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July 2014 

METHOD 8021B 

AROMATIC AND HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING 

PHOTOIONIZATION AND/OR ELECTROLYTIC CONDUCTIVITY DETECTORS

1.0 SCOPE AND APPLICATION 

1.1 Method 8021 is used to determine volatile organic compounds in a variety of solid 

waste matrices. This method is applicable to nearly all types of samples, regardless of water 

content, including ground water, aqueous sludges, caustic liquors, acid liquors, waste solvents, 

oily wastes, mousses, tars, fibrous wastes, polymeric emulsions, filter cakes, spent carbons, 

spent catalysts, soils, and sediments. The following compounds can be determined by this 

method: 

Appropriate Technique 

Analyte CAS No.a Purge and 

Trap 

Direct 

Injection 

Vacuum 

Distillation 

Headspace 

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 
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Appropriate Technique 

Analyte CAS No.a Purge and 

Trap 

Direct 

Injection 

Vacuum 

Distillation 

Headspace 

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 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. 

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 technique (e.g., azeotropic 

distillation, equilibrium headspace or vacuum distillation) 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. Analytes that are inefficiently purged from 

water will not be detected when present at low concentrations, but they can be measured with 
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acceptable accuracy and precision when present in sufficient amounts. Determination of some 

structural isomers (i.e., xylenes) may be hampered by coelution. 

1.3 Lower Limit of Quantitation (LLOQ) - The laboratory shall establish the LLOQ as 

the lowest point of quantitation, which in most cases is the lowest concentration in the 

calibration curve. LLOQ verification is recommended for each project application to validate 

quantitation capability at low analyte concentration 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 sample 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. LLOQs will be proportionately higher for 

sample extracts and samples that require dilution or 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 measurement of purgeable organics at low 

μg/L concentrations and skilled in the interpretation of gas chromatograms. Each analyst must 

demonstrate the ability to generate acceptable results with this method. 

1.5 The toxicity or carcinogenicity of chemicals used 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 laboratory is responsible for maintaining 

awareness of Occupational Safety and Health Administration (OSHA) regulations regarding safe 

handling of chemicals used in this method. 

 

1.6 The following method analytes have been tentatively classified as known or 

suspected human or mammalian carcinogens: carbon tetrachloride, 1,4-dichlorobenzene, 1,2-

dichloroethane, hexachlorobutadiene, 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane, 

chloroform, 1,2-dibromoethane, tetrachloroethene, trichloroethene, 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 
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a

 Chemical Abstracts Service Registry Number 

2.0 SUMMARY OF METHOD 

2.1 Method 8021 provides gas chromatographic conditions for the detection of 

halogenated and aromatic volatile organic compounds. Samples can be analyzed using direct 

injection (Method 3585 for oily matrices), purge and 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 compounds. Detection is achieved by a 

photoionization detector (PID) and a Hall electrolytic conductivity detector (HECD) in series. 

The GC system may also be set up to use a single detector when an analyst is looking for only 

halogenated compounds (HECD) or aromatic compounds (PID). 

2.2 Tentative identifications are obtained by analyzing 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 measured by relating the response produced 

for that compound to the response produced by a compound 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 volatile organics (particularly 

chlorofluorocarbons and methylene chloride) through the sample container septum during 

shipment and storage. A trip blank prepared from organic-free reagent water and carried 

through sampling and subsequent storage and handling can serve as a check on such 

contamination. 

4.3 Sulfur dioxide is a potential interferant in the analysis for vinyl chloride. 

5.0 SAFETY 

This method does not address all safety issues associated 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 chemicals and instrumentation included in this 

method. A reference file of material safety data sheets (MSDSs) should be available to all 

personnel involved in these analyses. 

6.0 EQUIPMENT AND SUPPLIES 
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6.1 Sample introduction apparatus – Refer to the appropriate 5000 Series method for a 

listing of the equipment for each sample introduction technique. 

