **b nd**  **nd b** 

**1,4-Dichlorobenzene 106-46-7**  **b nd**  **nd b** 

**Dichlorodifluoromethane 75-71-8**  **b b**  **b b** 

**1,1-Dichloroethane 75-34-3**  **b b**  **b b** 

**1,2-Dichloroethane 107-06-2**  **b b**  **b b** **SW-846 Update V 8021B - 2 Revision 3**

**October 2012 Appropriate Technique** 

**Analyte CAS No.**  **a Purge and**  **Trap Direct** 

**Injection Vacuum** 

**Distillation Head** 

**space**
**1,1-Dichloroethene 75-35-4 b b b b** 

**cis-1,2-Dichloroethene 156-59-2**  **b nd**  **nd nd** 

**trans-1,2-Dichloroethene 156-60-5**  **b b**  **b b** 
**1,2-Dichloropropane 78-87-5**  **b nd**  **b b** 
**1,3-Dichloro-2-propanol 96-23-1**  **pp b**  **nd nd** 
**cis-1,3-Dichloropropene 10061-01-5**  **b b**  **b nd** 
**trans-1,3-Dichloropropene 10061-02-6**  **b b**  **b nd** 
**Epichlorhydrin 106-89-8**  **pp b**  **nd nd** 
**Ethylbenzene 100-41-4**  **b b**  **b b** 

**Hexachlorobutadiene 87-68-3**  **b nd**  **nd b** 
**Methylene chloride 75-09-2**  **b b**  **b b** 
**Naphthalene 91-20-3**  **b nd**  **nd b**  **Styrene 100-42-5**  **b b**  **b b** 

**1,1,1,2-Tetrachloroethane 630-20-6**  **b nd**  **nd b** 

**1,1,2,2-Tetrachloroethane 79-34-5**  **b b**  **b b** 

**Tetrachloroethene 127-18-4**  **b b**  **b b** 

**Toluene 108-88-3**  **b b**  **b b** 

**1,2,4-Trichlorobenzene 120-82-1**  **b nd**  **nd b** 

**1,1,1-Trichloroethane 71-55-6**  **b b**  **b b** 

**1,1,2-Trichloroethane 79-00-5**  **b b**  **b b** 

**Trichloroethene 79-01-6**  **b b**  **b b** 

**Trichlorofluoromethane 75-69-4**  **b b**  **b b** 
**1,2,3-Trichloropropane 96-18-4**  **b b**  **b b** 
**Vinyl chloride 75-01-4**  **b b**  **b b** 
**o-Xylene 95-47-6**  **b b**  **b b** 
**m-Xylene 108-38-3**  **b b**  **b b** 
**p-Xylene 106-42-3**  **b b**  **b b** 

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

***** **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-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 c**  **hemical. b Adequate response by this technique**  **i Inappropriate technique for this analyte**

**nd Not Determined pc Poor chromatographic behavior**  **pp Poor purging efficiency resulting in high limits of detection. This may require heated purge**  **(e.g., 40** ° **C) or a more appropriate sample preparation techniq ue (e.g., azeotropic**  **distillation, equilibrium headspace or vacuum disti llation) for good method performance.** 

**1.2 Levels of detection are compound dependent and vary with purging efficiency and**  **concentration. The applicable concentration range of this method is compound and instrument**  **dependent but is approximately 0.1 to 200 μg/L. An alytes that are inefficiently purged from**  **water will not be detected when present at low conc entrations, but they can be measured with** **SW-846 Update V 8021B - 3 Revision 3**

**October 2012 acceptable accuracy and precision when present in s**  **ufficient amounts. Determination of some structural isomers (i.e., xylenes) may be hampered**  **by coelution.**

**1.3 Lower Limit of Quantitation (LLOQ) - The labora tory shall establish the LLOQ as**  **the lowest point of quantitation, which in most cas es is the lowest concentration in the** 

**calibration curve. LLOQ verification is recommende d for each project application to validate**  **quantitation capability at low analyte concentratio n levels. This verification may be**  **accomplished with either clean control material (e. g., reagent water, solvent blank, Ottawa sand,**  **diatomaceous earth, etc.) or a representative sampl e matrix, free of target compounds.**  **Optimally, the LLOQ should be less than the desired regulatory action levels based on the**  **stated Data Quality Objectives (DQOs). The LLOQ of Method 8021A for an individual**  **compound is approximately 1 μg/kg (wet weight) for soil/sediment samples, 0.1 mg/kg (wet**  **weight) for wastes, and 1 μg/L for ground water. L LOQs will be proportionately higher for**  **sample extracts and samples that require dilution o r reduced sample size to avoid saturation of** 

**the detector.**

**1.4 This method is restricted for use by, or under the supervision of, analysts**  **experienced in the use of gas chromatographs for me asurement of purgeable organics at low**  **μg/L concentrations and skilled in the interpretati on of gas chromatograms. Each analyst must**  **demonstrate the ability to generate acceptable resu lts with this method.** 

**1.5 The toxicity or carcinogenicity of chemicals us ed in this method has not been**  **precisely defined. Each chemical should be treated as a potential health hazard, and exposure** 

**to these chemicals should be minimized. Each labor atory is responsible for maintaining**  **awareness of Occupational Safety and Health Adminis tration (OSHA) regulations regarding safe**  **handling of chemicals used in this method.**

