SW-846 Update V 8111-1 Revision 1 

 July 2014 

METHOD 8111 

 HALOETHERS BY GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION 

1.1 Method 8111 is a gas chromatographic method used to determine the 

concentration of haloethers. It describes wide-bore, open tubular, capillary column gas 

chromatography procedures using a dual column/dual detector approach. However, a single 

column/single detector approach is acceptable. The following Resource Conservation and 

Recovery Act (RCRA) analytes have been determined by this method: 

 Compound CAS No.a

 Bis(2-chloroethoxy) methane 111-91-1 

 Bis(2-chloroethyl) ether 111-44-4 

 Bis(2-chloro-1-methylethyl) etherb108-60-1 

 4-Chlorophenyl phenyl ether 7005-72-3 

a

 Chemical Abstracts Service (CAS) Registry Number 

b

 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. 

1.2 The following additional haloether compounds may also be analyzed by this 

method: 

 Compound CAS No. 

 4-Bromophenyl phenyl ether 101-55-3 

 2-Chlorophenyl 4-nitrophenyl ether 209-61-4 

 3-Chlorophenyl 4-nitrophenyl ether 2303-23-3 

 4-Chlorophenyl 4-nitrophenyl ether 1836-74-4 

 2,4-Dibromophenyl 4-nitrophenyl ether 2671-93-4 

 2,4-Dichlorophenyl 3-methyl-4-nitrophenyl ether 42488-57-3 

 2,6-Dichlorophenyl 4-nitrophenyl ether 2093-28-9 

 3,5-Dichlorophenyl 4-nitrophenyl ether NA 

 2,5-Dichlorophenyl 4-nitrophenyl ether 391-48-7 

 2,4-Dichlorophenyl 4-nitrophenyl ether 1836-75-5 

 2,3-Dichlorophenyl 4-nitrophenyl ether 82239-20-1 

 3,4-Dichlorophenyl 4-nitrophenyl ether 22532-80-5 

 4-Nitrophenyl phenyl ether 620-88-2 

 2,4,6-Trichlorophenyl 4-nitrophenyl ether 1836-77-7 

 2,3,6-Trichlorophenyl 4-nitrophenyl ether NA 

 2,3,5-Trichlorophenyl 4-nitrophenyl ether NA 

 2,4,5-Trichlorophenyl 4-nitrophenyl ether 22532-68-9 

 3,4,5-Trichlorophenyl 4-nitrophenyl ether NA 
SW-846 Update V 8111-2 Revision 1 

 July 2014 

 2,3,4-Trichlorophenyl 4-nitrophenyl ether NA 

NA = CAS numbers not assigned at this time. 

1.3 This method is restricted to use by, or under supervision of, analysts experienced in 

the use of a gas chromatograph (GC) and in the interpretation of gas chromatograms. 

2.0 SUMMARY OF METHOD 

2.1 Method 8111 provides GC conditions for the detection of ppb concentrations of 

haloethers in water and soil or ppm concentrations in waste samples. 

2.2 Prior to use of this method, appropriate sample extraction techniques must be used 

for environmental samples (refer to Chapter Two and Method 3500). 

2.3 Both neat and diluted organic liquids (Method 3580) may be analyzed by direct 

injection. 

2.4 Analysis is accomplished by GC utilizing an instrument equipped with a wide-bore 

capillary column and an electron capture detector (ECD). 

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 Methods 3500, 3600, and 8000. 

4.2 The ECD responds to all electronegative compounds. Therefore, interferences are 

possible by other halogenated compounds, as well as phthalates and other oxygenated 

compounds such as organonitrogen, organosulfur, and organophosphorus compounds. Second 

column confirmation or gas chromatography/mass spectrometry (GC/MS) confirmation is 

necessary to ensure proper analyte identification unless previous characterization of the sample 

source will ensure proper identification. 

4.3 Dichlorobenzenes are known to co-elute with haloethers under some GC 

conditions. If these materials are present in a sample, it may be necessary to analyze the extract 

with two different column packings to completely resolve all of the compounds. 

