### SW-846 Update V 3511 - 1 Revision 1

**October 2012 METHOD 3511** 

**ORGANIC COMPOUNDS IN WATER BY MICROEXTRACTION**

**SW-846 is not intended to be an analytical training manual. Therefore, method procedures** 

**are written based on the assumption that they will be performed by analysts who are formally** 

**trained in at least the basic principles of chemica l analysis and in the use of the subject** 

**technology.**

**In addition, SW-846 methods, with the exception of required method use for the analysis of** 

**method-defined parameters, are intended to be guida nce methods which contain general** 

**information on how to perform an analytical procedu re or technique which a laboratory can use as** 

**a basic starting point for generating its own detai led standard operating procedure (SOP), either** 

**for its own general use or for a specific project a pplication. The performance data included in this** 

**method are for guidance purposes only, and are not intended to be and must not be used as** 

**absolute QC acceptance criteria or for the purpose of laboratory accreditation.** 

**1.0 SCOPE AND APPLICATION**

**For a summary of changes in this version, please se e Appendix A at the end of this** 

**document.**

**1.1 Method 3511 is a procedure for extracting selec ted volatile and semivolatile** 

**organic compounds from water. The microscale appro ach minimizes sample size and solvent** 

**usage, thereby reducing the supply costs, health an d safety risks, and waste generated.** 

**1.2 This method was validated for several mono- and poly-cyclic aromatic** 

**hydrocarbons (MAHs and PAHs) and can be applied to any combination of these compounds.** 

**1.3 This method also may be used to extract selecte d volatile organic compounds** 

**(VOCs) or semivolatile organic compounds (SVOCs) wh ich are slightly soluble or insoluble in** 

**water at neutral pH if the extraction performance i s demonstrated to be satisfactory using an** 

**appropriate analytical technique.**

**1.4 Prior to employing this method, analysts are ad vised to consult the base method** 

**for each type of procedure that may be employed in the overall analysis (e.g., Methods 3500,** 

**3600, 5000, and 8000) for additional information on quality control procedures, development of** 

**QC acceptance criteria, calculations, and general g uidance. Analysts also should consult the** 

**disclaimer statement at the front of the manual and the information in Chapter Two for guidance** 

**on the intended flexibility in the choice of method s, apparatus, materials, reagents, and supplies,** 

**and on the responsibilities of the analyst for demo nstrating that the techniques employed are** 

**appropriate for the analytes of interest, in the ma trix of interest, and at the levels of concern.** 

**In addition, analysts and data users are advised th at, except where explicitly required in a** 

**regulation, the use of SW-846 methods is** not **mandatory in response to Federal testing**

**requirements. The information contained in this me thod is provided by EPA as guidance to be** 

**used by the analyst and the regulated community in making judgments necessary to generate** 

**results that meet the data quality objectives for t he intended application.** 

**1.5 Use of this method is restricted to use by, or under supervision of, appropriately** 

**experienced and trained personnel. Each analyst mu st demonstrate the ability to generate** 

**acceptable results with this method.**

### SW-846 Update V 3511 - 2 Revision 1

**October 2012 2.0 SUMMARY OF METHOD** 

**2.1 Samples are prepared by liquid:liquid extractio n with organic solvent in field** 

**sampling containers. Careful manipulation of the s ample, solvent, and spiking solutions during** 

**the procedure minimizes loss of volatile compounds while maximizing extraction of volatile,** 

**semivolatile, and nonvolatile compounds.**

**2.2 Since volatile compounds are included in the me thod, their extraction from water** 

**requires special handling and particular attention to detail. Samples should be removed from the** 

**refrigerator shortly before extraction, and should not be allowed to warm to room temperature** 

**before the extraction solvent is added.**

**2.3 Samples should be prepared one at a time to the point of solvent addition (i.e., do** 

**not prepare a number of samples then add the solven t). Pay particular attention to minimizing** 

**the exposure of the sample and/or extract to air.**

**2.4 Determinative analysis is performed using the a ppropriate GC or GC/MS method** 

**(** e.g. **, 8015, 8021 and 8270). Reference 2 shows an examp le of a GC configuration used for the** 

**entire list of target analytes that may help reduce solvent tailing to prevent interference with any** 

**early-eluting target compounds in this method.**

**3.0 DEFINITIONS**

**Refer to the SW-846 chapter of terms and acronyms f or potentially applicable definitions.** 

**4.0 INTERFERENCES**

**4.1 Solvents, reagents, glassware, and other sample processing hardware may yield** 

**artifacts and/or interferences to sample analysis. All of these materials must be demonstrated to** 

**be free from interferences under the conditions of the analysis by analyzing method blanks.** 

**Specific selection of reagents and purification of solvents by distillation in all-glass systems may** 

**be necessary. Refer to each method for specific gu idance on quality control procedures and to** 

**Chapter Four for general guidance on the cleaning o f glassware.** 

**4.2 Refer to Method 3500 for additional information on interferences.