**1.6 The following method analytes have been tentati vely classified as known or**  **suspected human or mammalian carcinogens: carbon te trachloride, 1,4-dichlorobenzene, 1,2-**  **dichloroethane, hexachlorobutadiene, 1,1,2,2-tetrac hloroethane, 1,1,2-trichloroethane,**  **chloroform, 1,2-dibromoethane, tetrachloroethene, t richloroethene, and vinyl chloride. Pure** 

**standard materials and stock standard solutions of these compounds should be handled in a**  **hood. A National Institute for Occupational Safety and Health (NIOSH)/Mine Safety and Health**  **Administration (MSHA) approved toxic gas respirator should be worn when the analyst handles**  **high concentrations of these toxic compounds.**

**1. 7 Other non-RCRA compounds which are amenable to analysis by Method 8021** 

**include:**

**Analyte CAS No.**  **a**
**n-Butylbenzene 104-51-8** 

sec **-Butylbenzene 135-98-8** 

tert

**-Butylbenzene 98-06-6** 

**2-Chlorotoluene 95-49-8**  **1,3-Dichloropropane 142-28-9**  **2,2-Dichloropropane 594-20-7**  **1,1-Dichloropropene 563-58-6**  **Isopropylbenzene 98-82-8**  **p-Isopropyltoluene 99-87-6**  **n-Propylbenzene 103-65-1**  **1,2,3-Trichlorobenzene 87-61-6 1,2,4-Trimethylbenzene 95-63-6**  **1,3,5-Trimethylbenzene 108-67-8 SW-846 Update V 8021B - 4 Revision 3** 

**October 2012 a**  **Chemical Abstracts Service Registry Number**

**2.0 SUMMARY OF METHOD**

**2.1 Method 8021 provides gas chromatographic condit ions for the detection of**  **halogenated and aromatic volatile organic compounds . Samples can be analyzed using direct**  **injection (Method 3585 for oily matrices), purge an d trap (Methods 5030/5035), headspace**  **(Method 5021), or vacuum distillation (Method 5032) . Groundwater samples may be analyzed**  **using Method 5030, Method 5021, or Method 5032. A temperature program is used in the gas**  **chromatograph (GC) to separate the organic compound s. Detection is achieved by a**  **photoionization detector (PID) and a Hall electroly tic conductivity detector (HECD) in series.**  **The GC system may also be set up to use a single de tector when an analyst is looking for only**  **halogenated compounds (HECD) or aromatic compounds (PID).** 

**2.2 Tentative identifications are obtained by analy zing standards under the same**  **conditions used for samples and comparing resultant GC retention times. Confirmatory**  **information can be gained by comparing the relative response from the two detectors.**  **Concentrations of the identified components are mea sured by relating the response produced**  **for that compound to the response produced by a com pound that is used as an internal** 

**standard.**

**3.0 DEFINITIONS**

**Refer to Chapter One, the individual determinative methods, and the manufacturer's**  **instructions for definitions that may be relevant.**

**4.0 INTERFERENCES**

**4.1 Refer to the appropriate 5000 Series method and Method 8000.** 

**4.2 Samples can be contaminated by diffusion of vol atile organics (particularly**  **chlorofluorocarbons and methylene chloride) through the sample container septum during**  **shipment and storage. A trip blank prepared from o rganic-free reagent water and carried**  **through sampling and subsequent storage and handlin g can serve as a check on such** 

**contamination.**

**4.3 Sulfur dioxide is a potential interferant in th e analysis for vinyl chloride.** 

**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 OSHA**  **regulations regarding the safe handling of the chem icals and instrumentation included in this**  **method. A reference file of material safety data s heets (MSDSs) should be available to all**  **personnel involved in these analyses.**

**6.0 EQUIPMENT AND SUPPLIES SW-846 Update V 8021B - 5 Revision 3** 

**October 2012 6.1 Sample introduction apparatus – Refer to the ap**  **propriate 5000 Series method for a listing of the equipment for each sample introducti**  **on technique.**

**6.2 GC – capable of temperature programming; equipp ed with variable-constant**  **differential flow controllers, subambient oven cont roller, PID and HECD connected with a short**  **piece of uncoated capillary tubing, 0.32 - 0.5 mm I D, and a data system.** 

**6.2.1 Primary Column – 60 m x 0.75 mm ID VOCOL wide -bore capillary column**  **with 1.5-μm film thickness (Supelco), or equivalent**

**6.2.2 Confirmation column – 60 m x 0.53 ID SPB-624 wide-bore capillary**  **column with 3.0-μm film thickness (Supelco) has bee n suggested as one possible option.**  **Other columns that will provide appropriate resolut ion of the target compounds may also**  **be employed for confirmation, or confirmation may b e performed using gas**  **chromatography/mass spectrometry (GC/MS).**

**6.2.3 PID (Tracor Model 703, or equivalent)**

**6.2.4 HECD (Tracor Hall Model 700-A, or equivalent)**

**6.3 Syringes – 5 mL glass hypodermic equipped with Luer-Lok tips** 

**6.4 Syringe valves – 2 way equipped with Luer ends (polytetrafluoroethylene (PTFE) or**  **Kel-F)**

**6.5 Microsyringe – 25 μL equipped with a 2 in. x 0. 006 in. ID, 22**  ° **bevel needle (Hamilton #702N or equivalent)** 