4.4 Contamination by carryover can occur whenever high concentration and low 

concentration samples are sequentially analyzed. To reduce carryover, the syringe used for 

injection must be thoroughly rinsed between samples with solvent. Whenever a highly 

concentrated sample is encountered, it should be followed by the analysis of a solvent blank to 

check for cross-contamination. Additional solvent blanks interspersed with the sample extracts 

should be considered whenever the analysis of a solvent blank indicates cross-contamination 

problems. 
SW-846 Update V 8111-3 Revision 1 

 July 2014 

4.5 Some compounds co-elute using this procedure. In these cases, the compounds 

must be reported as co-eluting. The mixture may be reanalyzed for peak confirmation by 

GC/MS techniques if concentration permits (see Method 8270). 

 4.6 Solvents, reagents, glassware, and other sample processing hardware may yield 

discrete artifacts and/or elevated baselines causing misinterpretation of gas chromatograms. All 

these materials must be demonstrated to be free from interferences under the condition of the 

analysis, by analyzing reagent blanks. 

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 

Occupational Health and Safety Administration (OSHA) regulations regarding the safe handling 

of the chemicals and instrumentation included in this method. A reference file of material safety 

data sheets should be available to all personnel involved in these analyses. 

6.0 EQUIPMENT AND SUPPLIES 

6.1 GC – An analytical system complete with a GC suitable for on-column and 

split/splitless injection, and all necessary accessories, including syringes, analytical columns, 

gases, and two ECDs. A data system for measuring peak areas and/or peak heights is 

recommended. 

6.2 Suggested GC columns – Alternative columns may be used to provide the 

separation required to resolve all target analytes listed in Sec. 1.1 of this method. Refer to 

Chapter 1 and Method 8000 for additional information regarding quality control (QC) 

requirements and column performance. 

6.2.1 Column 1 – 30 m x 0.53 mm ID fused silica open tubular column, crosslinked and chemically bonded with 95 percent dimethyl and 5 percent 

diphenyl-polysiloxane (DB-5, RTx-5, SPB-5, or equivalent), 0.83 μm or 1.5 μm film 

thickness 

6.2.2 Column 2 – 30 m x 0.53 mm ID fused silica open tubular column crosslinked and chemically bonded with 14 percent cyanopropylphenyl and 86 percent 

dimethyl-polysiloxane (DB-1701, RTx-1701, or equivalent), 1.0 μm film thickness 

6.3 Column rinsing kit (optional) – Bonded-phase column rinse kit (Agilent, Catalog no. 

430-3000 or equivalent) 

6.4 Microsyringes – 100 μL, 50 μL, 10 μL (Hamilton 701 N or equivalent), and 50 μL 

(Blunted, Hamilton 705SNR or equivalent) 

6.5 Balances – Analytical, capable of accurately weighing 0.0001 g, and top-loading, 

capable of accurately weighing 0.01 g 

6.6 Volumetric flasks, Class A – 10 mL to 1000 mL 
SW-846 Update V 8111-4 Revision 1 

 July 2014 

7.0 REAGENTS AND STANDARDS 

7.1 Reagent-grade chemicals shall be used in all tests. Unless otherwise indicated, it 

is intended that all reagents 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 Solvents – All solvents must be pesticide quality or equivalent. 

7.2.1 Hexane, C6H14

7.2.2 Acetone, CH3COCH3

7.2.3 Isooctane, (CH3)3CCH2CH(CH3)2

7.3 Stock standard solutions (1000 mg/L) – May be prepared from pure standard 

materials or can be purchased as certified solutions 

 

7.3.1 Prepare stock standard solutions by accurately weighing about 0.0100 g 

of pure compound. Dissolve the compound in isooctane or hexane and dilute to volume in 

a 10-mL volumetric flask. If compound purity is 96 percent or greater, the weight can be 

used without correction to calculate the concentration of the stock standard solution. 