** 

**5.0 SAFETY**

**There are no significant safety issues specific to this method. However, SW-846** 

**methods do not purport to address all safety issues associated with their use. The laboratory is** 

**responsible for maintaining a safe work environment and a current awareness file of OSHA** 

**regulations regarding the safe handling of the chem icals listed in this method. A reference file of** 

**material safety data sheets (MSDSs) should be avail able to all personnel involved in these** 

**analyses.**

### SW-846 Update V 3511 - 3 Revision 1

**October 2012 6.0 EQUIPMENT AND SUPPLIES** 

**The mention of trade names or commercial products i n this manual is for illustrative** 

**purposes only, and does not constitute an EPA endor sement or exclusive recommendation for** 

**use. The products and instrument settings cited in SW-846 methods represent those products** 

**and settings used during method development or subs equently evaluated by the Agency.** 

**Glassware, reagents, supplies, equipment, and setti ngs other than those listed in this manual** 

**may be employed provided that method performance ap propriate for the intended application has** 

**been demonstrated and documented.**

**6.1 VOA vials - 40-mL capacity, disposable, pre- cleaned with** 

**Polytetrafluoroethylene (PTFE)-lined caps**

**6.2 Vials - Amber glass, 2-mL capacity, with PTFE-l ined screw or crimp top** 

**6.3 Centrifuge - Capable of at least 500 G’s**

**6.4 Syringes - gastight, contaminant-free, 2.0-mL, 1.0-mL, 10-**  μ **L**

**6.5 Analytical balance - Capable of weighing to 0.0 1 g** 

**6.6 Pasteur glass pipettes - 1mL, disposable**

**7.0 REAGENTS AND STANDARDS**

**7.1 Reagent grade chemicals must be used in all tes ts. Unless otherwise indicated,** 

**it is intended that all reagents conform to the spe cifications of the Committee on Analytical** 

**Reagents of the American Chemical Society, where su ch specifications are available. Other** 

**grades may be used, provided it is first ascertaine d that the reagent is of sufficiently high purity t**  **o**

**permit its use without lessening the accuracy of th e determination.** 

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

**organic-free reagent water as defined in Chapter On e.** 

**7.3 Sodium sulfate (granular, anhydrous), Na 2**  

### SO **4** 

### . Purify by heating at 400 ° **C for**

**four hours in a shallow porcelain bowl. Store unus ed portion of sodium sulfate in a desiccator or** 

**sealed container.**

**7.4 Extraction and exchange solvents**

**The choice of solvent will depend on the analytes o f interest and no single solvent is** 

**universally applicable to all analyte groups. What ever solvent system is employed**  including

**those specifically listed in this method, the analy st**  must **demonstrate adequate performance for**

**the analytes of interest, at the levels of interest . At a minimum, such a demonstration will** 

**encompass the initial demonstration of proficiency described in Method 3500, using a clean** 

**reference matrix. Method 8000 describes procedures that may be used to develop performance** 

**criteria for such demonstrations as well as for mat rix spike and laboratory control sample results.** 

**All solvents should be pesticide quality or equival ent. Solvents may be degassed prior to** 

**use.**

**7.4.1 Methylene chloride, CH 2**  

### Cl **2**



### .

### SW-846 Update V 3511 - 4 Revision 1

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

**See the introductory material to this chapter, Orga nic Analytes, Sec. 4.1.** 

**Samples should be extracted as soon as after collec tion as possible, but no longer than 14** 

**days from the date of collection for acid preserved samples. If samples are not acidified, the** 

**extraction should be performed within 7 days from d ate of collection.** 

**9.0 QUALITY CONTROL**

**9.1 Refer to Chapter One for guidance on quality as surance (QA) and quality control** 

**(QC) protocols. When inconsistencies exist between QC guidelines, method-specific QC criteria** 

**take precedence over both technique-specific criter ia and the criteria given in Chapter One, and** 

**technique-specific QC criteria take precedence over the criteria in Chapter One. Any effort** 

**involving the collection of analytical data should include development of a structured and** 

**systematic planning document, such as a Quality Ass urance Project Plan (QAPP) or a Sampling** 

**and Analysis Plan (SAP), which translates project o bjectives and specifications into directions for** 

**those that will implement the project and assess th e results. Each laboratory should maintain a** 

**formal quality assurance program. The laboratory s hould also maintain records to document the** 

**quality of the data generated. All data sheets and quality control data should be maintained for** 

**reference or inspection.**

**9.2 Initial demonstration of proficiency and lower limit of quantitation (LLOQ)** 

**Each laboratory must demonstrate initial proficienc y with each sample preparation and** 

**determinative method combination it utilizes by gen erating data of acceptable accuracy and** 

**precision for target analytes in a clean matrix. T he laboratory must also repeat the** 

**demonstration of proficiency whenever new staff mem bers are trained or significant changes in** 

**instrumentation are made. See Method 8000D, Sec. 9 .3 for information on how to accomplish a** 

**demonstration of proficiency.**

**The laboratory shall establish the LLOQ as the lowe st 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 c lean 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 DQOs.**