**6.6 Microsyringes – 10, 100 μL**

**6.7 Syringes – 0.5, 1.0, and 5 mL, gas-tight with s hut-off valve** 

**6.8 Bottles – 15 mL, PTFE-lined fitted with screw-c ap or crimp top** 

**6.9 Analytical balance – 0.0001 g**

**6.10 Volumetric flasks, Class A – Appropriate sizes with ground glass stoppers** 

**7.0 REAGENTS AND STANDARDS**

**7.1 Reagent-grade inorganic chemicals shall be used in all tests. Unless otherwise**  **indicated, it is intended that all inorganic reagen ts shall conform to the specifications of the**  **Committee on Analytical Reagents of the American Ch emical Society (ACS), where such**  **specifications are available. Other grades may be used, provided it is first ascertained that the**  **reagent is of sufficiently high purity to permit it s use without lessening the accuracy of the** 

**determination.**

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

**7.3 Methanol, CH 3**  **OH – Pesticide quality or equivalent, demonstrated to be free of**  **analytes. Store away from other solvents. SW-846 Update V 8021B - 6 Revision 3** 

**October 2012 7.4 Vinyl chloride, (99.9% pure), CH**  **2 CHCl – Vinyl chloride is available from Ideal Gas**  **Products, Inc., Edison, New Jersey and from Matheso n, East Rutherford, New Jersey, as well**  **as from other sources. Certified mixtures of vinyl chloride in nitrogen at 1.0 and 10.0 ppm (v/v)** 

**are available from several sources.**

**7.5 Stock standards – Stock solutions may either be prepared from pure standard**  **materials or purchased as certified solutions. Pre pare stock standards in methanol using**  **assayed liquids or gases, as appropriate. Because of the toxicity of some of the organohalides,**  **primary dilutions of these materials should be prep ared in a hood.** 

**NOTE : If direct injection is used, the solvent system o**  **f standards must match that of the sample. It is not necessary to prepare high concen**  **tration aqueous mixed standards when using direct injection.** 

**7.5.1 Place approximately 9.8 mL of methanol in a 1 0-mL tared ground glass**  **stoppered volumetric flask. Allow the flask to sta nd, unstoppered, for about 10 minutes**  **until all alcohol-wetted surfaces have dried. Weig h the flask to the nearest 0.1 mg.** 

**7.5.2 Add the assayed reference material, as descri bed below.** 

**7.5.2.1 Liquids: Using a 100-μL syringe, immediatel y add two or more**  **drops of assayed reference material to the flask; t hen reweigh. The liquid must fall**  **directly into the alcohol without contacting the ne ck of the flask.** 

**7.5.2.2 Gases: To prepare standards for any compoun ds that boil** 

**below 30** ° **C (e.g., bromomethane, chloroethane, chloromethane, dichlorodifluoromethane, trichlorofluoromethane, vi**  **nyl chloride), fill a 5-mL valved gas-tight syringe with the reference standard to th**  **e 5.0 mL mark. Lower the needle to 5 mm above the methanol meniscus. Slowly**  **introduce the reference standard above the surface of the liquid. The heav**  **y gas rapidly dissolves in the methanol. This may also be accomplished by using a**  **lecture bottle equipped with a septum. Attach PTFE tubing to the side-arm relie**  **f valve and direct a gentle stream of gas into the methanol meniscus.** 

**7.5.3 Reweigh, dilute to volume, stopper, and then mix by inverting the flask**  **several times. Calculate the concentration in mg/L from the net gain in weight. When**  **compound purity is assayed to be 96% or greater, th e weight may be used without** 

**correction to calculate the concentration of the st ock standard. Commercially prepared**  **stock standards may be used at any concentration if they are certified by the manufacturer**  **or by an independent source.**

**7.5.4 Transfer the stock standard solution into a b ottle fitted with a PTFE-lined**  **screw cap or crimp top. Store, with minimal headsp ace, at -10**  ° **C to -20** ° **C and protect from light. Standards should be returned to the fr**  **eezer as soon as the analyst has completed mixing or diluting the standards to preve**  **nt the evaporation of volatile target compounds.** **SW-846 Update V 8021B - 7 Revision 3**

**October 2012 7.5.5 Frequency of standard preparation** 

**7.5.5.1 Standards for the permanent gases should be monitored**  **frequently by comparison to the initial calibration curve. Fresh standards should be**  **prepared if this check exceeds a 20% drift. Standa rds for gases usually need to be**  **replaced after one week or as recommended by the st andard manufacturer, unless**  **the acceptability of the standard can be documented . Dichlorodifluoromethane and**  **dichloromethane will usually be the first compounds to evaporate from the standard**  **and should, therefore, be monitored very closely wh en standards are held beyond** 

**one week.**

**7.5.5.2 Standards for the non-gases should be monit ored frequently**  **by comparison to the initial calibration. Fresh st andards should be prepared if this**  **check exceeds a 20% drift. Standards for non-gases usually need to be replaced**  **after six months or as recommended by the standard manufacturer, unless the**  **acceptability of the standard can be documented. S tandards of reactive**  **compounds such as 2-chloroethyl vinyl ether and sty rene may need to be prepared**  **more frequently.**

