FINAL REPORT DETERMINATION OF ANALYTICAL METHODS … · search for standards or reference compounds, a search of the NIST/EPA/NIH mass spectral library, and consideration of other

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FINAL REPORT

DETERMINATION OF ANALYTICAL METHODS FOR PAHs

SDMS DocID 458920

prepared by;

Michael Zimmerman

Quality Assurance Technical Support Laboratory ICF Technology

2700 Chandler Ave., Building C Las Vegas, Nevada 89120

January 28, 199A Contract Nus.ber: 68D900^1

Vork Assignment A.3

prepared for:

Work Assignment Manager

Angelo Carasea Analytical Operations Branch

U.S. Environmental Protection Agency Washington. D.C. 20460

OFFICE OF E.Kr.;-.;LNCY A.SIi Ri.KZDIAL .".ESFG:. U.S, ENVIROS'XENTAL FROTECTION AGENCY

WASHINGTON. D.C. 20460

TABLE OF CONTENTS

PAGE

EXECUTIVE SUMMARY 1

RACKGROUND AND PURPOSE 1

TECHNICAL APPROACH . . . 2

RESULTS AND DISCUSSION 3

CONCLUSIONS AND RECOMMENDATIONS 8

ACKNOVLEDCEMENTS 9

REFERENCES 10

LIST OF TABLES

Table 1. List of PAHs 12

Table 2. PAH Method Sujn:?.ary 13

Table 3. Compound Summary 17

Table 4. PAH Precision and Accuracy 21

APPENDICES

Appendix 1. Summary Spreadsheet 24

>

FINAL REPORT

DETERMINATION OF ANALYTICAL METHODS FOR PAHs

EXECUTIVE SUMMARY

A list of twenty-nine (29) polynuclear aromatic hydrocarbons (PAHs) was reviewed to Identify several aspects of applicable water and soil/solid analytical methods. Our review has included a search for EPA and other published methodolgy, a limited survey of commercial laboratory capability, a search for standards or reference compounds, a search of the NIST/EPA/NIH mass spectral library, and consideration of other Issues related to analysis of these compounds in water and soil samples. This final report represents the conclusion of Subtask 6.

Nine of the twenty-nine compounds were found in the target compound lists of several EPA methods. Commercially available standards were found for twelve of the compounds. The newest release of the NIST/EPA/NIH mass spectral database contains entries fcr tventy-six of the compounds. Other information is detailed in the following sections. A summary spreadsheet of our review is provided in Appendix 1.

Based on :he availability of reference materials, a target list of twelve of the iistied PAHs can be analyzed, depending on chromatographic resolution and sample prepai-ation recoveries. Analysis using current PAH analytical techniques for sa.ijple preparation, cleanup, chromatography, and detection should apply with little or no modification. Analysis of the seventeen unavailable compounds will be qualitatively and quantitatively tentative until reference standards can be found.

BACKGROUND AND PURPOSE

The purpose of this Vork Assignment (UA) is to identify analytical methods and other related issues for water and soil analysis targeting the twenty-nine PAHs listed in Table 1.

Polynuclear aromatic hydrocarbons (PAHs) are defined as organic compounds containing two or more aromatic rings (1). Compounds containing a heteroatoa in their structure are known as heterocyclic aromatic compounds (HACs) and include nitrogen-containing azaarenes and sulfur-containing thiaarenes which are not included in the subject EPA list. PAHs are ubiquitous contaminants in the environment which have gained considerable attention due to their carcinogenic character. A recent reference of c cii c inoj;-:;."! c a:..i l','. i s ir:c i •_d.. ~. .-.11 t-jt of.e c-f thf listed coirpounds (2).

Tv-.r sccertpd n^~?r!clature of PAHs from the International Union of Pure •""•' •'' y ' "' - ; s ' y.- 'iriA"' i : .Îv. .-t r r-.' l p - - • c'.:r r':les for determining the

A

'"ffi-" '^^'i.^

2. ..s n.'u.v ling st. ru. t. nrc s as possible are abovt- a;.d *. ci ti.c '. : j : ' ol a horlz'^ntal row.

3. If more than one orientation fulfills these requl rerrienr s , i h t one witVi '.'.. minimum number of ring structures at the lower left is chosen.

4. The carbon atoms are numbered in a clockwise direction starting with the atom In the most clockwise position of the uppermost ring structure or the uppermost ring which is furthest to the right and is not engaged In ring fusion.

Isomers are distinguished by lettering the peripheral sides of the molecule starting with 'a' for the side between carbon atoms 1 and 2 and continuing clockwise around the molecule. One example, phenanthrene, is shown below: _

t

Nomenclature for selected PAHs and HACs are given in reference 1.

TECHNICAL APPROACH

Subtask I. Analytical Methods

The search for analytical methods was performed by searching the Environirental Monitoring Methods Index (EMMI, Version 1.0, Dececber, 1991), reviewing all of the methods maintained at the ICF/QATS laboratory, searching the literature using DIALOG, and contacting several chemists who have considerable experience in PAH analysis. The electronic literature search included CA SEARCH (Chemical Abstracts), Analytical Abstracts, and National Technical Information Service (NTIS). Precision and accuracy data were collected from several EPA publications.

Subtask 2. Connaercial Laboratory Capabilities

A limited survey of the capabilities and expertise of the commercial laboratory community was performed by talking with eight Individuals, all senior members of the analytical community with considerable experience in PAH analysis. These individuals are personal contacts who represent both CLP and non-CLP laboratories. A cover letter explaining our task and the list of PAHs was telefaxed to most of these individuals for their review.

Subtask 3. Standards

Trie £.vailability of ccnîercial standards was evaluatea by reviewing the EMMI search results which Include standard suppliers, searching the supplier catalogs in the ICF/QATS laboratory, and sollcltir.g th>; V:-lp c : t \: rt.y-trhree -•-r-lf-rr by telefax. Syr*- tf- - " - ^ z i c - l l a b o r a U r i e s ar-,! r;:'- • '.'"-•^•.-'

.:..•.: T-ut ions , ail p.trr.". .re VT.': ccntf.cted

^

Subtask 4. NIST/EPA/NIH Mass Spectral Library

The presence of reference mass spectra in the NIST/EPA/NIH mass spectral database was evaluated using the.library containing 53,994 entries in release 1.0, 1992. Searches were performed by c^reating artificial spectra based on molecular weight and searching the library for Chemical Abstracts Number (CAS No.). The NIST office in Maryland also searched the most recent PC version of the library for three compounds that were not found in our library.

Subtask 5. Other Experience and Concems

Our experience and concerns with analysis of these PAHs are detailed in the following section. Costs, safety, and disposal issues related to the unregulated and unavailable PAHs are very difficult to define.