**In order to demonstrate the entire sample preparati on and analysis process at the lower** 

**limit of quantitation (LLOQ), a LLOQ check standard (not part of an initial calibration) is prepared** 

**by spiking a clean control material with the analyt e(s) of interest at the predicted LLOQ** 

**concentration level(s). Alternatively, a represent ative sample matrix may be spiked with the** 

**analytes of interest at the predicted LLOQ concentr ation levels. The LLOQ check is carried** 

**through the same preparation procedures as environm ental samples and other QC samples.** 

**Recovery of target analytes in the LLOQ check stand ard should be within established** 

**in-house limits, or other such project-specific acc eptance limits, to demonstrate acceptable** 

**method performance at the LLOQ. Until the laborato ry has sufficient data to determine** 

**acceptance limits, the LCS criteria ± 20% may be us ed for the LLOQ acceptance criteria. This** 

### SW-846 Update V 3511 - 5 Revision 1

**October 2012 acknowledges the poorer overall response at the low**  **end of the calibration curve.**

**Historically-based LLOQ acceptance criteria should be determined as soon as practical once** 

**sufficient data points have been acquired.**

**9.4 Refer to Method 3500 for additional quality con trol procedures.** 

**9.5 Before processing any samples, the analyst shou ld demonstrate that all parts of** 

**the equipment in contact with the sample and reagen ts are interference-free. This is** 

**accomplished through the analysis of a method blank . Each time samples are extracted,** 

**cleaned up, and analyzed, and when there is a chang e in reagents, a method blank should be** 

**prepared and analyzed for the compounds of interest as a safeguard against chronic laboratory** 

**contamination.**

**9.6 Any method blanks, matrix spike samples, or rep licate samples should be** 

**subjected to the same analytical procedures (Sec. 1 1.0) as those used on actual samples.** 

**9.7 Each extraction batch of twenty or fewer sample s should include a minimum of a** 

**method blank, a laboratory control sample (LCS), a matrix spike sample, and a matrix spike** 

**duplicate or laboratory duplicate sample.**

**9.8 All field and QC samples should be spiked with an appropriate mix of surrogate** 

**compounds in order to track extraction efficiency.**

**9.9 Any QC samples should be subjected to exactly t he same analytical procedures** 

**as those used on field samples.**

**10.0 CALIBRATION AND STANDARDIZATION**

**There are no calibration or standardization steps d irectly associated with this extraction** 

**procedure.**

**11.0 PROCEDURE**

**Refer to Sec. 9 for a list of number and types of QC samples that should be included with** 

**each batch of 20 or fewer field samples.**

**11.1 For each QC sample to be extracted and analyz ed, prepare one vial as described** 

**below (Sec. 11.3).**

**11.2 If volatile compounds are target analytes of i nterest, the QC vials must be** 

**prepared far enough in advance that the water has t ime to chill before extraction. However,** 

**these vials should not be allowed to sit in the ref rigerator for more than 24 hours, or their integrit**  **y**

**may be suspect.**

**11.3 For each method blank or LCS QC sample, fill a 40 m**  **L glass VOA vial with a**

**PTFE-lined septum screw top with reagent water.**

**11.4 If volatile compounds are target analytes of i nterest, make sure that all field and** 

**QC samples are chilled to less than 4** ° **C before proceeding.**

### SW-846 Update V 3511 - 6 Revision 1

**October 2012 11.5 Working with a single field or QC sample at a**  **time, remove the cap from the VOA**

**vial, and use a disposable pipette to remove approx imately 5 mL of water. Alternatively, remove** 

**enough sample volume from the vial to prevent vesse l overflow, however, too much volume** 

**removed will create a potential for headspace and l oss of volatile constituents. In addition, the** 

**amount of time used to process volatile compound ex tracts up to the point of solvent addition** 

**needs to be kept to a minimum in order to avoid fur ther volatile constituent losses. Replace the** 

**vial cap.**

**The volume removed should be disposed of according to the guidelines set forth by the** 

**laboratory for the disposal of laboratory wastes.**

**11.6 After removing the 5 mL, weigh the capped VOA vial for each field and QC** 

**sample. Record the weight to the nearest 0.1 grams**

**.**

**11.7 Remove the cap and add 10** μ **g of the surrogate standard compounds in acetone.**

**The surrogates recommended are fluorobenzene, 2-flu orobiphenyl, and 5-a-androstane. Other** 

**compounds may be used as surrogates, depending upon the desired target analytes and project** 

**requirements.**

**11.7.1 It should be noted that more surrogate stand ard may be added to the** 

**water if the sample is suspected to be highly conta minated (i.e., the contamination may** 

**interfere with the recovery of lower concentration levels of surrogate standard).