**7.6 Prepare secondary dilution standards, using sto ck standard solutions, in methanol,**  **as needed, that contain the compounds of interest, either singly or mixed together. The**  **secondary dilution standards should be prepared at concentrations such that the aqueous**  **calibration standards prepared in Sec. 7.5 will bra cket the working range of the analytical**  **system. Secondary dilution standards should be sto red with minimal headspace for volatiles**  **and should be checked frequently for signs of degra dation or evaporation, especially just prior to**  **preparing calibration standards from them. Seconda ry standards for gases should be replaced**  **after one week unless the acceptability of the stan dard can be documented. When using**  **premixed certified solutions, store according to th e manufacturer's documented holding time**  **and storage temperature recommendations. The analy st should also handle and store** 

**standards as stated in Sec. 7.5.4 and return them t o the freezer as soon as standard mixing or**  **diluting is completed to prevent the evaporation of volatile target compounds.** 

**7.7 Calibration standards - There are two types of calibration standards used for this** 

**method: initial calibration standards and calibrati on verification standards. When using**  **premixed certified solutions, store according to th e manufacturer's documented holding time**  **and storage temperature recommendations.**

**7.7.1 Initial calibration standards should be prepa red at a minimum of five**  **concentrations from the secondary dilution of stock standards (see Secs. 7.5 and 7.6) or**  **from a premixed certified solution. Prepare these solutions in organic-free reagent water.** 

**At least one of the calibration standards should co rrespond to a sample concentration at or**  **below that necessary to meet the DQOs of the projec t. The remaining standards should**  **correspond to the range of concentrations found in typical samples but should not exceed**  **the working range of the GC system. Initial calibr ation standards should be mixed from**  **fresh stock standards and dilution standards when g enerating an initial calibration curve.**  **See Sec. 11 of Method 8000 for guidance on initial calibration.** 

**7.7.2 Calibration verification standards should be prepared at a concentration**  **near the mid-point of the initial calibration range from the secondary dilution of stock**  **standards (see Secs. 7.5 and 7.6) or from a premixe d certified solution. Prepare these**  **solutions in organic-free reagent water. See Sec. 11 of Method 8000 for guidance on** 

**calibration verification. SW-846 Update V 8021B - 8 Revision 3** 

**October 2012 7.7.3 It is the intent of the Environmental Protect**  **ion Agency (EPA or the Agency) that all target analytes for a particular a**  **nalysis be included in the initial calibration and calibration verification standard(s). These ta**  **rget analytes may not include the entire list of analytes (Sec. 1.1) for which the method ha**  **s been demonstrated. However, the laboratory must not report a quantitative result fo**  **r a target analyte that was not included in the calibration standard(s).** 

**7.7.4 The calibration standards should also contain the internal standards**  **chosen for the analysis if internal standard calibr ation is used.** 

**7.8 In order to prepare accurate aqueous standard s olutions, the following precautions** 

**must be observed:**

**NOTE : Prepare calibration solutions for use with direct**  **injection analyses in water at the concentrations required.** 

**7.8.1 Do not inject more than 20 μL of alcoholic st andards into 100 mL of water.** 

**7.8.2 Use a 25-μL Hamilton 702N micro syringe or eq uivalent (variations in**  **needle geometry will adversely affect the ability t o deliver reproducible volumes of**  **methanolic standards into water).**

**7.8.3 Rapidly inject the alcoholic standard into th e filled volumetric flask.**  **Remove the needle as fast as possible after injecti on.** 

**7.8.4 Mix aqueous standards by inverting the flask three times.** 

**7.8.5 Fill the sample syringe from the standard sol ution contained in the**  **expanded area of the flask (do not use any solution contained in the neck of the flask).** 

**7.8.6 Never use pipets to dilute or transfer sample s or aqueous standards.** 

**7.8.7 Standards should be stored and handled accord ing to guidance in Secs.** 

**7.5.4 and 7.5.5.**

**7.9 Internal standards – It is recommended that a s piking solution containing**  **fluorobenzene and 2-bromo-1-chloropropane in methan ol be prepared, using the procedures** 

**described in Secs. 7.5 and 7.6. It is further reco mmended that the secondary dilution standard**  **be prepared at a concentration of 5 mg/L of each in ternal standard compound. The addition of**  **10 μL of such a standard to 5.0 mL of sample calibr ation standard would be equivalent to 10**  **μg/L. External standard quantitation may also be u sed.** 

**7.10 Surrogate standards – The analyst should monit or both the performance of the**  **analytical system and the effectiveness of the meth od in dealing with each sample matrix by**  **spiking each sample, standard, and reagent blank wi th two or more surrogate compounds. A**  **combination of 1,4-dichlorobutane and bromochlorobe nzene is recommended to encompass the**  **range of the temperature program used in this metho d. From stock standard solutions prepared**  **as in Sec. 7.5, add a volume to give 750 μg of each surrogate to 45 mL of organic-free reagent**  **water contained in a 50-mL volumetric flask, mix, a nd dilute to volume for a concentration of**  **15 ng/μL. Add 10 μL of this surrogate spiking solu tion directly into the 5-mL syringe with every**  **sample and reference standard analyzed. If the int ernal standard calibration procedure is used,**  **the surrogate compounds may be added directly to th e internal standard spiking solution (Sec.**  **7.9). SW-846 Update V 8021B - 9 Revision 3** 