RESULTS AND DISCUSSION

Subtask 1. Analytical Methods

EPA and other standard methods were found for nine of the twenty-nine compounds:

benzo(b)fluoranthene ^ indenod . 2, 3-cd>pyrene * benzo(j)fluoranthene 3-methylcholanthrene dibenz(a,h)anthracene benz(a)ar;thracene, 7, 12-dimethyl dlbenzo(a,h)pyrene ** benzo(a)pyrene * dibenzo(a,i)pyrene **

Four coopounds (*). are targeted in up to twenty-two EPA or other standard Methods, including the CLP. Two compounds, denoted with ( * * ) , are targeted only in SW-846 Method 8100, a GCFID PAH-specific method. The other three compounds are listed in from two to four methods, including Methods 8250, 8270A, 8100, 1625, 525, and D4763.

No EPA or other standard methods were found for the following twenty compounds:

benzo(c)phenanthrene, 4-methyl 3-methylcholanthrene, 1,2-dlhydro benzo(c)phenanthrene, 5-methyl benz(a)anthracene, 5,6-dihydro-7,12-dimethyl benzo(c)phenanthrene, 6-methyl dibenzo(a,l)pyrene chrysene, 5-ethyl benz(a)anthracene, 6-methyl chrysene, 5-methyl ber.z (a)anthracene, 7-Eethyl cyclopenta(c,d)pyrene benz(a)anthracene , o - L.i L i i y i

dibenz(a,c)anthracene benz(a)anthracene, 1 2 - c e t h y l dibenz(a,j)anthracene, 5,6-dib}dro :r.cl;r.threne , 11 , 12 -dihvdro d ib e nz o(a,e)f1uo r in thene

/T

The suJti.'T.arized infoniat i on U^LJ:.. d ii; :j..:-..,.,k . i i. . >.:;.;•'..' d -.:• t.,:lc-.'. and 3. Table 2 includes summaries of EPA methods used for PAH analysis, including method title and number, source of methods, compounds analyzed for, preparation technique, instrumental technique, matrix(ces), detection limit definition and units, and detection limits for one of the listed compounds, benzo(a)pyrene. Table 3 is a summary for each of the nine EPA target compounds, organized in a format similar to the EMMI database from which it was largely derived. Although we have made every effort to search all of the available references, including the methods from the states of California and Washington, it is entirely possible that some of these compounds appear in some state, health, or other regulatory methodolgy which we have not found.

Many other references were found for the analysis of the PAHs which are not targeted In EPA and other regulatory methods (3, 4, 5, 6, 7, 8). These references include a compilation of electron impact mass spectra for ten of the compounds (3), prediction of high-performance liquid chromatographic (HPLC) retention indices for twenty-two of the listed compounds (4), relationships between liquid chromatography and PAH molecular shape for sixteen of the listed PAHs (5), nuclear magnetic resonance (NMR) spectroscopy for seven of the compounds (6), and negative ion chemical ionization (NCI) mass spectrometry for three compounds (7). Recent literature contains many other references for air particulate analysis, combustion and fuel analysis, synthesis, and biological studies.

Precision and accuracy information for the four P.AHs most frequently targeted in EPA metiiods is listed in Tabic -, This ^:ii^rz.a^ L...n --s cG::, :;lcd from Che hardcopy of our most current copies of the n:ethcds (9, 10, 11, 12) and includes historical quarterly blind data frsm QBiri'88 through QB3ri"92 (13). With the exception of one small set of data for spiked clay from SW-846 method 8270A, all of the precision and accuracy data that we have found Is from water analyses.

Eight of the methods list precision and accuracy data deriving from two sources. SW-846 Methods 8100 and 8310 (Sept 1986), EMSLC Method 610, and Standard Method 6440, which are HPLC-UV/FL and GCFID methods, list precision and accuracy information from a multllaboratory study involving 16 labs analyzing six water matrices over a range of 0.1 to 425 ug/L. Similarly, the GCMS data in SW-846 Methods 8250, 8270A, EMSLC Method 625, and Standard Method 6410, all derive from a multllaboratory study involving 15 laboratories analyzing at least four water matrices over a range of 5 to 1300 ug/L. Precision and accuracy data in Methods 525 and 1625 are from smaller sets of four, seven, or eight replicate analyses in clean water.

Referenced sample preparation methodology for PAHs in water includes liquid-liquid separatory funnel techniques (SW-846 Method 3510), continuous liquid extraction (SW-846 Method 3520). and 1iquid-sol id extraction (LSE). Judging by the poor recoveries in .Method 325 urir.g LSt. this technique appears to be the least desirable water preparation technique. Soils and solids are generally extracted using Scx l . l c t extraction {S'.--£^t- y:-::].c:ds 35AO s.r.d 3341). •:1 trascr.i c-.T i'-'H ''?y-F-'46 .'.e'rhod 3550), and s-.:pe rr r i t •;,- 1 fluid extraction

(^

rforrard in far less tiir,':- than traditional soxhlet tt-L i.niqvie.s , t ..r. \ i• .rt-ctly coupled to detention devices using SFf, a:id u'. ,i ;i;>i ;, ::. • ,:^..:11;require large solvent volumes. We understand that SFE, as a result of input from Hewlett Packard and Environment Canada, is a current topic for evaluation by OSW in expanding the scope of Method 3560 (Supercritical Fluid Extraction) to Include PAHs and chlorinated phenol^.

Sample clean-up techniques for PAHs Include silica gel techniques (SW846 Method 3630), florisil chromatography (SW-846 Method 3620), gel permeation chromatography (GPC, SW-846 Methoq 3 6 ^ 0 ) , and alumina column chromatography (SW-846 Method 3611). GPC removes' interfering lipids from biological sources. Florisil, silica gel, and alumina clean-ups are suggested for removal or fractionation of polar and dissimilar nonpolar Interferences.

Final instrumental detection techniques for PAHs are almost always coupled with either liquid chromatography (LC or HPLC)) or gas chromatography (GC). The most common detectors for liquid chromatography are ultraviolet (U\') and fluorescent (FL) instruments. HPLC methods include SW-846 Method 8310, EPA Method 550.1 for drinking water, and EPA Method 610 for wastewater. A quick turnaround HPLC method using wavelength programmed U\' and FL detectors has been described for water, soil, and waste oil matrices (16). One HPLC thermospray mass spectrometry (HPLC/TSP/MS) EPA method, SW-846 Method 8321, is currently used for disperse azo dyes and organosposphorus compounds. Although P.AHs are not targeted in this method, mass spectrometry is a viable PAH detection technique with HPLC.

Jas chromatography techniques include flar:;e ionization detectors (GCFID), described in SW-846 Method 8100, and mass spectrometry (GCMS), described in CLP OLM02, SW-846 Methods 8250 and 8270A, EPA Methods 625, 525, and 1625, among others. High efficiency capillary columns (CGC) are the desired choice for GC analysis. Although mass spectrometry is the most versatile technique providing the most confident qualitative analysis, SW-846 Method 8100, a GCFID method, includes 24 target PAHs, the largest set of target PAHs in any EPA method that we have reviewed. GC-Fourier Transform Infrared (GC-FTIR) coupled with GCMS has also been described for PAH analysis (17, 1 8 ) . We have not reviewed any immunological or radioimmunoassay (RIA) methods.