** 

**11.7.2 The LCS and matrix spike QC samples should h ave 10**  μ **g of the**

**appropriate compounds of interest added.**

**11.8 Add exactly 2.0 mL of methylene chloride (DCM) (using a class A volumetric** 

**pipette or gas-tight syringe) and approximately 12 g of anhydrous sodium chloride to the VOA vial.** 

**Replace the vial cap. At this point, the next samp le may be processed to the point of solvent** 

**addition and the subsequent steps performed for eac h sample batch.** 

**11.9 Shake each vial vigorously for 5 minutes, or u ntil the sodium chloride dissolves** 

**completely.**

**11.10 Allow the phases to separate. Centrifugation may be useful for separating the** 

**phases. If the emulsion interface between layers i s more than one-third the size of the solvent** 

**layer, the analyst should employ mechanical techniq ues to complete the phase separation. The** 

**optimum technique depends upon the sample and may i nclude stirring, filtration of the emulsion** 

**through glass wool, centrifugation, or other physic al methods.** 

**11.11 Using a 2.0-mL gas-tight syringe, transfer ap proximately 1.5 mL of the lower** 

**(DCM) layer to a 2 mL vial fitted with a PTFE lined screw cap, taking precautions to exclude any** 

**water from the syringe. Add a small amount (~50 mg ) of anhydrous sodium sulfate to the vial,** 

**cap, and shake for 2 minutes.**

**11.12 Using a 1.0 mL gas-tight syringe, transfer ex actly 1.0 mL of the dried extract to a** 

**2 mL vial fitted with a PTFE lined screw cap. Add 50**  μ **g of the internal standard compounds to**

**each vial, using an appropriate volume not to overf low the vial or dilute the extract. The internal** 

**standards recommended are** o **-terphenyl and 2,4-difluorotoluene. Other compound s may be** 

**used as internal standards, depending upon the desi red target analytes and project requirements.** 

**Cap the vial and invert several times to mix the co ntents.** 

### SW-846 Update V 3511 - 7 Revision 1

**October 2012 11.13 Discard the remaining contents of the VOA via**  **ls according to laboratory waste**

**disposal guidelines. Shake off the last few drops with short, brisk wrist movements. If needed,** 

**rinse the vial with a water soluble solvent to ensu re that the extraction solvent is removed.** 

**Reweigh the capped vial, and record the weight to t he nearest 0.1 g. The difference between** 

**this weight, and the weight determined in Sec. 11.6 is equal to the volume of water extracted, in** 

**mL.**

**11.14 Extracts should be stored in the freezer or o ver ice until analysis.** 

**12.0 DATA ANALYSIS AND CALCULATIONS**

**There are no data analysis and calculation steps d irectly associated with this procedure.** 

**Follow the directions given in the determinative me thod.** 

**13.0 METHOD PERFORMANCE**

**13.1 Performance data and related information are p rovided in SW-846 methods only** 

**as examples and guidance. The data do not represen t required performance goals for users of** 

**the methods. Instead, performance criteria should be developed on a project-specific basis, and** 

**the laboratory should establish in-house QC perform ance criteria for the application of this** 

**method.**

**13.2 Single-laboratory precision data were obtai ned for MAHs and PAHs at four** 

**different spiking concentrations in reagent water. Three replicates were prepared at three levels,** 

**and six replicates at one level. Extracts were ana lyzed by Method 8100, set up to include the** 

**MAHs along with the PAHs. Data summary tables are included in this method. For guidance** 

**purposes, the data are reported in detail in Refere nce 1.** 

**14.0 POLLUTION PREVENTION**

**14.1 Pollution prevention encompasses any techniqu e that reduces or eliminates the** 

**quantity and/or toxicity of waste at the point of g eneration. Numerous opportunities for pollution** 

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

**environmental management techniques that places pol lution prevention as the management** 

**option of first choice. Whenever feasible, laborat ory personnel should use pollution prevention** 

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

**source, the Agency recommends recycling as the next best option.** 

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

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

Reduction **, a free publication available from the American Ch emical Society (ACS), Committee on** 

**Chemical Safety, http://portal.acs.org/portal/fileF etch/C/WPCP_012290/pdf/WPCP_012290.pdf.** 

**15.0 WASTE MANAGEMENT**

**The Environmental Protection Agency requires that l aboratory waste management** 

**practices be conducted consistent with all applicab le rules and regulations. The Agency urges** 

**laboratories to protect the air, water, and land by minimizing and controlling all releases from** 

**hoods and bench operations, complying with the lett er and spirit of any sewer discharge permits** 

### SW-846 Update V 3511 - 8 Revision 1

**October 2012 and regulations, and by complying with all solid an**  **d hazardous waste regulations, particularly the**