**October 2012 8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE** 

**See Chapter 4, Organic Analytes, Sec. 4.1 for more information on this topic.** 

**9.0 QUALITY CONTROL (QC)**

**9.1 General guidance**

**Refer to Chapter One for guidance on quality assura nce (QA) and QC protocols. When**  **inconsistencies exist between QC guidelines, method -specific QC criteria take precedence over**  **both technique-specific and Chapter One criteria; t echnique-specific QC criteria take**  **precedence over Chapter One criteria. Any effort i nvolving collection of analytical data should**  **include development of a structured and systematic planning document, such as a Quality**  **Assurance Project Plan (QAPP) or a Sampling and Ana lysis Plan (SAP), which translates**  **project objectives and specifications into directio ns for those who will implement the project and** 

**assess the results.**

**Each laboratory should maintain a formal QA program . The laboratory should also**  **maintain records to document the quality of the dat a generated. Development of in-house QC**  **limits for each method is encouraged, as described in Sec. 9.6 of Method 8000. Use of**  **instrument-specific QC limits is encouraged, provid ed such limits will generate data appropriate**  **for use in the intended application. All data shee ts and QC data should be maintained for**  **reference or inspection.**

**9.2 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.**

**9.2.1 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 standard**  **operating procedure (SOP) established by the labora tory.** 

**9.3 QC procedures necessary to evaluate the GC syst em operation are found in**  **Method 8000, Sec. 11 and include evaluation of rete ntion time windows, calibration verification,**  **and chromatographic analysis of samples.**

**9.4 Sample QC for preparation and analysis – The l aboratory must also have**  **procedures for documenting the effect of the matrix on method performance (precision,**  **accuracy, and detection limit). At a minimum, this includes the analysis of QC samples**  **including a method blank, a matrix spike, a duplica te, and a laboratory control sample (LCS) in**  **each analytical batch and the addition of surrogate s to each field sample and QC sample.** 

**9.4.1 Documentation of the effect of the matrix sho uld include the analysis of at**  **least one matrix spike and one duplicate unspiked s ample or one matrix spike/matrix spike** **SW-846 Update V 8021B - 10 Revision 3**

**October 2012 duplicate pair. The decision of 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 one matrix spike and a duplicate analysis of an uns**  **piked field sample. If samples are not expected to contain target analytes, laboratories s**  **hould use a matrix spike and matrix spike duplicate pair.** 

**9.4.2 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 the results of the matrix spike analysis indicate a potential problem**  **due to the sample matrix itself, the LCS results ar e used to verify that the laboratory can**  **perform the analysis in a clean matrix.**

**9.4.3 See Method 8000, Sec. 9 for the details on ca rrying out sample quality**  **control procedures for preparation and analysis.**

**9.5 Surrogate recoveries – The laboratory must eval uate surrogate recovery data from**  **individual samples versus the surrogate control lim its developed by the laboratory. See Method**  **8000, Sec. 9.0 for information on evaluating surrog ate data and developing and updating**  **surrogate limits.**

**9.6 Calibration verification acceptance criteria - For target compounds that boil below**  **30 °C or 1 atm pressure (e.g., bromomethane, chloro ethane, chloromethane,**  **dichlorodifluoromethane, trichlorofluoromethane, an d vinyl chloride), analysts may use a**  **calibration verification acceptance criterion of ± 20% difference from the initial calibration** 

**response.**

**9.7 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**  **laboratory and the nature of the samples. Whenever possible, the laboratory should analyze**  **standard reference materials and participate in rel evant performance evaluation studies.** 

**10.0 CALIBRATION AND STANDARDIZATION**

**10.1 Calibration – Refer to Method 8000 for proper calibration techniques.** 

**10.2 Calibration must take place using the same sam ple introduction method that will be**  **used to analyze actual samples (see Sec. 11.3.1).**

**10.3 The procedure for internal or external calibra tion may be used. Refer to Method**  **8000 for guidance on each of these procedures. SW-846 Update V 8021B - 11 Revision 3** 

**October 2012 11.0 PROCEDURE** 

**11.1 Volatile compounds are introduced into the GC either by direct injection (Method**  **3585 for oily matrices), purge and trap (Methods 50 30/5035), headspace (Method 5021), or by**  **vacuum distillation (Method 5032). Methods 5021, 5 030 or 5032 may be used directly on**  **groundwater samples. Methods 5021, 5032 or 5035 ma y be used for low-concentration**  **contaminated soils and sediments. For high-concent ration soils or sediments (>200 μg/kg),** 
**methanolic extraction, as described in Method 5035, may be necessary prior to purge and trap**  **analysis. For guidance on the dilution of oily was te samples for direct injection, refer to Method** 

**3585.**

**11.2 GC conditions (recommended)**

**11.2.1 Set up the GC system so that the PID is in s eries with the HECD. It may**  **be helpful to contact the manufacturer of the GC fo r guidance on the proper installation of**  **dual detector systems.**

**NOTE : Use of the dual detector system is not a requirem**  **ent of the method. The GC**

**system may also be set up to use a single detector when the analyst is looking**  **only for halogenated compounds (using the HECD) or only for aromatic**  **compounds (using the PID).**

**11.2.2 Oven settings: Carrier gas (Helium) flow rate: 6 mL/min.**  **Temperature program:**

**Initial temperature: 10**  ° **C, hold for 8 minutes Program ramp:**  **10** ° **C to 180** ° **C at 4** ° **C/min Final temperature:**  **180** ° **C, hold until all expected compounds have eluted.**

**11.2.3 The carrier gas flow is augmented with an ad ditional 24 mL of helium flow**  **before entering the PID. This make-up gas is neces sary to ensure optimal response from** 

