API 4597(95)

A P I PUBL*4597 95 B 0732270 0547807 866 I American Petroleum Institute

Analytical Method Performance for RCRA Programs Refinery and Other RCRA Analytes

Health and Environmental Sciences Department Publication Number 4597 August 1995

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Copyright American Petroleum Institute Provided by IHS under license with API Licensee=BP International/5928366101

Not for Resale, 06/29/2009 00:12:07 MDTNo reproduction or networking permitted without license from IHS

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A P I PUBL*4597 95 0732290 0 5 4 9 8 1 0 5 8 8

Analytical Method Performance for RCRA Programs

Refinery and Other RCRA Analytes

Health and Environmental Sciences Department

API PUBLICATION NUMBER 4597

PREPARED UNDER CONTRACT BY:

ENSECO-ROCKY MOUNTAIN ANALYTICAL LABORATORY 4955 YARROW STREET ARVADA, CO 80002

AND

TISCHLE F~KOCUREK 11 6 EAST MAIN ROUND ROCK, TX 78664

JULY 1994

American Petroleum Institute



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A P I P U B L X 4 5 9 7 95 E 0732290 05498113 4 1 4 E

FOREWORD

API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED.

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ITY FOR INFRINGEMENT OF LETTERS PAmNT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL-

Copyright O 1995 American Petroleum Institute

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ACKNOWLEDGMENTS

THE FOLLOWING PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT

API STAFF CONTACT

Roger Claff, Health and Environmental Sciences Department

ENVIRONMENTAL MONITORING WORKGROUP

Dominic Deangelis, Mobil Oil Corporation

Harry L. Gearhart, Conoco, Inc.

Lynn M. Lane, ARCO Productions

Francis C. McElroy, Exxon Research and Engineering Company

Lee N. Polite, Amoco Corporation

Tara Popik, BP Research

Ileana A. Rhodes, Shell Development Company

Harold Rhodes*, Texaco Exploration and Production, Inc.

Jerry L. Sides, Texaco Exploration and Production, Inc.

George H. Stanko, Shell Development Company

Allen W. Verstuyft, Chevron Research and Technology Company

* No longer with the company.

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A P I P U B L * 4 5 9 7 75 0732290 0549Bl13 297

TABLE OF CONTENTS

Section

EXECUTIVE SUMMARY ...................................................................................................... ES-I 1 INTRODUCTION ............................................................................................................ 1-1 2 STUDY DESIGN ............................................................................................................. 2-1

SAMPLE MATRICES ............................................................................................ 2.1 ANALYTES ........................................................................................................... 2-1 SPIKE LEVELS ..................................................................................................... 2 4 ANALYTICAL METHODS ...................................................................................... 2-5 NUMBER OF SAMPLES ....................................................................................... 2-6

3 METHOD PERFORMANCE ........................................................................................... 3-1 VOLATILES ........................................................................................................... 3-1

Recovery And Precision .............................................................................. 3-1 Method Detection Limits (MDLs) ................................................................. 3 4

Extraction .................................................................................................... 3-5 Cleanup ................... .................................................................................. 3-7 Recovery And Precision ............................................................................ 3-14 Method Detection Limits (MDLs) ............................................................... 3-16

Recovery And Precision ............................................................................ 3-19

SEM IVOLATI LES .................................................................................................. 3-5

METALS .............................................................................................................. 3-19

Method Detection Limits (MDLs) ............................................................... 3-22 4 RESULTS AND CONCLUSIONS ................................................................................... 4-1

VOLATILES ........................................................................................................... 4-1 SEMIVOLATILES .................................................................................................. 4-2 METALS ................................................................................................................ 4-3

REFERENCES ....................................................................................................................... R-1

LIST OF APPENDICES A B C D

Volatile Recovery. Individual Analytes ........................................................................... A-1 Volatile MDLs. Individual Analytes ................................................................................. B-1 Semivolatile Recovery. Individual Analytes .................................................................... C-1 Semivolatile MDLs. Individual Analytes ......................................................................... D-I



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A P I PUBL84597 95 I 0732290 0 5 4 9 8 3 4 123 6

Table

ES-1 2- 1 2-2 2-3 2-4 2-5 3- 1 3-2 3-3 3-4 3-5 3-6

3-7

3-8

3-9

3-1 O

3-1 1

3-1 2 3-1 3 3-1 4 3-1 5 3-16 3-1 7 3-1 8 3-1 9

LIST OF TABLES Paae

Refinery Analytes .......................................................................................... e5-2 Refinery Analytes ............................................................................................. 2-1

All Semivolatile Analytes ................................................................................... 2-3

Spiking Levels (Metals) ..................................................................................... 2-5