**hazardous waste identification rules and land dispo sal restrictions. For further information on** 

**waste management, consult** The Waste Management Manual for Laboratory Personne l **available**

**from the American Chemical Society at the address l isted in Sec. 14.2.** 

**16.0 REFERENCES**

**1. "Simultaneous Analysis of Monocyclic Aromatic Hy drocarbons in Water by** 

**Microextraction." EPRI Report TR-Research Project, April 1997.** 

**2. D. M. Munro. “Simultaneous Determination of Vol atile and Semivolatile Organic** 

**Compounds in Soil.”** Remediation Journal, **10, pp. 65-81, 2000.**

**http://onlinelibrary.wiley.com/doi/10.1002/rem.3440 100408/pdf** 

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

**The following pages contain the tables referenced b y this method.** 

### SW-846 Update V 3511 - 9 Revision 1

**October 2012 TABLE 1** 

**EXAMPLE MICROEXTRACTION GC/FID RECOVERY DATA FOR**

**MAHs AND PAHs IN REAGENT WATER SPIKED AT 8.57** μ **g/L 1** 

**Compound Sample A**  **Sample B Sample C**  **Std.**

**Dev.**

**Conc. 2**  **% Rec. Conc.**  **2 % Rec.**  **Conc. 2**  **% Rec. (Conc.**  **2 )** 

**Benzene 9.59**  **112 7.40**  **86 8.80**  **103 1.1** 

**Toluene 9.03**  **105 9.44**  **110 9.36**  **109 0.22** 

**Ethylbenzene 8.60**  **100 8.81**  **103 8.87**  **103 0.14** 

**m/p-Xylene 17.0**  **99 18.1**  **106 18.1**  **106 0.60** 

**Styrene 6.86**  **80 7.17**  **84 6.99**  **82 0.16** 

**o-Xylene 9.94**  **116 10.3**  **120 10.5**  **123 0.31** 

**1,2,4-Trimethylbenzene 7.44**  **87 8.53**  **100 8.35**  **97 0.59** 

**Naphthalene 7.02**  **82 7.36**  **86 7.48**  **87 0.24** 

**2-Methylnaphthalene 7.11**  **83 7.76**  **91 7.96**  **93 0.45** 

**1-Methylnaphthalene 7.98**  **93 8.45**  **99 8.80**  **103 0.41** 

**Acenaphthylene 8.44**  **98 8.45**  **99 8.74**  **102 0.17** 

**Acenaphthene 9.23**  **108 9.73**  **114 9.61**  **112 0.26** 

**Dibenzofuran 6.72**  **78 7.01**  **82 6.99**  **82 0.16** 

**Fluorene 6.17**  **72 6.62**  **77 7.35**  **86 0.60** 

**Phenanthrene 7.43**  **87 7.90**  **92 7.74**  **90 0.24** 

**Anthracene 4.76**  **56 6.19**  **72 6.24**  **73 0.84** 

**Fluoranthene 8.12**  **95 8.53**  **100 8.57**  **100 0.25** 

**Pyrene 8.49**  **99 8.78**  **102 8.92**  **104 0.22** 

**Benz(a)anthracene 6.59**  **77 6.88**  **80 6.46**  **75 0.21** 

**Chrysene 5.78**  **67 5.92**  **69 6.14**  **72 0.18** 

**Benzo(b)fluoranthene 3**  **14.8 172**  **14.8 172**  **12.0 141**  **1.6**

**Benzo(k)fluoranthene 3**  **16.6 194**  **10.4 122**  **8.60 100**  **4.2**

**Benzo(a)pyrene 6.60**  **77 6.24**  **73 6.94**  **81 0.35** 

**Indeno(1,2,3-cd)pyrene 5.45**  **64 6.16**  **72 5.37**  **63 0.43** 

**Dibenz(a,h)anthracene 5.62**  **66 5.90**  **69 5.10**  **60 0.40** 

**Benzo(g,h,i)perylene 6.15**  **72 6.41**  **75 6.50**  **76 0.18** 

**1** 

### Three reagent water samples were spiked at 8.57 μ **g/L with all target compounds (in acetone),**

**and then extracted and analyzed by the method. A s mall spiking volume at high analyte** 

**concentration was used to maximize the analyte/wate r interaction prior to the extraction step.** 

**2** 

### Concentration units are μ **g/L.