**both detectors.**

**11.2.4 These halogen-specific systems eliminate mis identifications due to non**  **organohalides which are coextracted during the purg e step. A Tracor Hall Model 700-A**  **detector was used to gather the example single labo ratory accuracy and precision data**  **presented in Table 2. The operating conditions use d to collect these data are:** 

**Reactor tube: Nickel, 1/16 in OD**
**Reactor temperature: 810** ° **C Reactor base temperature: 250**  ° **C Electrolyte: 100%**  n- **Propyl alcohol Electrolyte flow rate: 0.8 mL/min**  **Reaction gas: Hydrogen at 40 mL/min Carrier gas plus make-up gas: Helium at 30 mL/min** 

**11.2.5 A sample chromatogram obtained with this col umn is presented in Figure**  **1. This column was used to develop the method perf ormance statements in Sec. 13.** 

**Estimated retention times that can be achieved unde r these conditions are given in Table**  **1. Other columns or element-specific detectors may be used if the requirements of Sec. 9** 

**are met. SW-846 Update V 8021B - 12 Revision 3** 

**October 2012 11.3 Gas chromatographic analysis** 

**11.3.1 Introduce volatile compounds into the GC usi ng either Methods**  **5030/5035 (purge-and-trap method) or the direct inj ection method (see Sec. 11.3.1.1), by**  **Method 5021 (headspace) or by Method 5032 (vacuum d istillation). If the internal**  **standard calibration technique is used, add 10 μL o f internal standard to the sample prior**  **to purging.**

**11.3.1.1 Direct injection – In very limited applica tions (e.g., aqueous**  **process wastes), direct injection of the sample int o the GC system with a 10-μL**  **syringe may be appropriate. The detection limit is very high (approximately 10,000**  **μg/L), therefore, it is only permitted where concen trations in excess of 10,000 μg/L**  **are expected or for water-soluble compounds that do not purge. The system must**  **be calibrated by direct injection (bypassing the pu rge-and-trap device).** 

**11.3.1.2 Refer to Method 3585 for guidance on the d ilution and direct**  **injection of waste oil samples.**

**11.3.1.3 Samples may be purged at temperatures abov e those being**  **recommended as long as all calibration standards, s amples, and QC samples are**  **purged at the same temperature and acceptable metho d performance is** 

**demonstrated.**

**11.3.2 Follow Sec. 9 in Method 8000 for instruction s on the analysis sequence,**  **appropriate dilutions, establishing daily retention time windows, identification criteria, and** 

**calibration verification. Include a mid-concentrat ion standard after each group of 10**  **samples in the analysis sequence.**

**11.3.3 Table 1 summarizes the estimated retention t imes on the two detectors**  **for a number of organic compounds analyzable using this method.** 

**11.3.4 Record the sample volume purged or injected and the resulting peak**  **sizes (in area units or peak heights).**

**11.3.5 Calculation of concentration is covered in M ethod 8000.** 

**11.3.6 Second column confirmation – A 60-m x 0.53 I D SPB-624 wide-bore**  **capillary column with 3.0-μm film thickness (Supelc o) has been suggested as one possible**  **option for confirming compound identifications. Ot her columns that will provide**  **appropriate resolution of the target compounds may also be employed for confirmation, or**  **confirmation may be performed using GC/MS.**

**11.3.7 If the response for a peak is off scale (i.e ., beyond the calibration range of**  **the standards), prepare a dilution of the sample wi th organic-free reagent water. The**  **dilution must be performed on a second aliquot of t he sample which has been properly**  **sealed and stored prior to use.**

**11.3.8 For target compounds that boil below 30 °C a t 1 atm pressure (e.g.,** 
**bromomethane, chloroethane, chloromethane, dichloro difluoromethane,**  **trichlorofluoromethane, and vinyl chloride), analys ts may use a calibration verification**  **acceptance criteria of within ± 20% difference from the initial calibration response.** **SW-846 Update V 8021B - 13 Revision 3**

**October 2012 12.0 DATA ANALYSIS AND CALCULATIONS** 

**12.1 See Method 8000, Sec. 11 for information regar ding data analysis and** 

**calculations.**

**12.2 Results must be reported in units commensurat e with their intended use and all**  **dilutions must be taken into account when computing final results.** 

**13.0 METHOD PERFORMANCE**

**This method was tested in a single laboratory using organic-free reagent water which was**  **spiked at 10 μg/L. Single laboratory precision and accuracy data for each detector are**  **presented for the method analytes in Table 2.**

**14.0 POLLUTION PREVENTION**

**14.1 Pollution prevention encompasses any technique 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 operation. 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 EPA recommends recycling as the next be st 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 p ractices be conducted consistent**  **with all applicable rules and regulations. Laborat ories are urged to protect air, water, and land**  **by minimizing and controlling all releases from hoo ds and bench operations, complying with the**  **letter and spirit of any sewer discharge permits an d regulations and complying with all solid and**  **hazardous waste regulations, particularly the hazar dous waste identification rules and land**  **disposal restrictions. For further information on waste management, consult**  The Waste Management Manual for Laboratory Personnel **available from the ACS at the address listed in**