Commercially prepared stock standard solutions may be used at any concentration if they 

are certified by the manufacturer or by an independent source. 

7.3.2 For those compounds which are not adequately soluble in hexane or 

isooctane, dissolve the compound initially with a small volume of toluene, ethyl acetate or 

acetone and dilute to volume with isooctane or hexane. 

7.4 Composite stock standard – This standard can be prepared from individual stock 

solutions. For composite stock standards containing less than twenty-five components, transfer 

exactly 1 mL of each individual stock solution at 1000 mg/L, add solvent, mix the solutions, and 

bring to volume in a 25 mL volumetric flask. For example, for a composite containing twenty 

individual standards, the resulting concentration of each component in the mixture, after the 

volume is adjusted to 25 mL, will be 40 mg/L. This composite solution can be further diluted to 

obtain the desired concentrations. 

7.5 Calibration standards – These should be prepared at a minimum of five 

concentrations with dilution of the composite stock standard with isooctane or hexane. The 

standard concentrations should correspond to the expected range of concentrations present in 

the field samples and should bracket the linear range of the detector. 

7.6 Recommended internal standard – Prepare a solution of 1000 mg/L of 

4,4'-dibromobiphenyl. For spiking, dilute this solution to 50 ng/μL. (This concentration may need 

to be more dilute depending on the detector sensitivity. The internal standard response should 

be approximately 50 to 90% of full scale.) Use a spiking volume of 10 μL/ml of extract. The 

spiking concentration of the internal standards should be kept constant for all samples and 

calibration standards. Store the internal standard spiking solutions at 4 °C in 

polytetrafluoroethylene (PTFE) sealed containers in the dark. 

7.7 Recommended surrogate standards – The performance of the method should be 

monitored using surrogate compounds. Surrogates are added to all samples, method blanks, 

matrix spikes, and calibration standards. Prepare a solution of 1000 mg/L each of 

2,4-dichlorodiphenyl ether and 2,3,4-trichlorodiphenyl ether and dilute them to 20 ng/μL. Use a 
SW-846 Update V 8111-5 Revision 1 

 July 2014 

spiking volume of 100 μL for a 1 L aqueous sample. (This concentration may need to be 

adjusted depending on the detector sensitivity. The surrogate standard response should be 

approximately 100% of full scale.) 

7.8 Store the standard solutions (stock, composite, calibration, internal, and surrogate) 

at 4°C or cooler in PTFE-sealed containers in the dark. All standard solutions must be replaced 

after six months or sooner if routine QC (Sec. 9.0) indicates a problem. 

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 

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

8.2 Extracts should be stored in the dark at or below 4 °C and be analyzed within 40 

days of extraction. 

9.0 QUALITY CONTROL 

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. 
SW-846 Update V 8111-6 Revision 1 

 July 2014 

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 quality control 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, 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 Before processing any samples, the analyst should demonstrate (through 

the analysis of a method blank) that interferences from the analytical system, glassware, 

and reagents are under control. Each time a set of samples is analyzed or there is a 

change in reagents, a method blank should be analyzed as a safeguard against chronic 

laboratory contamination. The blanks should be carried through all stages of sample 

preparation and measurement. 

 9.4.2 Documenting 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 

duplicate pair. The decision on 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, then 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. 

 9.4.3 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 that the laboratory 

can perform the analysis in a clean matrix. 

 9.4.4 See Method 8000, Sec. 9 for the details on carrying out sample QC 

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 for information on evaluating surrogate data and developing and updating 

surrogate limits. 

 9.6 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. 

9.7 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. 
SW-846 Update V 8111-7 Revision 1 

 July 2014 

10.0 CALIBRATION AND STANDARDIZATION 

10.1 Prepare calibration standards using the procedures in Sec. 7.0. Refer to Method 

8000 for proper calibration procedures. The procedure for internal or external calibration may be 

used. 