**

**3** 

### High compound recovery was caused by an unidentifi **ed interference, possibly a silicone**

**compound. SW-846 Update V** **3511 - 10 Revision 1** **October 2012 TABLE 2** **EXAMPLE MICROEXTRACTION GC/FID RECOVERY DATA FOR MAHs AND PAHs IN REAGENT WATER SPIKED AT 42.9** μ**g/L 1** **Compound Sample A** **Sample B Sample C** **Sample D Sample E** **Sample F Std.** **Dev. Conc.** **2 % Rec.** **Conc. 2** **% Rec. Conc.** **2 % Rec.** **Conc. 2** **% Rec. Conc.** **2 % Rec.** **Conc. 2** **% Rec. (Conc.** **2 )** **Benzene 45.0** **105 41.3** **96 29.5** **69 44.9** **105 43.0** **100 43.6** **102 5.9** **Toluene 44.5** **104 45.8** **107 43.9** **102 45.4** **106 46.0** **107 46.3** **108 0.93** **Ethylbenzene 45.9** **107 47.1** **110 45.7** **107 47.5** **111 47.7** **111 48.4** **113 1.1** **m/p -** **Xylene 92.3** **108 95.1** **111 91.9** **107 95.3** **111 95.7** **112 98.0** **114 2.3** **Styrene 40.7** **95 41.9** **98 40.9** **95 42.1** **98 42.4** **99 43.4** **101 1.0** **o -** **Xylene 49.6** **116 51.2** **120 49.3** **115 50.8** **119 51.3** **120 52.4** **122 1.2** **1,2,4 -** **Trimethylbenzene 44.0** **103 45.9** **107 44.8** **104 45.6** **106 45.4** **106 46.5** **109 0.88** **Naphthalene 42.8** **100 44.0** **103 43.2** **101 43.8** **102 43.7** **102 43.8** **102 0.45** **2 -** **Methylnaphthalene 43.3** **101 44.8** **105 43.6** **102 43.9** **103 44.3** **103 43.7** **102 0.54** **1 -** **Methylnaphthalene 45.4** **106 46.9** **109 46.0** **107 46.0** **107 45.7** **107 45.2** **106 0.58** **Acenaphthylene 46.0** **107 47.4** **111 46.6** **109 46.3** **108 46.5** **109 46.0** **107 0.51** **Acenaphthene 47.7** **111 48.8** **114 48.2** **112 47.7** **111 48.2** **112 46.9** **109 0.67** **Dibenzofuran 43.6** **102 45.0** **105 44.3** **103 44.0** **103 44.0** **103 43.3** **101 0.60** **Fluorene 44.8** **104 45.6** **106 45.4** **106 44.5** **104 44.7** **104 44.3** **103 0.53** **Phenanthrene 46.1** **108 47.5** **111 47.3** **110 46.4** **108 46.9** **109 46.1** **107 0.61** **Anthracene 37.4** **87 38.6** **90 38.4** **90 38.0** **89 37.7** **88 37.4** **87 0.51** **Fluoranthene 46.3** **108 48.0** **112 48.0** **112 46.9** **109 47.0** **110 45.9** **107 0.84** **Pyrene 46.5** **109 48.6** **113 47.7** **111 47.2** **110 47.4** **111 47.4** **111 0.68** **Benz(a)anthracene 41.9** **98 44.8** **105 44.3** **103 42.8** **100 43.0** **100 42.6** **99 1.1** **Chrysene 42.8** **100 44.8** **105 44.1** **103 43.5** **102 43.9** **102 43.1** **101 0.72** **Benzo(b)fluoranthene 47.2** **110 50.6** **118 49.8** **116 46.9** **109 48.4** **113 50.8** **119 1.7** **Benzo(k)fluoranthene 52.2** **122 50.5** **118 46.8** **109 46.9** **109 47.5** **111 46.7** **109 2.3** **Benzo(a)pyrene 39.2** **91 41.3** **96 40.7** **95 40.0** **93 40.0** **93 40.5** **95 0.73** **Indeno(1,2,3 -** **cd)pyrene 49.8** **116 45.7** **107 38.4** **89 42.7** **100 42.5** **99 41.3** **96 3.9** **Dibenz(a,h)anthracene 35.4** **83 36.7** **86 35.3** **82 35.5** **83 35.4** **83 35.7** **83 0.52** **Benzo(g,h,i)perylene 38.3** **89 39.7** **93 39.2** **91 38.7** **90 38.5** **90 38.9** **91 0.50** **1 Six reagent water samples were spiked at 42.9** μ**g/L with all target compounds (in acetone), and the n extracted and analyzed by the method. A small sp** **iking volume at high analyte concentration was used to maximize the analyte/wate** **r interaction prior to the extraction step. 2** **Concentration units are μg/L.**