Subtask 2. Commercial Laboratory Survey

Analysis of the list of PAHs was discussed with the following individuals. The list of PAHs was sent to each of them along with a cover letter explaining our information gathering effort.

Steven Wise Jane Chuang N:rT - Ii,t c r ] : j t i r r;_:l S c c i e t - r.S Bc t t<-: ; r Col v:;:' • .3 I.:.': t e l e : (301) 975-3112 tele: (614) 424-5222 FAX: (301) 926-8671 FAX: (614) 424-4185

7

Dr . ired DL-.ROOS '.'.u o". vii Studi iev Huntington / Twin Cities Testing ICF K a i s e r E n g i n e e r s tele: (612) 645-3601 t e l e : (510) 4 1 9 - 5 4 4 6 FAX: (612) 659-7515 FAX: (510) 4 1 9 - 5 3 5 5

Chuck Miller Gary Robertson ICF Kaiser Engineers EMSL-Las Vegas tele: (509) 946-2110 tele: (702) 798-2215 FAX: (509) 943-5143

Willie Lljinsky

formerly of the National Cancer Institute Frederick, Maryland tele: (301) 371-5677

All of these people expressed an interest and willingness to examine the

list of PAHs. At least two of these laboratory representatives also indicated

a willingness to perform analysis. The most common comment on the potential

analysis of these PAHs was a concern that for those compounds which are

unavailable in standard or reference form, analysis would be both

qualitatively and quantitatively tentative, requiring some combination of

GCMS, N'MR, or GCFTIR, to confidently identify some of the isomers. Several

individuals indicated that at first glance, analysis of the listed PAHs should

be possible with any of the GCMS methods. Several people also expressed

relief that the list does not contain any heterocyclic compounds, many of

whichL are kr.cwn to behave poorlv ir. traditional GC analysis.

Specific commercial costs for analysis of the list of PAHs have been

discussed only briefly. Although rhe cost of standards for two of the

additional compounds Is relatively high, no significant cost difference from

traditional PAH analysis is expected, provided analysis of the rare compounds

is not dependent on obtaining rare or nonexistent standards and is not

constrained with unrealistic QA/QC criteria.

Subtask 3. Standards

Commercial sources of standards were found for twelve of the twenty-nine

compounds. In addition to the compounds which appear on the target lists of

EPA methods, which are readily available from many different suppliers,

sources were found for the following three compounds:

CAS No, Compound Name Source Form Cost

27208-37-3 Cyclopenta(cd)pyrene Chemsyn Solid $ 610 / 25 mg 215-5 8-7 Diber'.z(a,c) anthracene Ultra Solid $ 35 / 10 mg

Ace Sid Solid $ 18 / 10 iLg 191-30-0 Libenzo(a, npvrene Chen-.svn Solid $ 115 / 10 rag

.-.cc Std CnV.nc-.-n $ 30

•--rative and

^

.'ute, is a speciaîv cneiricai i:..,:iuf ac t ..rer in Lt-nexa, K •.:•.••. iS ; t 1 e : \ Z^ ' ' ^ . . ..•-.;33-66a3, FAX: (913) 888-3582j. Another excellent supplier of rare PAHs

was found in Crescent Chemical of Hauppauge, NY (tele: 1-800-877-3225, FAX (516) 348-0913).

Several contacts. Including Triangle Labs and the National Cancer Institute (NCI) in Frederick, Maryland, mentioned private collections of rare PAHs. Given the number of literature references for most of the compounds, it seems likely that such collections of these compounds do exist.

Subtask 4. NIST/EFA/UIH Mass Spectral Database

With the following exceptions, all of the PAHs were found in the NIST/EPA/NIH mass spectral database:

CAS No, Compound Name

5385-75-1 Dibenzo(a,e)fluoranthene 189-64-0 Dibenzo(a,h)pyrene 189-55-9 Dibenzo(a,i)pyrene

The results of our search of NIST revision 1.0, 1992, were checked against the newest NIST PC version of the library. Personnel at NIST confirmed the absence of these entries. The Wiley cass spectral lihrar;.- vas not examined.

Most PAHs have relatively simple electron impact mass spectra, dorrinated by a molecular ion (M+), Ions at (M+)-l, (M+)-2, (M+)-3, and a doubly charged ion at (M+)/2. Ions at (M+)-26, (M+)-27, and (M-t-)-28. which derive from expulsion of C2H2 from the molecular ions, are also observed. Methylated compounds yield a (M-i-)-L5 ion. Differences between the mass spectra of isomeric compounds are very small, making definitive library matching very difficult. Confident PAH identification in GCMS analysis usually requires reference retention times.

Subtask 5. Summary

In the absence of reference jQippminfl*?, n n r y w ^ M n r m t i n r t techniques can be expected to provide only tentative identifications of the 17 unavailable ? ^ S ~ . BaSFd on our experience and the comments of the people contacted for this review, £CMS analysis is the most promising technique for analysis of these compounds. In most commercial envirormaental laboratories, GCMS capabilities include all of the requirements for PAH analysis. HPLC analysis, •-'• : c"n if; ran; ;.-:"! arl-.- •-seful for thern'llv ialilo cci~.:ôunds . in certain, cases might provide resolution very different from GC resolution and eight be a preferred technique for resolving some of the listed isomers. HPLCHS

.; : dent an,\ ^ •" - • F : . : -. . . . - •, ; .i n. ib 1 ^

f

•„ i; ;, • .• s t- ,n .dard:^ , ' ni- :: 1 ; n','. : : .:. -.-x •: ! v nrv .,.. i; :. inTit.,:f;.i .;n'.' benz(a)anthracene (molecular weight 242), four of vhich are listed in each case, will be difficult to confidently identify with mass spectrometry techniques despite the prejjLDC^„pX,XgXgr.e"cg mass sj)e,c,tral_ -i brary entries. Similar mass "spectra will also be encountered with the molecular weight (MW) 256, 258, and 302 Isomers. We do not expect that the mass spectra for compounds in these isomer sets are different enough to provide unambiguous identification. Chromatographic resolution or reference retention indices of these isomers will be required for positive identification.

The three molecular weight (MW) 302 compounds are the heaviest and probably the latest elutlng compounds on the list. Two of these compounds, dlbenzo(a,h)pyrene and dlbenzo(a,1)pyrene, are target compounds in SW-846 Method 8100, a GCFID technique. The third MV 302 compound, dibenzo(a,l)pyrene, does not appear on any target list but is available as a standard. The ability to resolve two of these high molecular weight PAHs is evidence of the power of capillary gas chromatography and demonstrates analytical capability without mass spectrometry or other specific detectors. Tb.e ability to resolve dibenzo(a, l)pyrene will be easy to define since all three compounds are available.

