**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 use d to determine the** 

**concentration of haloethers. It describes wide-bor e, 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 b y 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) ether b**  **108-60-1 4-Chlorophenyl phenyl ether**  **7005-72-3**

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

**b Chemical name was changed by the Integrated Risk I**  **nformation 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 ma y 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 ethe r 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 82239-2**  **0-1 3,4-Dichlorophenyl 4-nitrophenyl ether 22532-8**  **0-5 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 2253**  **2-68-9 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 s upervision of, analysts experienced in**  **the use of a gas chromatograph (GC) and in the inte rpretation of gas chromatograms.** 

**2.0 SUMMARY OF METHOD**

**2.1 Method 8111 provides GC conditions for the dete ction 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 3 580) may be analyzed by direct**  **injection.**

**2.4 Analysis is accomplished by GC utilizing an ins trument 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 compoun ds. 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 spec trometry (GC/MS) confirmation is**  **necessary to ensure proper analyte identification u nless previous characterization of the sample**  **source will ensure proper identification.**

**4.3 Dichlorobenzenes are known to co-elute with hal oethers under some GC**  **conditions. If these materials are present in a sam ple, it may be necessary to analyze the extract**  **with two different column packings to completely re solve all of the compounds.** 

**4.4 Contamination by carryover can occur whenever h igh concentration and low**  **concentration samples are sequentially analyzed. T o 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 fo llowed 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 sol vent 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 Meth**  **od 8270).**

**4.6 Solvents, reagents, glassware, and other sampl e processing hardware may yield** 

**discrete artifacts and/or elevated baselines causin g misinterpretation of gas chromatograms. All** 

**these materials must be demonstrated to be free fro m interferences under the condition of the**  **analysis, by analyzing reagent blanks.**

**5.0 SAFETY**

**This method does not address all safety issues asso ciated with its use. The laboratory is**  **responsible for maintaining a safe work environment and a current awareness file of**  **Occupational Health and Safety Administration (OSHA ) regulations regarding the safe handling** 

**of the chemicals and instrumentation included in th is method. A reference file of material safety**  **data sheets should be available to all personnel in volved in these analyses.** 

**6.0 EQUIPMENT AND SUPPLIES**

**6.1 GC – An analytical system complete with a GC su itable for on-column and**  **split/splitless injection, and all necessary access ories, including syringes, analytical columns,**  **gases, and two ECDs. A data system for measuring p eak 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 informatio n regarding quality control (QC)**  **requirements and column performance.**

**6.2.1 Column 1 – 30 m x 0.53 mm ID fused silica ope n tubular column, cross**  **linked and chemically bonded with 95 percent dimeth yl and 5 percent**  **diphenyl-polysiloxane (DB-5, RT**

**x -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 ope n tubular column cross**  **linked and chemically bonded with 14 percent cyanop ropylphenyl and 86 percent**  **dimethyl-polysiloxane (DB-1701, RT**

**x -1701, or equivalent), 1.0 μm film thickness** 

**6.3 Column rinsing kit (optional) – Bonded-phase co lumn 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 we ighing 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 te sts. Unless otherwise indicated, it**  **is intended that all reagents conform to the specif ications of the Committee on Analytical**  **Reagents of the American Chemical Society (ACS), wh ere such specifications are available.**  **Other grades may be used, provided it is first asce rtained that the reagent is of sufficiently high**  **purity to permit its use without lessening the accu racy of the determination.** 

**7.2 Solvents – All solvents must be pesticide quali ty or equivalent.** 

**7.2.1 Hexane, C 6**  **H 14** 

**7.2.2 Acetone, CH 3**  **COCH 3** 

**7.2.3 Isooctane, (CH 3**  **) 3**  **CCH 2**  **CH(CH 3**  **) 2** 

**7.3 Stock standard solutions (1000 mg/L) – May be p repared from pure standard**  **materials or can be purchased as certified solution s** 

**7.3.1 Prepare stock standard solutions by accuratel y weighing about 0.0100 g**  **of pure compound. Dissolve the compound in isoocta ne 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 concentrat ion 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 independ ent source.** 

**7.3.2 For those compounds which are not adequately soluble in hexane or**  **isooctane, dissolve the compound initially with a s mall volume of toluene, ethyl acetate or** 