### SW-846 Update V 3511 - 11 Revision 1

**October 2012 TABLE 3** 

**EXAMPLE MICROEXTRACTION GC/FID RECOVERY DATA FOR**

**MAHs AND PAHs IN REAGENT WATER SPIKED AT 857** μ **g/L 1** 

**Compound Sample A**  **Sample B Sample C**  **Std.**

**Dev.**

**Conc. 2**  **% Rec. Conc.**  **2 % Rec.**  **Conc. 2**  **% Rec. (Conc.**  **2 )** 

**Benzene 819**  **96 866**  **101 797**  **93 35** 

**Toluene 905**  **106 931**  **109 937**  **109 17** 

**Ethylbenzene 922**  **108 933**  **109 978**  **114 30** 

**m/p-Xylene 1840**  **107 1860**  **109 1950**  **114 59** 

**Styrene 878**  **102 878**  **102 935**  **109 33** 

**o-Xylene 946**  **110 951**  **111 998**  **116 28** 

**1,2,4-Trimethylbenzene 933**  **109 928**  **108 991**  **116 35** 

**Naphthalene 908**  **106 951**  **111 939**  **110 22** 

**2-Methylnaphthalene 909**  **106 955**  **111 940**  **110 23** 

**1-Methylnaphthalene 909**  **106 955**  **111 940**  **110 23** 

**Acenaphthylene 905**  **106 962**  **112 937**  **109 29** 

**Acenaphthene 913**  **107 958**  **112 945**  **110 23** 

**Dibenzofuran 906**  **106 949**  **111 938**  **109 22** 

**Fluorene 910**  **106 956**  **112 941**  **110 24** 

**Phenanthrene 909**  **106 954**  **111 943**  **110 23** 

**Anthracene 887**  **103 930**  **108 922**  **108 23** 

**Fluoranthene 909**  **106 954**  **111 946**  **110 24** 

**Pyrene 902**  **105 943**  **110 948**  **111 26** 

**Benz(a)anthracene 907**  **106 947**  **110 942**  **110 22** 

**Chrysene 937**  **109 992**  **116 968**  **113 28** 

**Benzo(b)fluoranthene 894**  **104 875**  **102 930**  **108 28** 

**Benzo(k)fluoranthene 924**  **108 1120**  **131 961**  **112 104** 

**Benzo(a)pyrene 898**  **105 967**  **113 937**  **109 34** 

**Indeno(1,2,3-cd)pyrene 895**  **104 942**  **110 933**  **109 25** 

**Dibenz(a,h)anthracene 900**  **105 1010**  **118 941**  **110 56** 

**Benzo(g,h,i)perylene 908**  **106 974**  **114 949**  **111 33** 

**1** 

### Three reagent water samples were spiked at 857 μ **g/L with all target compounds (in acetone),**

**and then extracted and analyzed by the method. A s mall spiking volume at high analyte** 

**concentration was used to maximize the analyte/wate r interaction prior to the extraction step.** 

**2** 

### Concentration units are μ **g/L.**

### SW-846 Update V 3511 - 12 Revision 1

**October 2012 TABLE 4** 

**EXAMPLE MICROEXTRACTION GC/FID RECOVERY DATA FOR**

**MAHs AND PAHs IN REAGENT WATER SPIKED AT 8570** μ **g/L 1** 

**Compound Sample A**  **Sample B Sample C**  **Std.**

**Dev.**

**Conc. 2**  **% Rec. Conc.**  **2 % Rec.**  **Conc. 2**  **% Rec. (Conc.