Cyclopenta(c,d)pyrene, one of the non-target but available PAKs, has been identified in at least one set of PAH analyses using GCMS when several other traditional target PAHs were present (19). The molecular weight of this compound, 226, is unique in this set of compounds, and along with a reliable n.;tcnticn, tirtc-. uniz.bi e.uous • dent i f i cat i or. should be possible. The relatively lev molecular weight of this compound also suggests that this co:::pound might be the eariiest eluting analyte on the list.

The third non-target available compound, dibenz(a,c)anthracene, shares molecular weight 278 with only one other PAH on the list. The other molecular weight 278 compound, dibenzo(a,h)anthracene, is a target compound in several methods and standards are readily available. If chromatographic conditions allow resolution o£ the these two compounds, analysis is straightforward.

Safety and disposal issues related to the unregulated compounds are completely undefined. Given the carcinogenic nature of many PAHs, the same precautions exercised with regulated PAHs should be exercised with the unregulated compounds unless other information becomes available.

CONCLUSIONS AND RECOMMENDATIONS

The commercial availaMlity_o,f„^3"dards for the! is ted PAHs suggests that a target compormd^nTt^pf- Jt,weJLv£._Qi_Jth ei5lZEMll£an,Jifi..analjze ^ ly in the- cor„~-rcial laboratory comraunity. Any cf the common P.AH final detection tcchniquts. including GCFID, CC.KS,'HPLC-UV, and HPLC-FL, are likely to provide cttection at ppb levels, depending on saicple matrix and interferences, A GCMS : : ^':.:. i ~.-:e n.: t ui'.liV.c the CLP z-?:. L ' . 'o ' i a r . i le a:pr.;ach or Method 83'uA can i?e

\ t a;..ii'."sis vit;,..ut u:crea£or;3ble fr:\tra c o s t s o r

Rolativclv .sirr.ple t xpc n irr; r:t s ran be t n-.'i s i >.m cl to dti; ntiatt .n.i.sris

/

c: such a target list. Chromatographic resolution and sample preparation are the primary concerns in such experiments. Analysis for the other rare compounds will be qualitatively and quantitatively tentative in the commercial laboratory community until reference materials can be found. The only viable commercial approach for the unavailable PAHs is analysis as "Reverse Search" compounds, the approach taken by the Office of Science and Technology in the Effluent Guidelines program (20). This approach involves looking for mass spectra of the compounds in specified regions of the chromatogram for qualitative identification. Chromatographic performance of some of these compounds might be predicted from the retention indices in references 4 and 5. Quantitation can be performed using the current procedures for tentatively Identified compounds (TICs).

ACKNOWLEDGEMENTS

We would like to acknowledge the helpful contributions of Jane Chuang of Battelle - Columbus, Dr. Fred DeRoos of Huntington/Twin Cities Testing, Gary Robertson of EMSL-Las Vegas, Steven Wise of NIST, Dr. Marcus Cooke of Triangle Labs, Dr. George Breuer of the University of Iowa, Willie Lijinskv, foTKerly of NCI, and Carolyn Studney and Chuck Miller of ICF-Kaiser.

We are also gr 'teful for the DIALOG search strategy and expertise of .Mr. Ralph Sulliv;in of ICF/QATS.

II

REFERENCES

1. Francis I. Onuska, Analysis of Trace Organics in the Aquatic Environment, CRC Press, 1989, ch. 6, and references therein.

2. A.M. Richard and Y.T Woo, A CASE-SAR Analysis of Polycyclic Aromatic Hydrocarbon Carcinogenicity, Genet. Toxicol. Div., USEPA, RTP, N C , in Mutat. Res, 242, 1990.

3. Stephen Safe and Otto Hutzinger, Mass Spectrometry of Pesticides and Pollutants, CRC Press, 1973, ch. 6, and references therein.

4. R.H. Rohrbaugh and P.C. Jurs, Molecular Shape and the Prediction of High Performance Liquid Chromatographic Retention Indexes of Polycyclic Aromatic Hydrocarbons, Anal. Chem., 59, 7, 1987.

5. S.A. Wise, et. al., Relationship Between Reversed-phase C18 Chromatographic Retention and the Shape of Polycyclic Aromatic Hydrocarbons, J. Chromatographic Science, 19, 1981.

6. L.K. Reefer, et. al . , Analysis of Mixtures of Isomeric Pol^-nuclear Hydrocarbons by Nuclear Magnetic Resonance Spectrometry, Anal. Chem., 43, 11, 1971.

" . R C. Doughertv, et.al., Negative Chemical Ionization Mass Spectra of Scrse Polynuclear Aromatic Hydrocarbons, USEPA/ORD, EPA-600/9-82-013, 1982.

£. M.L, Lee, M.V. Novotny, and K.D. Bartle, Analytical Chemistry of Polycyclic Aromatic Compounds, Academic Pess, New York, 1982, and references therein.

9. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW-846, 3rd Edition, USEPA, November, 1992, and, September, 1986.

10. J.W. Elchelberger, T.D. Behymer, and W.L. Budde, Method 525, Revision

2.1, 1988

11. USEPA Office of Water Regulations and Standards, Method 1625, June, 1989.

12. Standard Methods, 18th Edition, 1992.

13. RAS Historical Database Maintenance, ICF/QATS TGD 5-5, June 24, 1992.

14. G.M. Brilis and P.J. Marsden, Comparative Evaluation of Soxhlet and

Sonication in the Determination of Polynuclear Aromatic Hydrocarbons in Soil, Che-r.ospherf , Vol.2], pp01-°'', 19^0 .

1:. J.F. Ar..-.'loto, et.al., .Analvsis of Pclycyclic Arc n;atic Cor.ponnds by Supercritical Fluid Cl.vc- s.tczr^^\].w -y.ASS Spectrorret rv . 39th .•AS.M5 -r reference, p l " ! , l l , .:•• -•--/>• -

\ >

--. i

REFERENCES (continued)

16. M.W. Dong, J.X. Duggan, and S. Stefanou, A Quick Turnaround HPLC Method for the Analysis of Polynuclear Aromatic Hydrocarbons in Soil, Water, and Waste Oil, LC-GC, vol 11, p 802, November, 1993.

17. K.S. Chlu, K. Blemann, K. Krishnan, and S.L. Hill, Stuctural Characterization of PAHs by Combined GC/MS and GC/FTIR, Analytical Chemistry, 56, 1610, 1984.

18. S.E. Schepple, G.J. Greenwood, and B.L. Crynes, Proceedings of the 23rd ASMS Conference, Houston, Tx, 1975.

19. Thomas Kelly, Jane C. Chuang, et.al.. Field Measurements of Atmospheric Polynuclear Aromatic Hydrocarbon Concentrations and Phase Distribution at TAMS Sites, Measurements of Toxic and Related Air Pollutants, USEPA/AWMA, 1992.