10.2 Refer to Method 8000 for procedures for establishing retention time windows. 

11.0 PROCEDURE 

11.1 Extraction and cleanup 

11.1.1 Refer to Chapter Two and Method 3500 for guidance on choosing the 

appropriate extraction procedure. In general, water samples are extracted at a neutral, or 

as-is, pH with methylene chloride, using either Method 3510 or 3520. Solid samples are 

extracted using any of the extraction methods for solids listed in Method 3500, as 

appropriate. 

11.1.2 If necessary, the samples may be cleaned up using Method 3620 (Florisil) 

and/or Method 3640 (Gel Permeation Chromatography). See Chapter Two and Method 

3600 for general guidance on cleanup and method selection. Method 3660 may be used 

for sulfur removal. 

11.1.3 Prior to gas chromatographic analysis, the extraction solvent should be 

exchanged to hexane. The exchange is performed during the Kuderna Danish (KD) 

procedures listed in each of the extraction methods. Any methylene chloride remaining in 

the extract will cause a very broad solvent peak. 

NOTE: Some of the haloethers are very volatile and significant losses will occur in 

concentration steps, if care is not exercised. It is important to maintain a 

 constant, gentle evaporation rate and not to allow the liquid volume to fall 

below 1 to 2 mL before the K-D apparatus is removed from the hot water 

bath. 

11.2 GC conditions – Retention time information for each of the target analytes is 

presented in Table 1. Retention times of additional haloether compounds are presented in 

Table 2. GC operating conditions under which these retention times were obtained are 

provided in the appropriate table. Figures 1 and 2 illustrate typical chromatography of the 

haloethers. 

11.3 Calibration 

11.3.1 Prepare calibration standards using the procedures in Sec. 7. Refer to 

Method 8000 for proper calibration procedures. The procedure for internal or external 

calibration may be used. 

11.3.2 Refer to Method 8000 for procedures for establishing retention time 

windows. 
SW-846 Update V 8111-8 Revision 1 

 July 2014 

11.4 Gas chromatographic analysis 

11.4.1 Method 8000 provides instructions on calibration, establishing retention 

time windows, the analysis sequence, appropriate dilutions, and identification criteria. 

11.4.2 Automatic injections of 1 μL are recommended. Hand injections of no 

more than 2 μL may be used if the analyst demonstrates quantitation precision of ≤10 

percent relative standard deviation (RSD). The solvent flush technique may be used if the 

amount of solvent is kept at a minimum. If the internal standard calibration technique is 

used, add 10 μL of the internal standard to each 1 mL of sample extract prior to injection. 

11.4.3 Tentative identification of an analyte occurs when a peak from a sample 

extract falls within the absolute retention time window. Normally, confirmation is required. 

Confirmation techniques include analysis on a second column with dissimilar stationary 

phase, by GC/MS (full scan or selected ion monitoring (SIM)), or by using a different 

detector and getting comparable data. See Method 8000 for further information. 

11.4.3.1 If partially overlapping or co-eluting peaks are present, install 

columns with a dissimilar liquid phase or use a GC/MS technique. 

11.4.3.2 Interferences that prevent analyte identification and/or 

quantitation may possibly be removed by the cleanup techniques mentioned above. 

11.4.4 Record both the volume injected (to the nearest increment) and the 

resulting peak size in area units or peak height. Using either the internal or the external 

calibration procedure (Method 8000), determine the quantity of each component peak in 

the sample chromatogram which corresponds to the compounds used for calibration 

purposes. 

11.4.5 If the responses exceed the linear range of the system, dilute the extract 

and reanalyze. Peak height measurements are recommended, rather than peak area 

integration, when overlapping peaks may cause errors in area integration. 

11.4.6 If the peak response is less than 2.5 times the baseline noise level, the 

validity of the quantitative result may be questionable. The analyst should consult with the 

source of the sample to determine whether further concentration of the sample is 

warranted. 

11.4.7 Determine the concentration of each identified analyte using the 

calculation formulas in Sec. 11 of Method 8000. 

