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

**July 2014 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

**July 2014 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

**July 2014 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

**July 2014 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 lowest point of quantitation, which in most cases,

is the lowest concentration in the calibration curv e. LLOQ verification is recommended for each projec t

application to validate quantitation capability at low analyte concentration levels. This verificatio n may

be accomplished with either clean control material (e.g., reagent water, solvent blank, Ottawa sand,

diatomaceous earth, etc.) or a representative sampl e matrix, free of target compounds. Optimally, the

LLOQ should be less than the desired regulatory actio n 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 analyte(s) of int erest at the predicted LLOQ concentration level(s).

Alternatively, a representative sample matrix may b e spiked with the analytes of interest at the predi cted

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

**July 2014** LLOQ concentration levels. The LLOQ check is carried t hrough the same preparation procedures as

environmental samples and other QC samples.

Recovery of target analytes in the LLOQ check standa rd should be within established in-house

limits, or other such project-specific acceptance l imits, to demonstrate acceptable method performance

at the LLOQ. Until the laboratory has sufficient dat a to determine acceptance limits, the LCS criteria

± 20% may be used for the LLOQ acceptance criteria. This acknowledges the poorer overall response

at the low end of the calibration curve. Historica lly-based LLOQ acceptance criteria should be

determined as soon as practical once sufficient dat a 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).**

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

**July 2014 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.**

**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** 

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

**July 2014 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.** 

**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

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

**July 2014** 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** 

**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

**July 2014 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**

**July 2014 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**

**July 2014 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**

**July 2014 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. 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 July 2014.** 

**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.**