20. Review of the Contract Laboratory Program Organic Target Compourid List, USEPA Analytical Operations Branch, SMOA'iar Report, June 1, 1992.

/ ^

— : r r \

Table 1. List of PAHs

CAS No. Compound Name

205-99-2 i y Benzo(b)fluoranthene \

205-82-3 Benzo(J)fluoranthene

4076-40-8 Benzo(c)phenanthrene, 4-methyl



54986-62-8 Chrysene, 5-ethyl

3697-24-3 Chrysene, 5-methyl

27208-37-3 Cyclopenta(c,d)pyrene

53-70-3 Dibenz(a,h)anthracene

215-58-" Dibenz(a,c)anthracene

16361-01-6 Dibenz(a,j)anthracene, 3,6-dihydro

5385-:'5-l Dibenzo(a,e)fluoranthene

lS9-bu-0 Diben2o(a,h>pyrene

189-55-9 Dibenzo(a , i")pvrenie

191-30-0 Dlbenzo(a,l)pyrene, synonym, Dlbenzo(def,p)chrysene

193-39-5 Indeno(1,2,3-cd)pyrene

56-49-5 3-Methylcholanthrene

3343-10-0 3-Methylcholanthrene, 1,2-dihydro

35281-29-9 Benz(a)anthracene, 5,5-dihydro-1,12-dimethyl

35281-31-3 Benz(a)anthracene, 7,12-dihydro-7,12-dimethyl

57-97-6 Benz(a)anthracene, 7,12-dlmethyl

316-14-3 Benz(a)anthracene, 6-methyl



2422-'^9-9 Benz ( a anthracene , 12 -rrethvl

3 -.Methylcholanthrene , 11 , 12 -dihvdr^

A

'"'S^ Table 2. w PAH Method Summai y

6410 6440 D4657 D4763 OHC OLM02.1 Number: Soil/Solid

Source of APHA APHA ASTM ASTM USEPA USEPA Method S candard Standard 11 02 11 02 CLP CLP

Methods Methods

Target Base/ PAHs PAHs Organics Organics Semlvols Compounds Neutrals 16 16 63-90 126 64 (TCLs). Niimber 81 of TCLs

Number of 16 (4 from 16 (4 from 16 (4 from 16 (4 from 16 (4 from Target PAHs subject subject subject subject subject

list) list) list) list) list

Sample Prep Liq-liq Liq-liq Liq-liq 1-gram 30-gram Technique Sep fun. Sep fun. Sep fun. ext. Ultra-

pH 2 & 11 neutral pH silica gel sonication

Instrumental GCMS GCFID HPLC-l".',FL Fluor CGCMS CGCMS Technique HPLC-irV.FL GCMS

Sanple Wastewater Wastewater Water and Soils Soils Matrix(ces) Wastewater Solids Solids

Detection MDLs, MDLs vig/L ppm CRQLs CRQLs Limit ug/L mgAg 330 UgAg Dafinition, Units

B«nso(«>fêttii 2.5 ug/L 0.023 ugA 0.002 20 mgAg 330 UgAg Detection ppm Limits

Method Titles:

6410: Extractable Base/Neutrals and Acids, (equivalent to 625)

6440: Polynuclear Aromatic Hydrocarbons, (equivalent to 610)

D4657: Standard Test Method for Polynuclear Aromatic Hydrocarbons in Water.

D4763: Standard Practice for Iderit if icat ion of Chemicals in Water by Fluorescence Spectrc'sccf- .

OHC: Organics Analysis, Mult i-n;edi a , High Concentrat icn ; USEPA Cor.cract Laboratorv Program, Statement of Work. 9/iS.

/ <

Table 2 (continued). PAH Method Summary

Method OLM02.1 - 1625 - BNW 1625 - S 525 550 550.1^8 [ Number: 1 Water

Source o t USEPA USEPA USEPA USEPA USEPA USEPA

Mathod CLP EAD EAD EMSLC EMSLC EMSLC

Target Semlvols Semlvols- Semlvols. Semlvols. PAHs PAHs Coapounds 64 Base/ 176 42 16 16

(TCLs), Number Neutrals

of TCLs 162

Nunber of 16 (4 from 24 (6 from 24 (6 from 13 (5 from 16 (4 from 16 (4 from

Target PAHs subject subject subject subj ect subject s ubj ect list list list list) list) list)

Sample Prep Cont. pH 2 Cont. pH Ultrasoni- LSE .liq- Liq-liq LSE (liq-

Technique GPC 12 -13 cation solid solid ext) GPC GPC ext. )

Instrumental GCMS CGCMS CGCMS CGCMS HPLC-U\',FL HPLC-UV,PL Technique CGCMS

Sample Water, Water, Soil Drinking Drinking Drinking

1 Katrix(ces) Wastewater Wastewater Water *H a t e r W -: e r

Detection CRQLs EDLs, MDLs, .MliLS , -MlJLs, .MDLs ,

Lljnlt 10 ug/L ug/L ug/kg ug i- ug/L ug/L

Definition, Units

B«nso<A>]ên« 10 ug/L 10-ug/L 15 UgAg 0.04 ug/L 0.029 ug/L 0.016 ug/L

Limits

Method Titles;

OLM02.1 - W: Organics Analysis, Multi-Media, Multi-Concentration; USEPA Contract Laboratory Program, Statement of Work, 12/93. Water.

1625 - BNW: Semivolatile Organic Compounds by Isotope Dilution GCMS. Base Neutrals in Water.

525: Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography / .Mass Spectrometry.

tinaticn of Polycyclic Ar<-n.3tic Hycrtvr Liquid-Liquid Extraction and HPLC with -Died U .raviolc: ar.d

\ ^

Table 2 (continued), PAH Method Summary

VTethod 610 625 625-S 8100 8250 8270A - S ^Number:

Source of USEPA USEPA USEPA USEPA USEPA USEPA Method EMSLC, Fed EMSLC, EMSLC OSW, OSW, OSW,

Reg. Fed. Reg. SW-846 1 SW-846 SW-846

Target PAHs, Semlvols. Semlvols. PAHs Semlvols. Semlvols. Compounds 16 84 80 24 113 228 (TCLs), Number of TCLs

Number of 16 (4 from 16 (4 from 16 (4 from 24 (9 from 16 (5 from 18 (6 from Target PAHs subject subject subject subject subject subject

list) list) list) list) list) list)

Sample Prep Liq-liq Liq-liq Repeat Matrix Matrix Matrix Technique Sep fun Sep fun. solvent dependent dependent dependent

Silica gel pH 2, 12 mixing, i 13 silica gel j

florisil GPC

i lnstru::;ental GCFID GCMS CGCMS GCFID GCMS CGC.' S J ' Technique HPLC-U\'.FL L..:M5

1 Sample Wastewater Wastewater Wastewater Water Water Soil Matrlx(c««) Sludge Soil Soil Waste

Waste Waste

I>«t«ctl<m MDLs, MDLs, MDLs, EQLs EQLs. EQLs

Daflnitlon, ug/L ug/L ugA 10 agAg UgAg

1 Units

Benzo(a)pyrene 0.023 ug/L 2.5 ug/L 2.5 ug/L 660 ug/kg Detection Limits

610: Polynuclear Aromatic Hydrocarbons, Federal Register, 49(209), 112-120, 1982

625: Base/Neutrals, Acids, and Pesticides, Federal Register, 44(233), 1979.