6.2 GC – capable of temperature programming; equipped with variable-constant 

differential flow controllers, subambient oven controller, PID and HECD connected with a short 

piece of uncoated capillary tubing, 0.32 - 0.5 mm ID, 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 been suggested as one possible option. 

Other columns that will provide appropriate resolution of the target compounds may also 

be employed for confirmation, or confirmation may be 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 shut-off valve 

6.8 Bottles – 15 mL, PTFE-lined fitted with screw-cap 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 reagents shall conform to the specifications of the 

Committee on Analytical Reagents of the American Chemical 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 its 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, CH3OH – Pesticide quality or equivalent, demonstrated to be free of 

analytes. Store away from other solvents. 
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7.4 Vinyl chloride, (99.9% pure), CH2CHCl – Vinyl chloride is available from Ideal Gas 

Products, Inc., Edison, New Jersey and from Matheson, 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. Prepare 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 prepared in a hood. 

NOTE: If direct injection is used, the solvent system of standards must match that of the 

sample. It is not necessary to prepare high concentration aqueous mixed standards 

when using direct injection. 

7.5.1 Place approximately 9.8 mL of methanol in a 10-mL tared ground glassstoppered volumetric flask. Allow the flask to stand, unstoppered, for about 10 minutes 

until all alcohol-wetted surfaces have dried. Weigh the flask to the nearest 0.1 mg. 

7.5.2 Add the assayed reference material, as described below. 

7.5.2.1 Liquids: Using a 100-μL syringe, immediately add two or more 

drops of assayed reference material to the flask; then reweigh. The liquid must fall 

directly into the alcohol without contacting the neck of the flask. 

7.5.2.2 Gases: To prepare standards for any compounds that boil 

below 30 °C (e.g., bromomethane, chloroethane, chloromethane,

dichlorodifluoromethane, trichlorofluoromethane, vinyl chloride), fill a 5-mL valved 

gas-tight syringe with the reference standard to the 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 heavy 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 relief 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, the weight may be used without 

correction to calculate the concentration of the stock 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 bottle fitted with a PTFE-lined 

screw cap or crimp top. Store, with minimal headspace, at -10 °C to -20 °C and protect 

from light. Standards should be returned to the freezer as soon as the analyst has 

completed mixing or diluting the standards to prevent the evaporation of volatile target 

compounds. 
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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. Standards for gases usually need to be 

replaced after one week or as recommended by the standard 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 when standards are held beyond 

one week. 

7.5.5.2 Standards for the non-gases should be monitored frequently 

by comparison to the initial calibration. Fresh standards 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. Standards of reactive 

compounds such as 2-chloroethyl vinyl ether and styrene may need to be prepared 

more frequently. 

7.6 Prepare secondary dilution standards, using stock 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 bracket the working range of the analytical 

system. Secondary dilution standards should be stored with minimal headspace for volatiles 

and should be checked frequently for signs of degradation or evaporation, especially just prior to 

preparing calibration standards from them. Secondary standards for gases should be replaced 

after one week unless the acceptability of the standard can be documented. When using 

premixed certified solutions, store according to the manufacturer's documented holding time 

and storage temperature recommendations. The analyst should also handle and store 

standards as stated in Sec. 7.5.4 and return them to 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 calibration verification standards. When using 

premixed certified solutions, store according to the manufacturer's documented holding time 

and storage temperature recommendations. 

7.7.1 Initial calibration standards should be prepared 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 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 typical samples but should not exceed 

the working range of the GC system. Initial calibration standards should be mixed from 

fresh stock standards and dilution standards when generating 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 premixed certified solution. Prepare these 

solutions in organic-free reagent water. See Sec. 11 of Method 8000 for guidance on 

calibration verification. 
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7.7.3 It is the intent of the Environmental Protection Agency (EPA or the 

Agency) that all target analytes for a particular analysis be included in the initial calibration 

and calibration verification standard(s). These target analytes may not include the entire 

list of analytes (Sec. 1.1) for which the method has been demonstrated. However, the 

laboratory must not report a quantitative result for 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 calibration is used. 