**acetone and dilute to volume with isooctane or hexa ne.** 

**7.4 Composite stock standard – This standard can be prepared from individual stock**  **solutions. For composite stock standards containin g less than twenty-five components, transfer**  **exactly 1 mL of each individual stock solution at 1 000 mg/L, add solvent, mix the solutions, and**  **bring to volume in a 25 mL volumetric flask. For e xample, for a composite containing twenty**  **individual standards, the resulting concentration o f 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 prepare d at a minimum of five**  **concentrations with dilution of the composite stock standard with isooctane or hexane. The**  **standard concentrations should correspond to the ex pected range of concentrations present in**  **the field samples and should bracket the linear ran ge of the detector.** 

**7.6 Recommended internal standard – Prepare a solut ion of 1000 mg/L of**  **4,4'-dibromobiphenyl. For spiking, dilute this sol ution to 50 ng/μL. (This concentration may need**  **to be more dilute depending on the detector sensiti vity. The internal standard response should**  **be approximately 50 to 90% of full scale.) Use a s piking volume of 10 μL/ml of extract. The**  **spiking concentration of the internal standards sho uld 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 performan ce of the method should be**  **monitored using surrogate compounds. Surrogates ar e 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-trichlorodiphe nyl 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. Th e 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 m ore information on this topic.** 

**8.2 Extracts should be stored in the dark at or bel ow 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 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 directions for t hose 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 significant c hange to instrumentation or procedure**  **occurs, the laboratory must demonstrate that accept able precision and bias can still be obtained**  **by the changed conditions. Whenever new staff memb ers are trained, an analyst IDP must be**  **performed.**

**9.2.1 Demonstration of proficiency for new analysts**

**Each laboratory should have a training program whic h documents that a new**  **analyst is capable of performing the method, or por tion 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 Proce dure (SOP) established by the**  **laboratory. SW-846 Update V 8111-6 Revision 1**  **July 2014 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 quality control for preparation and anal ysis – 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 la boratory 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 s hould 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 analyz ed as a safeguard against chronic**  **laboratory contamination. The blanks should be car ried 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 s ample or one matrix spike/matrix spike**  **duplicate pair. The decision on whether to prepare and analyze duplicate samples or a**  **matrix spike/matrix spike duplicate must be based o n knowledge of the samples in the**  **sample batch. If samples are expected to contain t arget analytes, 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, laboratori es should use a matrix spike and matrix**  **spike duplicate pair.**

**9.4.3 An LCS should be included with each analytic al 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 that the laboratory**  **can perform the analysis in a clean matrix.**

**9.4.4 See Method 8000, Sec. 9 for the details on c arrying out sample QC**  **procedures for preparation and analysis.**

**9.5 Surrogate recoveries – The laboratory must eva luate surrogate recovery data from**  **individual samples versus the surrogate control lim its developed by the laboratory. See Method**  **8000, Sec. 9 for information on evaluating surrogat e data and developing and updating**  **surrogate limits.**

**9.6 It is recommended that the laboratory adopt ad ditional 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.** 

**9.7 Lower Limit of Quantitation (LLOQ)**

**The laboratory shall establish the LLOQ as the low est point of quantitation, which in most**  **cases, is the lowest concentration in the calibrati on curve. LLOQ verification is recommended**  **for each project application to validate quantitati on 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 le ss 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 proced ures in Sec. 7.0. Refer to Method**  **8000 for proper calibration procedures. The proced ure for internal or external calibration may be** 

**used.**

**10.2 Refer to Method 8000 for procedures for establ ishing retention time windows.** 

**11.0 PROCEDURE**

**11.1 Extraction and cleanup**

**11.1.1 Refer to Chapter Two and Method 3500 for gui dance on choosing the**  **appropriate extraction procedure. In general, wate r samples are extracted at a neutral, or**  **as-is, pH with methylene chloride, using either Met hod 3510 or 3520. Solid samples are**  **extracted using any of the extraction methods for s olids 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 sel ection. Method 3660 may be used** 

**for sulfur removal.**

**11.1.3 Prior to gas chromatographic analysis, the e xtraction solvent should be**  **exchanged to hexane. The exchange is performed dur ing 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 sign**  **ificant losses will occur in concentration steps, if care is not exercised. It**  **is important to maintain a constant, gentle evaporation rate and not to allo**  **w 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 additiona l 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 proc edures 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 esta blishing 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 calibra tion, establishing retention**  **time windows, the analysis sequence, appropriate di lutions, 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 demonstra tes quantitation precision of**  ≤ **10 percent relative standard deviation (RSD). The sol**  **vent flush technique may be used if the amount of solvent is kept at a minimum. If the int**  **ernal 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 occur s when a peak from a sample** 