625-S: Protocol for the Analysis of Extractable Organic Priority Pollutants in

Industrial and Municipal Vs?tewater Treatirent Sludge.

.Mf thcd S100, "PolvT'. i-1 i- HvdrcrnrbDns."

S2 50: Method S2iO, "Gas Cnr'~.T -Mass >?ec tro.-re trv for Se.Tiv- iat:

/,y

Table 2 (continued). PAH Method Summary

Method 8270A - W 8310 03113 03118

Number:

Soxirce of USEPA USEPA USGS USGS

Method OSW OSW

SW-846 SW-846

Target Semlvol. PAHs PAHs Base-

Compounds 228 16 12 Neutrals

(TCLs), Number 46

of TCLs

Number of 18 (6 from 16 (4 from 12 (4 from 16 (4 from Target PAHs subject subject subject subj ect

list) list) list) list)

Sample Prep Matrix Matrix Liq-liq Liq-liq Technique dependent dependent Sep. fun. Sep. fun. 1

Instrumental CGCMS HPLC-UV,FL HPLC-U\' CGCFID Technique CGCMS

Saaple Wa t e r Wate r V ate:" Katrlx(ces) Wastewater Soil

Waste

Detection EQL. MDL, RNGE, EDL. Limit ug/L ug/L ug/L ug/L Daflnitlon, Unit*

Benz6(a)p7rene 10 ugA 0.023 ug/L 1.0 ugA 5.0 ug/L

Detection Limits

Method Titles:

8270A: Method 8270A, "Semivolatile Organic Compounds by Gas Chromatography / Mass Spectrometry (GC/MS): Capillary Column Technique."

8310: Method 8310 "Polynuclear Aomatic Hydrocarbons"

C3113: "Polynuclear Aronatic Hydrocarbor,s (P.S. ). total recoverable, High-perfor::.ince Liq.iid Chrcnatogra-hic . "

Cc:;.pounds. Totsl Fe : t •.•eri t. e Gas Chrorratoeraphic / .Mass Spec trorre trie "

A

; A S NO. ConxHJund NarrM

.•"OB 99 i Biinjo(b)nuor«oth«n«

205 82 3 B«nio(i)fluor«nth«n«

Method

9 4 1 0 6 4 4 0

0 4 8 S 7 OHC

0 L M 0 2

0 L M 0 2

1 0 2 5 1f l2S 5 2 6

6 5 0 5 6 0 . 1

eio 0 2 5 026-S 8 1 0 0 8 2 5 0

8 2 7 0 A 8 2 7 0 A 8 3 1 0 0 3 1 1 *

S2B S 1 0 0

TabI* 3. Cofnpound Summiny

Souro* of

APHA APHA

A S T M

CLP

CLP

CLP

EAD CAO EMSLC EMSLC EMSLC EMSLC EMSLC EMSLC OSW OSW OSW OSW OSW USOS

EMSLC OSW

ln« l rum«ntd T»chniqo«

GCMS HPLCFL HPLCUV CGCMS

CGCMS CGCMS

CGCMS CGCMS

CGCMS

HPLCFL HPLCFL HPLCFL GCMS GCMS CGCFID GCMS CGCMS CGCMS HPLCFL CGCMS

CGCMS CGCFID

Matr ix(c*a)

LS

W

BNW

S W

s w

w

D«t«ct ion Limita

MDL 4.8 ug/L MOL 0 . 0 1 8 u f l / L ufl/L CRQL 2 0 m g / V g CRQL 3 3 0 ug/kg

CRQL 10 ug/L

ML 10 ug/L

MDL 3 0 u g A ( g MOL 0.1 ug/L

MOL 0 . 0 0 3 0 ug/L MOL O.OOeOug/L MOL 0 . 0 1 8 ug/L MOL 4.8 ug/L MOL ug/L ug/L MOL 4.8 ug/L EQL SeOugAcg EQL 10 ug/L MOL 0 . 0 1 8 ug/L EDL 5.0 ugA.

MOL 0 .1 ugA. ug/L

p«0« 1 of 4

- ^

• ^

CAS No. Compound Nama

S3-70 3 Oibani(a,h)anthfacana

1 B^ B4 o Dihnn/o(a.h>pvrana

189 5S'> Dibflnio(a,i)pvrena

MatKod

6410 6440 04657 04783 OHC OLM02 OLM02 1625 1625 525 550 550.1 610 625 625-S 8100 8260 8270A 8 270 A 8310 03113 03118

8100

8100

Tabia 3. (continuad) Compound Summary

Souroa of Mathod

APHA APHA ASTM ASTM CLP CLP CLP EAD EAO EMSLC EMSLC EMSLC EMSLC EMSLC EMSLC OSW OSW OSW OSW OSW USOS USOS

OSW

OSW

InatrumantslTachniqua

GCMS HPLCFL HPLCUV FLUOR

CGCMS CGCMS CGCMS CGCMS CGCMS CGCMS

HPLCFL HPLCFL

HPLCFL GCMS GCMS

CGCFID GCMS CGCMS CGCMS HPLCFL HPLCUV CGCMS

CGCFID

CGCFID

Matrix(caa)

LS W BNW S W

s w

Dataction Limita

MOL 2 .5 ugA. MOL 0 . 0 3 0 ug/L ug/L DL 0 . 0 0 1 0 p p m CRQL 2 0 mg /kg CRQL . 3 3 0 u g A g CRQL . 10 ug/L ML 2 0 ug/L MOL 130 ug /kg MOL 0 .1 ug/L

MOL 0 . 0 1 9 ug/L MDL 0 . 0 3 5 ug/L

MOL 0 . 0 3 0 uoA. MOL 2 .6 ugA. MDL ug/L ug/L

MOL 2.5 ugA. EQL e e o ug /kg

EQL 10 ug/L MDL 0 . 0 3 0 u g A RNGE 1.0 ug/L EDL 5.0 ug/L

ug/L

ug/L

page 2 of 4

y •4

Tabia 3 . (contlnuadl C o m p O U f K l S u r r t m n r y

Souroa of Inatrumental Dataction CA5 Nd. Compound Nama Mathod Mathod TachrHqua Matrtx(caa) Limita

193.19 5 lr>dano<1,2.3-od)pvrana 6410 APHA GCMS MOL 3.7 ugA 6440 APHA HPLCFL MOL 0.043 ugA D46S7 ASTM HPLCUV ug/L OHC CLP CGCMS CRQL 20mgAig OLM02 • CLP CGCMS LS CRQL 330 ug/kg 0LM02 CLP CGCMS W CRQL 10 ug/L 1625 EAD CGCMS BNW ML 20 ugA. 1626 EAD CGCMS S MOL 260 ugAg 525 EMSLC CGCMS W MOL 0.1 ug/L 550 EMSLC HPLCFL MOL 0.011 ug/L 550.1 EMSLC HPLCFL MOL 0.036 ugA. 610 EMSLC HPLCFL MOL 0.043 ugA. 625 EMSLC GCMS MOL 3.7 ug/L 62S-S EMSLC GCMS MOL ug/L 8100 OSW CGCFID ug/L 8260 OSW GCMS MOL 3.7 ug/L 8270A OSW CGCMS S EQL 660 ug/kg 8 270 A OSW CGCMS w EQL 10 ugA 8310 OSW HPLCFL MDL 0.043 ugA. 03118 USGS CGCMS EDL 5.0 ugA.