7.8 In order to prepare accurate aqueous standard solutions, 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 standards into 100 mL of water. 

7.8.2 Use a 25-μL Hamilton 702N micro syringe or equivalent (variations in 

needle geometry will adversely affect the ability to deliver reproducible volumes of 

methanolic standards into water). 

7.8.3 Rapidly inject the alcoholic standard into the filled volumetric flask. 

Remove the needle as fast as possible after injection. 

7.8.4 Mix aqueous standards by inverting the flask three times. 

7.8.5 Fill the sample syringe from the standard solution 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 samples or aqueous standards. 

7.8.7 Standards should be stored and handled according to guidance in Secs. 

7.5.4 and 7.5.5. 

7.9 Internal standards – It is recommended that a spiking solution containing 

fluorobenzene and 2-bromo-1-chloropropane in methanol be prepared, using the procedures 

described in Secs. 7.5 and 7.6. It is further recommended that the secondary dilution standard 

be prepared at a concentration of 5 mg/L of each internal standard compound. The addition of 

10 μL of such a standard to 5.0 mL of sample calibration standard would be equivalent to 10 

μg/L. External standard quantitation may also be used. 

7.10 Surrogate standards – The analyst should monitor both the performance of the 

analytical system and the effectiveness of the method in dealing with each sample matrix by 

spiking each sample, standard, and reagent blank with two or more surrogate compounds. A 

combination of 1,4-dichlorobutane and bromochlorobenzene is recommended to encompass the 

range of the temperature program used in this method. 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, and dilute to volume for a concentration of 

15 ng/μL. Add 10 μL of this surrogate spiking solution directly into the 5-mL syringe with every 

sample and reference standard analyzed. If the internal standard calibration procedure is used, 

the surrogate compounds may be added directly to the internal standard spiking solution (Sec. 

7.9). 
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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 assurance (QA) and QC protocols. When 

inconsistencies exist between QC guidelines, method-specific QC criteria take precedence over 

both technique-specific and Chapter One criteria; technique-specific QC criteria take 

precedence over Chapter One criteria. Any effort involving 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 Analysis Plan (SAP), which translates 

project objectives and specifications into directions 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 data 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, provided such limits will generate data appropriate 

for use in the intended application. All data sheets and QC data should be maintained for 

reference or inspection. 

9.2 Initial demonstration of proficiency (IDP) 

Prior to implementation of a method, each laboratory 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 significant change to instrumentation or 

procedure occurs, the laboratory must demonstrate that acceptable precision and bias can still 

be obtained by the changed conditions. Whenever new 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 analyst is responsible. This demonstration 

should document that the new analyst is capable of successfully following the standard 

operating procedure (SOP) established by the laboratory. 

9.3 QC procedures necessary to evaluate the GC system operation are found in 

Method 8000, Sec. 11 and include evaluation of retention time windows, calibration verification, 

and chromatographic analysis of samples. 

9.4 Sample QC for preparation and analysis – The laboratory 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 duplicate, and a laboratory control sample (LCS) in 

each analytical batch and the addition of surrogates to each field sample and QC sample. 

9.4.1 Documentation of the effect of the matrix should include the analysis of at 

least one matrix spike and one duplicate unspiked sample or one matrix spike/matrix spike 
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duplicate pair. The decision of whether to prepare and analyze duplicate samples or a 

matrix spike/matrix spike duplicate must be based on knowledge of the samples in the 

sample batch. If samples are expected to contain target analytes, laboratories may use 

one matrix spike and a duplicate analysis of an unspiked field sample. If samples are not 

expected to contain target analytes, laboratories should use a matrix spike and matrix 

spike duplicate pair. 