**Sec. 14.2 above. SW-846 Update V 8021B - 14 Revision 3** 

**October 2012 16.0 REFERENCES** 

**1. "Volatile Organic Compounds in Water by Purge-an d-Trap Capillary Column Gas**  **Chromatography with Photoionization and Electrolyti c Conductivity Detectors in Series,**  **Method 502.2, Rev. 2.0 (1989); Methods for the Dete rmination of Organic Compounds in**  **Drinking Water," U.S. Environmental Protection Agen cy, Environmental Monitoring**  **Systems Laboratory, Cincinnati, OH, EPA/600/4-88/03 9, December, 1988.** 

**2. "The Determination of Halogenated Chemicals in W ater by the Purge and Trap Method,"**  **Method 502.1; U.S. Environmental Protection Agency, Environmental Monitoring and**  **Support Laboratory, Cincinnati, OH 45268, September , 1986.** 

**3. "Volatile Aromatic and Unsaturated Organic Compo unds in Water by Purge and Trap Gas**  **Chromatography, Method 503.1;" U.S. Environmental P rotection Agency, Environmental**  **Monitoring and Support Laboratory, Cincinnati, OH, September, 1986.** 

**4. J. A. Glaser, D. L. Forest, G. D. McKee, S. A. Q uave, W. L. Budde, "Trace Analyses for** 
**Wastewaters,"** Environ. Sci. Technol **., 1981, 15, 1426.**

**5. T. A. Bellar, J. J. Lichtenberg, "The Determinat ion of Synthetic Organic Compounds in**  **Water by Purge and Sequential Trapping Capillary Co lumn Gas Chromatography," U.S.**  **Environmental Protection Agency, Environmental Moni toring and Support Laboratory,**  **Cincinnati, OH, 45268.**

**17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION D ATA** 

**The following pages contain the tables referenced b y this method.** **SW-846 Update V 8021B - 15 Revision 3**

**October 2012 TABLE 1** 

**CHROMATOGRAPHIC RETENTION TIMES FOR VOLATILE ORGANI C COMPOUNDS WITH** 

**PID AND HECD DETECTORS**

**Analyte PID** 

**Ret. Time a** 

**minute HECD** 

**Ret. Time**

**minute**

**Dichlorodifluoromethane - b**  **8.47**

**Chloromethane - 9.47**  **Vinyl Chloride 9.88 9.93** 

**Bromomethane - 11.95** 

**Chloroethane - 12.37** 

**Trichlorofluoromethane - 13.49 1,1-Dichloroethene 16.14 16.18**  **Methylene Chloride - 18.39 trans-1,2-Dichloroethene 19.30 19.33**  **1,1-Dichloroethane - 20.99 2,2-Dichloropropane - 22.88**  **cis-1,2-Dichloroethane 23.11 23.14**

**Chloroform - 23.64** 

**Bromochloromethane - 24.16 1,1,1-Trichloroethane - 24.77**  **1,1-Dichloropropene 25.21 25.24**

**Carbon tetrachloride - 25.47**

**Benzene 26.10 -**  **1,2-Dichloroethane - 26.27**

**Trichloroethene 27.99 28.02**  **1,2-Dichloropropane - 28.66**

**Bromodichloromethane - 29.43**

**Dibromomethane - 29.59** 

**Toluene 31.95 -**  **1,1,2-Trichloroethane - 33.21**

**Tetrachloroethene 33.88 33.90 1,3-Dichloropropane - 34.00** 

**Dibromochloromethane - 34.73 1,2-Dibromoethane - 35.34** 

**Chlorobenzene 36.56 36.59**  **Ethylbenzene 36.72 -**  **1,1,1,2-Tetrachloroethane - 36.80 m-Xylene**  **36.98 - p-Xylene**  **36.98 - o-Xylene**  **38.39 - Styrene**  **38.57 - Isopropylbenzene 39.58 -** 

**Bromoform - 39.75**  **1,1,2,2-Tetrachloroethane - 40.35 1,2,3-Trichloropropane - 40.81**  **n-Propylbenzene 40.87 -**

**Bromobenzene 40.99 41.03**  **1,3,5-Trimethylbenzene 41.41 -**

**2-Chlorotoluene 41.41 41.45**

**4-Chlorotoluene 41.60 41.63 SW-846 Update V 8021B - 16 Revision 3** 

**October 2012 Analyte**  **PID**

**Ret. Time a** 

**minute HECD** 

**Ret. Time**

**minute**

**tert-Butylbenzene 42.92 - 1,2,4-Trimethylbenzene 42.71 -**  **sec-Butylbenzene 43.31 - p-Isopropyltoluene 43.81 -**  **1,3-Dichlorobenzene 44.08 44.11 1,4-Dichlorobenzene 44.43 44.47**  **n-Butylbenzene 45.20 -**  **1,2-Dichlorobenzene 45.71 45.74 1,2-Dibromo-3-Chloropropane - 48.57** 
**1,2,4-Trichlorobenzene 51.43 51.46**

**Hexachlorobutadiene 51.92 51.96 Naphthalene**  **52.38 - 1,2,3-Trichlorobenzene 53.34 53.37** 

**Internal Standards**

**Fluorobenzene 26.84 - 2-Bromo-1-chloropropane**  **- 33.08**

**a Retention times determined on 60 m x 0.75 mm ID VO**  **COL capillary column. Program:**

**Hold at 10** ° **C for 8 min, then program at 4** ° **C/min to 180** ° **C, and hold until all expected compounds have eluted.** 