' . f t ^ l S 3 MathyfohoJanthrana 1626 EAD CGCMS BNW EDL 10 ugA 1625 EAD CGCMS S MOL ug/kg 8100 OSW CGCFID ugA 8260 OSW GCMS MOL ug/L 8270A OSW CGCMS s EQL ugA. 8270A OSW CGCMS W EQL 10 ugA.

paga 3 of 4

^

Y.


) ; -97 6 B«nz(a)anthraoana, 7,12-dinrMthy<

50-.T2 8 B«mo{m}pYf*'^

Mathod

047SS 162B 1626 82SO 8270A 8 270 A

6410 6440 04457 D47ea OHC 0LM02 OLM02 1625 1625 525 550 550.1 610 62S 62S-8 8100 8260 8270A 8 270 A 8310 03113

cans

Tabia 3. (coni inu'wil

Compound ju r rv i i n rv

Source of Mathod

ASTM EAD EAD OSW OSW OSW

APHA APHA ASTM ASTM CLP CLP CLP EAD EAO EMSLC EMSLC EMSLC EMSLC EMSLC E I ^LC OSW OSW OSW OSW OSW USGS USGS

InatrumantalTechnique

FLUOR CGCMS CGCMS GCMS CGCMS CGCMS

GCMS HPLCFL HPLCUV FLUOR CGCMS CGCMS CGCMS CGCMS CGCMS CGCMS HPLCFL HPLCFL HPLCFL GCMS GCMS CGCFID GCMS CGCMS CGCMS HPLCFL HPLCUV CGCMS

Matrix(caB)

BNW S

S W

LS W BNW S W

S W

Detect ion Limita

OL ug/L EDL 10 ugA. MOL ugAcg MOL ugA. EQL ugAtg EQL 10 ugA.

MOL 2.5 ugA. MDL 0.023 ugA ugA DL 0.0020 ppm CRQL 20 mgAg CRQL 330 ug/kg CRQL 10 ugA ML 10ugA MOL ISugA f l MDL 0.04 ugA. MOL 0.029 ugA. MOL 0.016 ugA. MDL 0.023 ug/L MOL 2.5 ugA. MDL ugA. ug/L MOL 2.5 ugA. EQL 660 ugAg EQL 10 ugA MDL 0.023 ugA. RNGE 1.0 ugA. EDL 5.0 ugA.

paga 4 of 4

*;v

Tabia 4. P A H Praoiaion and Acouracy

Watar Analyaia

• 2 7 0 B , Novambar 1992 (from 8250) 8 1 0 0 . 8 3 1 0 , Sapt 1 9 8 6 CLP QB Data

HIetortoal Compi lat ion Singla Sirtgia Aoouraoy, anal yet Overall Acouracy, artalyat Overall

Q B 1 F r 8 8 - Q B 3 F Y 8 2 preciaion, precision, recovery, praoiaion. praciaion, Ava SO of X' «r' S' x ' ar' S'

Cofnpound Name %Rao %Rao (ugAi <ug/L> (ug/L) (ug/L) (ugA) <ugA)

> J (Vin7o(blfluoranthan« 7 0 . 7 18.1 0 .93C-1 .80 0 .22X + 0.43 0 . 2 9 X + 0 . 9 6 0 .78C + 0 . 0 1 0 .21 X • 0 . 0 1 0 .38X-0 .00 .1 Di>>«n7(e,hlanthr»cana 6 9 . 5 19.5 O . I S C - ^ 4 . 7 2 0 .30X + 8.51 0 . 5 9 X + 0 . 2 5 o.4ic.o.n 0 . 2 4 X - f 0 . 0 2 0 .45X + 0 .03 I ' , Irvln-Tod .2.3-od)pYrena 66 .8 18.2 O.79C-3 .10 0 . 2 9 X * 1 . 4 6 0 .50X.O.44 0 . 5 4 C + 0 . 0 6 0 . 2 9 X « 0 . 0 2 0 .42X- I .0 .01 11 B«nio(a)pvr»r>a 7 0 . 3 18 0 .90C-0 .13 0 .22X + 0 .48 0 .32X + 1.35 O . 5 0 C + 0 . 0 1 0 . 3 8 X - 0 . 0 1 0 . 5 3 X O . 0 1

Method 62S Method 0 1 0 6 4 1 0 , Standard Mnih<W«, I S i h ed, 1992 6 4 4 0 , Standa id Mathoda. 18 th ad, 1992

Sirvgl* Singia B iaaaa enalyet Overall Biaa m» anaiyat Overall Raoovery, preoiBton. praciaion. Recovery, praoiaion. praciaion.

»' »r' s- x ' ar' S ' CoiTipourwJ Name (uflAJ (ug/L) (ug/L) (ugA.) (ugAJ (ugA.)

•>n 2 nnruofbi ' luoranthana 0 .93C-1 .80 0 . 2 2 X + 0 . 4 3 0 . 2 9 X + 0 . 9 8 0 .78C + 0 .01 0 . 2 1 X 4 - 0 . 0 1 0.38X-O.O0

'O 1 Dit)anz(«,h)anthracer>a 0 .«8C- t ' 4 . 72 0 .30X + 8 . 5 1 0 .59X + 0 . 2 5 0 . 4 1 C - O . n 0 . 2 4 X 4 - 0 . 0 2 0.4SX + 0 .03

n ' , i i -Uno( i .? .3-od)pyTana 0 .78C-3 .10 0.29X * 1.4e 0 . 5 0 X ^ . 4 4 0 .54C + 0 . 0 6 0 .29X- t - 0 .02 0 . 4 2 X + 0 . 0 1

w' f< IV«nzo(al|iyrena 0 .90C-0 .13 0 .22X 4 0 .48 0 . 3 2 X + 1.35 0 .56C + 0 .01 0 .3SX-0 .01 0 .53X-0 .01