Volatile Recovery (Refinery Analytes) ............................................................... 3-2 Volatile Performance by Matrix (Refinery Analytes) .......................................... 3-3 Volatile MDLs (Analyte Groups) ........................................................................ 3-4

Comparison of Extraction Procedures for Semivolatiles (Refinery Analytes) ................................................................ 3-6 Nondetects after Cleanup for Semivolatiles

Comparison of Cleanup Procedures for Semivolatiles

Nondetects after Cleanup for Semivolatiles

Precision after Cleanup Treated and

All Volatile Analytes .......................................................................................... 2.2

Spiking Levels (Organics) ................................................................................. 2-4

Volatile Recovery (Analyte Groups) .................................................................. 3-1

Volatile MDLs (Refinery Analytes) .................................................................... 3-5

Standard Solution (All Analytes) ....................................................................... 3-8

Treated and Oily Wastes (Refinery Analytes) ................................................... 3-8

Treated and Oily Wastes (All Analytes) .......................................................... 3-10

Oily Wastes (All Analytes) .............................................................................. 3-12 Semivolatile Median Recovery (All Analytes) .................................................. 3-1 4

Semivolatile Median Recovery (Refinery Analytes) ......................................... 3.16

Semivolatile MDLs (Refinery Analytes) ........................................................... 3-19

Comparison of Metal Recoveries by GFAA .................................................... 3-21 Comparison of ICP and GFAA Performance .................................................. 3-22

Semivolatile Performance by Matrix (Refinery Analytes) ................................ 3.1 7 Semivolatile MDLs (Analyte Groups) .............................................................. 3-17

Comparison of Metal Recoveries by ICP ........................................................ 3-20

Metal MDLs .................................................................................................... 3-23



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A P I P U B L 8 4 5 9 7 95 0732290 0549815 ObT W

EXECUTIVE SUMMARY

STUDY OBJECTIVE The American Petroleum Institute (API) conducted a study to evaluate the Performance of analytical methods used in RCRA (Resource Conservation and Recovery Act) programs relevant to the petroleum industry.

The principal objective of this study was to assess the premise that the sample matrices encountered in petroleum refineries, especially oily waste matrices, present significant challenges to the sucessful performance of RCRA analytical methods by commercial environmental laboratories. As RCRA method performance data published by EPA are restricted to method performance in aqueous matrices, a related objective of this study was to generate typical method performance data for RCRA-regulated analytes in various nonaqueous sample matrices commonly encountered in the petroleum industry.

For analytes of concern to the petroleum industry, this report provides method performance data for recovery, precision, and method detection limits (MDLs) in four matrices. These matrices were: a dilute Toxicity Characteristic Leaching Procedure (TCLP) leaching solution'; a clean loamy soil; an oily waste mixture of separator sludge and slop oil emulsion; and a treated waste from a solvent extraction process. From another study, method performance data for reagent water were included for comparison.

This report also includes an evaluation of different extraction and cleanup techniques for semivolatiles. Extraction techniques that were evaluated were sonication extraction by EPA SW-846 Method 3550 using a 1:1 solution of methylene chloride and acetone, Method 3550 using 100% methylene chloride, and an EPA handbook method using simultaneous extraction/acid-base partitioning. Cleanup procedures investigated were alumina column and gel-permeation.

ANALYTES The primary focus of this study was on analytes normally or potentially present in refining wastes, and this report emphasizes those analytes. As part of this study, however, many other RCRA analytes were included, and this report also contains the data for these analytes. In total, this report presents data for 53 volatiles, 128 semivolatiles, and 7 metals. Of these analytes, those that are relevant to the petroleum industry2 are shown in Table ES-1 and include 12 volatiles, 29 semivolatiles, and the 7 metals.

' TCLP extraction fluid no. 1 (as per SW-846 Method 1311) diluted 1 5 wlh reagent water. Extraction fluid no. 1 is prepared by diluting 5.7 millileters (mL) of glacial acetic acid and 64.3 mL of I N sodium hydroxide with reagent water to a volume of 1,000 mL.

For this study, analytes specific to the petroleum refining industry were identified from the Ground Water Monitoring List for hazardous wastes in Appendix IX of 40 CFR 264 (Code of Federal Regulations) and the "Skinner" or "Refinety" List. The Skinner List is a subset of the list of hazardous constituents in Appendix VIII of 40 CFR 261 and has been used for refinery wastes delistings, land treatment demonstrations, and site closures related to petroleum refinery hazardous waste programs.