9.4.2 An LCS should be included with each analytical batch. The LCS consists 

of an aliquot of a clean (control) matrix similar to the sample matrix and of the same weight 

or volume. The LCS is spiked with the same analytes 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 are 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 carrying out sample quality 

control procedures for preparation and analysis. 

9.5 Surrogate recoveries – The laboratory must evaluate surrogate recovery data from 

individual samples versus the surrogate control limits developed by the laboratory. See Method 

8000, Sec. 9.0 for information on evaluating surrogate 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, chloroethane, chloromethane, 

dichlorodifluoromethane, trichlorofluoromethane, and 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 additional 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 relevant 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 sample introduction method that will be 

used to analyze actual samples (see Sec. 11.3.1). 

10.3 The procedure for internal or external calibration may be used. Refer to Method 

8000 for guidance on each of these procedures. 
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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 5030/5035), headspace (Method 5021), or by 

vacuum distillation (Method 5032). Methods 5021, 5030 or 5032 may be used directly on 

groundwater samples. Methods 5021, 5032 or 5035 may be used for low-concentration 

contaminated soils and sediments. For high-concentration 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 waste 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 series with the HECD. It may 

be helpful to contact the manufacturer of the GC for guidance on the proper installation of 

dual detector systems. 

 NOTE: Use of the dual detector system is not a requirement 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 additional 24 mL of helium flow 

before entering the PID. This make-up gas is necessary to ensure optimal response from 

both detectors. 

11.2.4 These halogen-specific systems eliminate misidentifications due to nonorganohalides which are coextracted during the purge step. A Tracor Hall Model 700-A 

detector was used to gather the example single laboratory accuracy and precision data 

presented in Table 2. The operating conditions used 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 column is presented in Figure 

1. This column was used to develop the method performance statements in Sec. 13. 

Estimated retention times that can be achieved under these conditions are given in Table 

1. Other columns or element-specific detectors may be used if the requirements of Sec. 9 

are met. 
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11.3 Gas chromatographic analysis 

11.3.1 Introduce volatile compounds into the GC using either Methods 

5030/5035 (purge-and-trap method) or the direct injection method (see Sec. 11.3.1.1), by 

Method 5021 (headspace) or by Method 5032 (vacuum distillation). If the internal 

standard calibration technique is used, add 10 μL of internal standard to the sample prior 

to purging. 

11.3.1.1 Direct injection – In very limited applications (e.g., aqueous 

process wastes), direct injection of the sample into 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 concentrations 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 purge-and-trap device). 

11.3.1.2 Refer to Method 3585 for guidance on the dilution and direct 

injection of waste oil samples. 

11.3.1.3 Samples may be purged at temperatures above those being 

recommended as long as all calibration standards, samples, and QC samples are 

purged at the same temperature and acceptable method performance is 

demonstrated. 

11.3.2 Follow Sec. 9 in Method 8000 for instructions on the analysis sequence, 

appropriate dilutions, establishing daily retention time windows, identification criteria, and 

calibration verification. Include a mid-concentration standard after each group of 10 

samples in the analysis sequence. 

11.3.3 Table 1 summarizes the estimated retention times 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 Method 8000. 

11.3.6 Second column confirmation – A 60-m x 0.53 ID SPB-624 wide-bore 

capillary column with 3.0-μm film thickness (Supelco) has been suggested as one possible 

option for confirming compound identifications. Other 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 with organic-free reagent water. The 

dilution must be performed on a second aliquot of the sample which has been properly 

sealed and stored prior to use. 

11.3.8 For target compounds that boil below 30 °C at 1 atm pressure (e.g., 

bromomethane, chloroethane, chloromethane, dichlorodifluoromethane, 

trichlorofluoromethane, and vinyl chloride), analysts may use a calibration verification 

acceptance criteria of within ± 20% difference from the initial calibration response. 
SW-846 Update V 8021B - 13 Revision 3 

July 2014 

12.0 DATA ANALYSIS AND CALCULATIONS 

12.1 See Method 8000, Sec. 11 for information regarding data analysis and 

calculations. 