11.5 Instrument maintenance 

11.5.1 Injection of sample extracts from waste sites often leaves a high boiling 

residue in the injection port area, splitters (when used), and the injection port end of the 

chromatographic column. This residue affects chromatography in many ways (e.g., peak 

tailing, retention time shifts, analyte degradation, etc.). Therefore, instrument maintenance 

is very important. Residue buildup in a splitter may limit flow through one leg and, 

therefore, change the split ratios. If this occurs during an analytical run, the quantitative 

data may be incorrect. Proper cleanup techniques will minimize the problem and 

instrument QC will indicate when instrument maintenance is required. 

11.5.2 Suggested chromatograph maintenance – Corrective measures may 

require remedial actions. 
SW-846 Update V 8111-9 Revision 1 

 July 2014 

11.5.2.1 Column rinsing – The column should be rinsed with several 

column volumes of an appropriate solvent. Both polar and nonpolar solvents are 

recommended. Depending on the nature of the sample residues expected, the first 

rinse might be water, followed by methanol and acetone; methylene chloride is a 

satisfactory final rinse and in some cases may be the only solvent required. The 

column should then be filled with methylene chloride and allowed to remain flooded 

overnight to allow materials within the stationary phase to migrate into the solvent. 

The column is then flushed with fresh methylene chloride, drained, and dried at 

room temperature with a stream of ultrapure nitrogen passing through the column. 

11.5.2.2 See Method 8000 for additional guidance on corrective action 

for capillary columns and the injection port. 

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 

13.1 Table 1 lists the retention times and recoveries of the target analytes. The 

recoveries presented were obtained from the analysis of spiked sandy loam soils. No recovery 

data is currently available on Bis(2-chloro-ethoxy) methane and Bis(2-chloroethyl) ether. 

13.2 Table 2 lists the compounds that may be determined by this method and their 

retention times. Figure 1 shows a chromatogram of the target analytes eluted from a pair of 

DB-5/DB-1701 columns and detected with ECD under the GC conditions listed 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 Environmental Protection Agency (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 
SW-846 Update V 8111-10 Revision 1 

 July 2014 

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 web address listed 

in Sec. 14.2 above. 

16.0 REFERENCES 

1. V. Lopez-Avila, E. Baldin, J. Benedicto, J. Milanes and W. F. Beckert, "Application of 

Open-Tubular Columns to SW-846 GC Methods," final report to the U.S. EPA on Contract 

68-03-3511, Mid-Pacific Environmental Laboratory, Mountain View, CA, 1990. 

2. S. Tsang, P. Marsden and N.Chau, "Performance Data for Methods 8041, 8091, 8111, and 

8121A," draft report to U.S. EPA on Contract 68-W9-0011, Science Applications 

International Corp., San Diego, CA, 1992. 

17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA 

The following pages contain the tables referenced by this method. 
SW-846 Update V 8111-11 Revision 1 

 July 2014 

TABLE 1 

RETENTION TIMES AND RECOVERIES OF TARGET HALOETHERS

Analyte 

RT 

(min) 

Spiking Conc. 

(μg/g) 

Recovery 

(%) 

RSD 

(%) 

Bis(2-chloro-1-methylethyl) ether 3.06 2.5 112 4.3 

4-Chlorophenyl phenyl ether 15.75 5.0 91.5 3.5 

4-Bromophenyl phenyl ether 18.21 0.5 97.0 2.1 

 Column: DB-5, 30 m x 0.53 mm ID 

 Temperature program: 125 °C (1.0 min hold) to 135 °C at 2 °C/min 

 135 °C to 200 °C at 5 °C/min 

 200 °C to 275 °C at 10 °C/min, (3.5 min hold) 

 Injector: Packed, wide-bore liner 

 Injector temperature: 200 °C 

 Detector: ECD 

 Detector temperature: 320 °C 

 Nitrogen carrier gas: 5 mL/min 

 Nitrogen makeup gas: 55 mL/min 
SW-846 Update V 8111-12 Revision 1 

 July 2014 

TABLE 2 

 RETENTION TIMES OF ADDITIONAL HALOETHER COMPOUNDS 

Peaka

 Compound 

Retention Time (min) 