**extract falls within the absolute retention time wi ndow. Normally, confirmation is required.**  **Confirmation techniques include analysis on a secon d column with dissimilar stationary**  **phase, by GC/MS (full scan or selected ion monitori ng (SIM)), or by using a different**  **detector and getting comparable data. See Method 8 000 for further information.** 

**11.4.3.1 If partially overlapping or co-eluting pea ks are present, install**  **columns with a dissimilar liquid phase or use a GC/ MS technique.** 

**11.4.3.2 Interferences that prevent analyte identif ication and/or**  **quantitation may possibly be removed by the cleanup techniques mentioned above.** 

**11.4.4 Record both the volume injected (to the near est 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 co mpounds 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 recomm ended, rather than peak area**  **integration, when overlapping peaks may cause error s 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 question able. The analyst should consult with the**  **source of the sample to determine whether further c oncentration of the sample is** 

**warranted.**

**11.4.7 Determine the concentration of each identifi ed analyte using the** 

**calculation formulas in Sec. 11 of Method 8000.**

**11.5 Instrument maintenance**

**11.5.1 Injection of sample extracts from waste site s 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 chrom atography in many ways (e.g., peak**  **tailing, retention time shifts, analyte degradation , etc.). Therefore, instrument maintenance**  **is very important. Residue buildup in a splitter m ay 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 w ill minimize the problem and** 
**instrument QC will indicate when instrument mainten ance is required.** 

**11.5.2 Suggested chromatograph maintenance – Correc tive 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 rins**  **ed with several column volumes of an appropriate solvent. Both pol**  **ar and nonpolar solvents are recommended. Depending on the nature of the sample**  **residues expected, the first rinse might be water, followed by methanol and acet**  **one; methylene chloride is a satisfactory final rinse and in some cases may be t**  **he only solvent required. The column should then be filled with methylene chlorid**  **e 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 chl**  **oride, drained, and dried at room temperature with a stream of ultrapure nitroge**  **n 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 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**

**13.1 Table 1 lists the retention times and recoveri es of the target analytes. The**  **recoveries presented were obtained from the analysi s 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 determ ined 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 th e 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 g eneration. Numerous opportunities for pollution**  **prevention exist in laboratory operation. The Envi ronmental 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 addre ss their waste generation. When wastes**  **cannot be feasibly reduced at the source, the EPA r ecommends recycling as the next best**  **option.**

**14.2 For information about pollution prevention tha t may be applicable to laboratories** 

**and research institutions consult** Less is Better: Laboratory Chemical Management for Waste

Reduction **, a free publication available from the ACS, Commit tee on Chemical Safety,**  **http://portal.acs.org/portal/fileFetch/C/WPCP_01229 0/pdf/WPCP_012290.pdf** 

**.**

**15.0 WASTE MANAGEMENT**

**The EPA requires that laboratory waste management 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** **SW-846 Update V 8111-10 Revision 1 July 2014**  **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 web address listed**

**in Sec. 14.2 above.**

**16.0 REFERENCES**

**1. V. Lopez-Avila, E. Baldin, J. Benedicto, J. Mila nes and W. F. Beckert, "Application of**  **Open-Tubular Columns to SW-846 GC Methods," final r eport to the U.S. EPA on Contract**  **68-03-3511, Mid-Pacific Environmental Laboratory, M ountain View, CA, 1990.** 

**2. S. Tsang, P. Marsden and N.Chau, "Performance Da ta 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 D ATA** 

**The following pages contain the tables referenced b y 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**

**Peak a**  **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 20.8**  **4 7 3,5-Dichlorophenyl 4-nitrophenyl ether**  **14.55 21.33 8 2,5-Dichlorophenyl 4-nitrophenyl ether 14.55 21.5**  **4 9 2,4-Dichlorophenyl 4-nitrophenyl ether 15.08 22.3**  **0 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 30.0**  **3 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 thi ckness) and 30 m x**  **0.53 mm ID DB-1701 (1.0 μm film thickness) connecte d 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 ST UDIES** 

**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**  **July 2014 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, Rev ision 0.** 

**1. Improved overall method formatting for consisten cy 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 wer e made throughout to improve method**  **clarity.**

**3. The revision number was changed to 1 and the dat e 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 r eflect the current section numbers.**