12.2 Results must be reported in units commensurate 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 generation. Numerous opportunities for pollution 

prevention exist in laboratory operation. The EPA has established a preferred hierarchy of 

environmental management techniques that places pollution prevention as the management 

option of first choice. Whenever feasible, laboratory personnel should use pollution prevention 

techniques to address their waste generation. When wastes cannot be feasibly reduced at the 

source, the EPA recommends recycling as the next best option. 

14.2 For information about pollution prevention that 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, Committee on Chemical Safety, 

http://portal.acs.org/portal/fileFetch/C/WPCP_012290/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. Laboratories are urged to protect air, water, and land 

by minimizing and controlling all releases from hoods and bench operations, complying with the 

letter and spirit of any sewer discharge permits and regulations and complying with all solid and 

hazardous waste regulations, particularly the hazardous 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 

July 2014 

16.0 REFERENCES 

1. "Volatile Organic Compounds in Water by Purge-and-Trap Capillary Column Gas 

Chromatography with Photoionization and Electrolytic Conductivity Detectors in Series, 

Method 502.2, Rev. 2.0 (1989); Methods for the Determination of Organic Compounds in 

Drinking Water," U.S. Environmental Protection Agency, Environmental Monitoring 

Systems Laboratory, Cincinnati, OH, EPA/600/4-88/039, December, 1988. 

2. "The Determination of Halogenated Chemicals in Water 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 Compounds in Water by Purge and Trap Gas 

Chromatography, Method 503.1;" U.S. Environmental Protection Agency, Environmental 

Monitoring and Support Laboratory, Cincinnati, OH, September, 1986. 

4. J. A. Glaser, D. L. Forest, G. D. McKee, S. A. Quave, W. L. Budde, "Trace Analyses for 

Wastewaters," Environ. Sci. Technol., 1981, 15, 1426. 

5. T. A. Bellar, J. J. Lichtenberg, "The Determination of Synthetic Organic Compounds in 

Water by Purge and Sequential Trapping Capillary Column Gas Chromatography," U.S. 

Environmental Protection Agency, Environmental Monitoring and Support Laboratory, 

Cincinnati, OH, 45268. 

17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA 

The following pages contain the tables referenced by this method. 

 
SW-846 Update V 8021B - 15 Revision 3 

July 2014 

TABLE 1 

CHROMATOGRAPHIC RETENTION TIMES FOR VOLATILE ORGANIC COMPOUNDS WITH 

PID AND HECD DETECTORS 

Analyte 

PID 

Ret. Timea

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 

July 2014 

Analyte 

PID 

Ret. Timea

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 VOCOL 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 

July 2014 

TABLE 2 

SINGLE LABORATORY ACCURACY AND PRECISION DATA 

FOR VOLATILE ORGANIC COMPOUNDS IN WATERa

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 NDd

 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 

July 2014 

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 using 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 determined by internal standard method 

using a purge and trap. Internal standards were: Fluorobenzene 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 

July 2014 
SW-846 Update V 8021B - 20 Revision 3 

July 2014 

METHOD 8021B 

AROMATIC AND HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING 

PHOTOIONIZATION AND/OR ELECTROLYTIC CONDUCTIVITY DETECTORS 

 
SW-846 Update V 8021B - 21 Revision 3 

July 2014 

Appendix A 

Changes in this version from the December 1996, Revision 2. 

1. Improved overall method formatting for consistency with new SW-846 methods style 

guidance. The format was updated to Microsoft Word .docx. This includes the additions 

of all sections required by the new format. 

2. Many minor editorial and technical revisions were made throughout to improve method 

clarity. 

3. The revision number was changed to 3 and the date published was changed to July 

2014. 

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) were removed from the method. 

Language describing LLOQ was added.