C " True value for the concentrat ion, in u g A

X' * Expected recovery fo i one or mora meaauremant* of a aampla containing n concentrat ion of C, In ug/L

ar' m Expected ainolo ar>aly«t ataiKlard deviat ion of meeauramenta at an

avernga concentrat ion of X, in ug/L S ' • Expected inlarlnboratory atar>dard deviat ion of meaaurenMnta at an

everaga concentrat ion found of X, in ug/L X •• Average recovery found for measurement* of aamplea containir>g a

concentrat ion of C. in ug/L

page 1 of 3

JO

Tabia 4 . (continued) PAH Preciaion and Accuracy

Watar Ar\elyais

Mathod 6 2 5 ( R a v 2 . 1 ) Kêthod 525 (Rev 2.1) Method 5 2 5 (Rev 2.1) Mathod 5 2 5 (Rav 2.1) 2 .0 u g A , ITMS 0 .2 ugA., ITMS 2.0 u g A , Magr>etic Sector MS 0 .2 ug/L, Magnetic Sector M t

Mean Method Mean Method Mean Mathod Mean Mathod Acouracy Accurecy Accurecy Aoouraoy % of True SO aa % Of % of True SO ea % of % of Tn je SO ae % of % of T m e SO ae % of

Compoiovd Name Corw T r u a C e i M Cor>o True Cone. Cone True Corto Coito True Cone

•eruto(S)*fuorentf>er»a 105 7 . 5 82 10 100 9.3 1 0 0 25

Dlbenr! • , h )enthr acena 15 15 I S 10 38 9.0 4 6 5 20 10 20 15 4 2 3.8 4 0 30

Beruio(»)pyTer»e 4 0 10 15 15 43 7.5 3 8 10

Method 1825 Rav. C, J u n * 1 9 8 9

Table 10 Initial Praoiaion arxl Aoouraoy

(Sac 8.2.3) (ugAJ Compound Nern«i a X

Beruolb )fluorentt>er>e 183 3 2 - B 4 S Olbeni(a,h)anThraoana 55 23 • 2 9 9 Indenot 1,2,3-cd)pyrana 55 23 2 9 9 Beruole lpyrene 26 6 2 - 1 9 6

page 2 of 3

Tabto 4 . (continued) PAH Praoiaion and Accurecy

Spikad Clay Ansiyai*

8270B , November 1992 Spiked Clay

bv Method 3541 (eutomated aoxhlet)


Average percent recovery

Percent

BSD

705 99 25? 70 31?L' 39 5S0^2 8

Benzo(b)fluoranthana Dibenz(a,h)anthracena

lndeno(1,2,3-od)pyrene Benio<a)pyran«

82 .7

R0.7 72 .2 71.7

5.0

6.3 4.3 4.1

page 3 of 3

W

Appandix 1 . PAH Summery

1 III IV

OtKier Methods StarxJard Std Unuaual NIST/EPA/NIH EMMI Method(*) or Referertces Vsrtdors Typa S td Coata MS Library Entry

CLP, et.al., see Not* below Ultra. AS. et.al soln X 8100. 625 Ultra, AS, et.al soln X

X X X X X

Chemeyn aolid • 6 1 0 / 2 5 m g X CLP, et.al.. see Note below Ultre, AS. et.al Boln X

Ultra. AS, et.al a o M • 3 0 / 1 0 m g X X

no entry 8100 Ultra, AS, et.al aoln na entry

8100 Ultra, AS, et.al aoln rto entry

AS, Cf>emsyn solid « 1 1 5 / 1 0 f n g X

CLP, at el, see Note below Ultra, AS, et.al aoln X 9100. 1625.8250. 8270A Ultra, AS. et.al • o i n X

X X

X 8260, 8270A, 1625, D4763 Ultra, AS, et.al aoln X

1 X 1 X 1 X 1 X

X X

1 X CLP, et .a l . , see No t * below Ultra, AS , et .a l . Xaoln

In addi t ion to the CLP, other nrvethoda l isted In EMMI for thaaa oompounda inck ide:

APHA 8 4 1 0 . 6 4 4 0 , AREAL lP-7. ASTM D 4 8 5 7 , EAD 1 6 2 5 (S&W), EMSLC 8 2 5 . 5 5 0 , 5 5 0 . 1 , 6 1 0 , 8 2 5 . 6 2 5 S, OSW 8 1 0 0 . 8 2 5 0 . e 2 7 0 A (S&W), 8 3 1 0 , USGS 0 3 1 1 9 , 0 3 1 1 8

AREAL methods are air methods.

Subtasks:

orTipo<y'vi Nome

' "* r» io(b)" ' ' xantherva t"«r«o(|)f ll "^ranth•r>• '•enzo(( Ip ' innanthreno, 4-mathy( ! en io(c)pênanthrone, 5-mathyf

" '1 ' 'en /o lc lphenenthrene, 8 - m a t h ^ ' " ' «? ' hryseoe. '> ethyl • ' 2'^ ^ Chrysene, ' . methyl

1 ! / ' I 'ycloper>i^(cd)pyrene 1 1 Olt>«ru(e.hl*nthraoer«a " .' l ) ibenz(e, ' ' 'enthracene

' I ' Dibenjr(e.T'' 'nthrflc»ne, 5,6-dihydro 1 Oiben io le . 'H luorenthena

nibenio(e.!i)pyrer>e >lberuo(». I! pyrerie

l iben/ofn. i jpyrene, or O<banzo(daf,p>ohryaerta >deno(1, ' -7 cdlpyrer»a -methvl' ' Hotanthrena

' rueihyî ^")lenthrene, 1,2-dihvdro 'enzlalenlNfeceno, 5,8-dihvdro-7,12-dinr>ath^

•t«n.f(«)«rir'>facena, 7,12-dlhydro-7,12-dirT>«thyf '•^HUr(a)ani'>raoer>a, 7,12.dlmathv< l lenzlelentt i racene, 6-mathV< '^n7(a)nr ' t l i rBcena. 7-rr>athv(

' ( ien/(e)Bnii \racene, B-mettiyf / ' " ' ' .enzfelent' iracone, 1 2-mathy1

" M •• I^n7(e)n"n, racene, 8 ,9,10,11- ta t rahydro-7,12-d innath290 i M f i '>,' 1 i-metf iyi i I ' l lanthrene, 11,12-dlhydro 2 7 0 ' ! ; i 1 " . ' iWnrolc)(ii enanthrone, 3-mathyi 2 4 2 > !, ' n <êrao(«)pyrer>a 2 8 2

W A 4 . 3

M W

262 2S2 242 242 242 2Se 242 226 2 7 t 279 290 302 302 302 302 276 26« 266 269 259 286 242 242 242 242

RataratMaa: 11 Mees Spectrometry of Pest ic ide* end Pol lutent t

S. Safe aryj O. Hutzinger. CRC Press, 1 9 7 3

X indioatas the preser ic f of NIST mas* spectral references.

Documents

FINAL REPORT DETERMINATION OF ANALYTICAL METHODS … · search for standards or reference compounds, a search of the NIST/EPA/NIH mass spectral library, and consideration of other