**b Dash (-) indicates detector does not respond.** **SW-846 Update V 8021B - 17 Revision 3**

**October 2012 TABLE 2** 

**SINGLE LABORATORY ACCURACY AND PRECISION DATA**

**FOR VOLATILE ORGANIC COMPOUNDS IN WATER a** 

**Analyte PID HECD** 

**Standard Recovery,**  **b**

**% Deviation** 

**of Recovery**  **Standard**

**Recovery, b** 

**% Deviation** 

**of Recovery** 

**Benzene 99 1.2 - c** 

**- Bromobenzene 99 1.7 97 2.7** 

**Bromochloromethane - - 96 3.0**

**Bromodichloromethane - - 97 2.9**

**Bromoform - - 106 5.5**

**Bromomethane - - 97 3.7 n-Butylbenzene 100 4.4 - -**  **sec-Butylbenzene 97 2.3 - - tert-Butylbenzene 98 2.3 - -** 

**Carbon tetrachloride - - 92 3.3**

**Chlorobenzene 100 1.0 103 3.7**

**Chloroethane - - 96 3.8**

**Chloroform - - 98 2.5**

**Chloromethane - - 96 8.9**

**2-Chlorotoluene ND d**  **ND 97 2.6**

**4-Chlorotoluene 101 1.0 97 3.1**
**1,2-Dibromo-3- chloropropane**  **- - 86 9.9**

**Dibromochloromethane - - 102 3.3 1,2-Dibromoethane - - 97 2.7** 

**Dibromomethane - - 109 7.4 1,2-Dichlorobenzene 102 2.1 100 1.5**  **1,3-Dichlorobenzene 104 1.7 106 4.3 1,4-Dichlorobenzene 103 2.2 98 2.3** 

**Dichlorodifluoromethane - - 89 5.9 1,1-Dichloroethane - - 100 5.7**  **1,2-Dichloroethane - - 100 3.8 1,1-Dichloroethene 100 2.4 103 2.9**  **cis-1,2-Dichloroethene ND ND 105 3.5 trans-1,2-Dichloroethene 93 3.7 99 3.7**  **1,2-Dichloropropane - - 103 3.8 1,3-Dichloropropane - - 100 3.4**  **2,2-Dichloropropane - - 105 3.6 1,1-Dichloropropene 103 3.6 103 3.4**  **Ethylbenzene 101 1.4 - -**

**Hexachlorobutadiene 99 9.5 98 8.3 Isopropylbenzene 98 0.9 - -**  **p-Isopropyltoluene 98 2.4 - - Methylene chloride - - 97 2.8**  **Naphthalene 102 6.3 - - n-Propylbenzene 103 2.0 - -**  **Styrene 104 1.4 - - SW-846 Update V 8021B - 18 Revision 3** 

**October 2012 Analyte**  **PID HECD**

**Standard Recovery,**  **b**

**% Deviation** 

**of Recovery**  **Standard**

**Recovery, b** 

**% Deviation** 

**of Recovery** 
**1,1,1,2-Tetrachloroethane - - 99 2.3 1,1,2,2-Tetrachloroethane - - 99 6.8** 

**Tetrachloroethene 101 1.8 97 2.4**

**Toluene 99 0.8 - - 1,2,3-Trichlorobenzene 106 1.9 98 3.1**  **1,2,4-Trichlorobenzene 104 2.2 102 2.1 1,1,1-Trichloroethane - - 104 3.4**  **1,1,2-Trichloroethane - - 109 6.2**

**Trichloroethene 100 0.78 96 3.5**

**Trichlorofluoromethane - - 96 3.4 1,2,3-Trichloropropane - - 99 2.3**  **1,2,4-Trimethylbenzene 99 1.2 - - 1,3,5-Trimethylbenzene 101 1.4 - -**  **Vinyl chloride 109 5.4 95 5.6 o-Xylene 99 0.8 - -**  **m-Xylene 100 1.4 - - p-Xylene 99 0.9 - -** 

**a This method was tested in a single laboratory usin**  **g water spiked at 10 μg/L.**

**b Recoveries and standard deviations were determined**  **from seven samples and spiked at 10 μg/L of each analyte. Recoveries were determine**  **d by internal standard method using a purge and trap. Internal standards were: F**  **luorobenzene for PID, 2-Bromo-1- chloropropane for HECD.** 

**c Detector does not respond.** 

**d ND = Not determined** **SW-846 Update V GAS CHROMATOGRAM OF VOLATILE ORGANICS** 

**8021B - 19 FIGURE 1** 

**GAS CHROMATOGRAM OF VOLATILE ORGANICS**

**Revision 3**

**October 2012 SW-846 Update V 8021B - 20 Revision 3** 

**October 2012 METHOD 8021B** 

**AROMATIC AND HALOGENATED VOLATILES BY GAS CHROMATOG RAPHY USING** 

**PHOTOIONIZATION AND/OR ELECTROLYTIC CONDUCTIVITY DE TECTORS** **SW-846 Update V 8021B - 21 Revision 3**

**October 2012 Appendix A**  **Changes in this version from the December 1996, Rev ision 2.** 

**1. Improved overall method formatting for consisten cy with new SW-846 methods style**  **guidance. The format was updated to Microsoft Word 2007.docx. This includes the**  **additions of all sections required by the new forma t.** 

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

**3. The revision number was changed to 3 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.**

**6. References to method detection limits (MDLs) wer e removed from the method.**  **Language describing LLOQ was added.**