DB-5 DB-1701 

 

1 4-Bromophenyl-phenyl ether 4.28 5.57 

2 Phenyl 4-nitrophenyl ether 6.85 10.86 

3 2-Chlorophenyl 4-nitrophenyl ether 10.44 16.31 

4 3-Chlorophenyl 4-nitrophenyl ether 10.78 16.70 

5 4-Chlorophenyl 4-nitrophenyl ether 11.37 17.68 

6 2,6-Dichlorophenyl 4-nitrophenyl ether 14.02 20.84 

7 3,5-Dichlorophenyl 4-nitrophenyl ether 14.55 21.33 

8 2,5-Dichlorophenyl 4-nitrophenyl ether 14.55 21.54 

9 2,4-Dichlorophenyl 4-nitrophenyl ether 15.08 22.30 

10 2,3-Dichlorophenyl 4-nitrophenyl ether 16.11 23.87 

11 3,4-Dichlorophenyl 4-nitrophenyl ether 16.65 24.54 

12 2,4,6-Trichlorophenyl 4-nitrophenyl ether 17.89 24.93 

13 2,3,6-Trichlorophenyl 4-nitrophenyl ether 19.40 27.27 

14 2,3,5-Trichlorophenyl 4-nitrophenyl ether 19.70 27.56 

15 2,4,5-Trichlorophenyl 4-nitrophenyl ether 20.03 28.05 

16 2,4-Dibromophenyl 4-nitrophenyl ether 21.63 30.03 

17 3,4,5-Trichlorophenyl 4-nitrophenyl ether 21.83 30.42 

18 2,3,4-Trichlorophenyl 4-nitrophenyl ether 22.28 31.18 

19 2,4-Dichlorophenyl 3-methyl-4-nitrophenyl ether 21.83 31.60 

 

IS 4,4’-Dibromobiphenyl 9.44 12.66 

SU-1 2,4-Dichlorodiphenyl ether 4.82 6.17 

SU-2 2,3,4-Trichlorodiphenyl ether 8.31 10.95 

a

 Peak numbers refer to the chromatogram in Figure 2. 

IS=Internal Standard 

SU=Surrogate 

The GC operating conditions for the above analysis were as follows: 

Columns: 30 m x 0.53 mm ID DB-5 (0.83 μm film thickness) and 30 m x 

0.53 mm ID DB-1701 (1.0 μm film thickness) connected to an 8 

in. injection tee (Supelco, Inc.). 

Temperature program: 180 °C (0.5 min hold) to 260 °C (1.0 min hold) at 2 °C/min 

Injector temperature: 250 °C 

Detector temperature: 320 °C 

Helium carrier gas: 6 mL/min 

Nitrogen makeup gas: 20 mL/min 
SW-846 Update V 8111-13 Revision 1 

 July 2014 

FIGURE 1 

GC/ECD CHROMATOGRAM OF TARGET ANALYTE HALOETHERS 

ANALYZED ON A DB-5 CAPILLARY COLUMN FOR RECOVERY STUDIES 

The GC operating conditions are listed in Table 1. 
SW-846 Update V 8111-14 Revision 1 

 July 2014 

FIGURE 2 

 GC/ECD CHROMATOGRAM OF HALOETHERS ANALYZED ON A 

 DB-5/DB-1701 FUSED-SILICA OPEN-TUBULAR COLUMN PAIR

 The GC operating conditions are listed in Table 2.
SW-846 Update V 8111-15 Revision 1 

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METHOD 8111 

HALOETHERS BY GAS CHROMATOGRAPHY 
SW-846 Update V 8111-16 Revision 1 

 July 2014 

Appendix A 

Changes in this version from the December 1996, Revision 0. 

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 1 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. The method flowchart on page 15 was updated to reflect the current section numbers.