**  **2 )** 

**Benzene 9470**  **111 8770**  **102 9070**  **106 351** 

**Toluene 8440**  **98 8710**  **102 8510**  **99 140** 

**Ethylbenzene 8750**  **102 8860**  **103 8860**  **103 64** 

**m/p-Xylene 17500**  **102 17700**  **103 17700**  **103 115** 

**Styrene NA**  **NC NA**  **NC NA**  **NC NC** 

**o-Xylene 8810**  **103 8910**  **104 8910**  **104 58** 

**1,2,4-Trimethylbenzene 8840**  **103 8940**  **104 8950**  **104 61** 

**Naphthalene 8520**  **99 8800**  **103 8480**  **99 174** 

**2-Methylnaphthalene 8400**  **98 8880**  **104 8540**  **100 247** 

**1-Methylnaphthalene 8420**  **98 8890**  **104 8540**  **100 244** 

**Acenaphthylene 8490**  **99 8750**  **102 8440**  **98 167** 

**Acenaphthene 8520**  **99 8790**  **103 8470**  **99 172** 

**Dibenzofuran 8450**  **99 8930**  **104 8600**  **100 246** 

**Fluorene 8550**  **100 8820**  **103 8510**  **99 169** 

**Phenanthrene 8680**  **101 8940**  **104 8640**  **101 163** 

**Anthracene 8230**  **96 8480**  **99 8150**  **95 172** 

**Fluoranthene 8560**  **100 8820**  **103 8520**  **99 163** 

**Pyrene 8630**  **101 8910**  **104 8600**  **100 171** 

**Benz(a)anthracene 8630**  **101 8890**  **104 8610**  **100 156** 

**Chrysene 8450**  **99 8750**  **102 8400**  **98 189** 

**Benzo(b)fluoranthene 8850**  **103 9110**  **106 8810**  **103 163** 

**Benzo(k)fluoranthene 8420**  **98 8660**  **101 8380**  **98 151** 

**Benzo(a)pyrene 8700**  **102 8960**  **105 8660**  **101 163** 

**Indeno(1,2,3-cd)pyrene 9480**  **111 9670**  **113 9480**  **111 110** 

**Dibenz(a,h)anthracene 8550**  **100 8970**  **105 8540**  **100 245** 

**Benzo(g,h,i)perylene 8990**  **105 9310**  **109 9030**  **105 174** 



### NA = Not available

**NC = Not calculated**

**1** 

### Three reagent water samples were spiked at 8570 μ **g/L with all target compounds (in**

**acetone), and then extracted and analyzed by the me thod. A small spiking volume at high** 

**analyte concentration was used to maximize the anal yte/water interaction prior to the** 

**extraction step.**

**2** 

### Concentration units are μ **g/L.**

### SW-846 Update V 3511 - 13 Revision 1

**October 2012 Appendix A:** 

**Summary of Revisions to Method 3511 (as compared to previous Revision 0, November 2002)** 

**1. Improved overall method formatting for consisten cy with new SW-846 methods style** 

**guidance. The format was updated to Microsoft Word 2007.docx.** 

**2. Minor editorial and technical revisions were mad e throughout to improve method clarity.** 

**3. The revision number was changed to1 and the date published was changed to May 2012.** 

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

**5. Added Updated IDP language and LLOQ verification standard language to Secs. 9.2 and** 

**9.3.**

**6. Added a reference in Sec. 16.**