ES-I



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A P I PUBLmY577 75 0 7 3 2 2 7 0 0 5 4 7 8 3 6 TT6

Table ES-I. Refini Volatiles

acetone benzene 2-butanone carbon disulfide 1,2-dibromoethane 1,sdioxane ethyl benzene methylene chloride styrene toluene m+p xylenes o-xylene

Metals

antimony arsenic chromium cobalt lead nickel selenium

I

y Analytes jemivolatiles

acenaphthene acenaphthylene anthracene benzenethiol benzo(a)anthracene benzo( b)fluoranthene benzo( k)fiuorant hene benzo(g , h,i) pery Iene benzo(a)pyrene bis(2-ethylhexy1)phthalate chrysene dibenzo(a, h)anthracene dibenzofuran 7,12-dmethylbenzanthracene 2,44imethyIphenol fluoranthene fluorene 1 h-indene indeno(l,2,3-cd)pyrene 3-methylcholanthrene 1 -methylnaphthalene 2-methylnaphthalene 2-methylphenol 3-& 4-methylphenol naphthalene phenanthrene phenol pyrene

Organic analytes were grouped according to common characteristics. Volatiles were divided into five groups: aromatic volatiles; halogenated volatiles; non-halogenated volatiles; 1,2-dibromoethane and 1,2-dibromo-3-chloropropane (EDB/DBCP); and a group consisting of acrolein, acrylonitrile, acetonitrile and related compounds. Volatile refinery analytes primarily belong to the aromatic and non-halogenated groups. Semivolatile analytes were divided into eleven groups: benzidines and amines, chlorinated hydrocarbons, haloethers, heterocyclics, nitroaromaticskyclic ketones, nitrosamines, organophosphorus pesticides, phenols, phthalate esters, polynuclear aromatic hydrocarbons (PNAs), and a group of miscellaneous analytes labelled "Other." Semivolatile refinery analytes primarily belong to the PNA and phenol groups.

STUDY FINDINGS AND CONCLUSIONS With a few exceptions, the laboratory methods contained in SW-846 appear to be adequate to analyze matrices typically found in petroleum refinery wastes. The performance criteria published in the methods can be used to indicate the expected variability in results obtained when the method is used correctly by a competent laboratory.

Cleanup procedures contained in SW-846, specifically in Methods 361 1 and 3650, improve detectability of semivolatile analytes in oily waste matrices. This study showed that these methods provide a tenfold increase in analyte detectability of phenols and polynuclear aromatics, with only a slight decrease in precision.

ES-2



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The sample matrix does not appear to directly affect the practical quantification limit (PQL). Rather, the PQL obtained for a given matrix is simply the published PQL for an aqueous matrix, adjusted by appropriate factors to account for operational method differences (e.g., sample size, final extract volume, and dilutions) in analyzing nonaqueous sample matrices.

Antimony is not listed as an analyte in SW-846 Method 3050, the digestion procedure for solid matrices. However, since there are no other EPA SW-846 methods for the digestion of solids for metals analysis, Method 3050 is frequently used for this purpose and is indicated in many EPA guidance documents. This study showed that antimony is not measurable in solid matrices using Method 3050.

Employing SW-846 methods to analyze petroleum refinery oily matrices for semivolatile organics results in low, but still acceptable, performance (precision and accuracy).

There appears to be no performance advantage to using the EPA-specified extraction solvent in Method 3550 (methylene ch1oride:acetone). Of the solvents studied (1 00% methylene chloride, methylene chloride:acetone, and methylene chloride with acid/base partitioning), the deciding factor for selection should be based on cost and health and safety factors.

As the RCRA program has evolved, more analytes have been added to regulatory lists. Many of these analytes are seldom encountered in environmental samples, due to low production and limited use. Examples of these analytes include propionitrile, famphur, methapyrilene, and hexachlorophene. This study confirmed that these and related analytes are not measurable using SW-846 methods. This observation is generally familiar to laboratory personnel, and is also indicated by performance criteria published with the methods.

ES-3



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A P I PUBL*459? 95 O732290 0 5 4 9 8 3 8 8 7 9 M

Section 1

INTRODUCTION

Monitoring is required for petroleum refineries to comply with a variety of hazardous waste program initiatives under RCRA (Resource Conservation and Recovery Act). In some cases, the testing requirements are not well understood either by those who must use the data or by those who perform the analyses. Earlier work by the American Petroleum Institute (API) documented the performance of the United States Environmental Protection Agency (EPAs) SW-846 [USEPA 19861 methods that are used to meet analytical requirements for certain regulations that impact the petroleum industry, specifically, ground water monitoring [API 19891 and toxicity characteristic testing (TCLP). For the most part, performance data listed in these methods are based on the analysis of reagent water and therefore, cannot be directly applied to matrices other than water.

This study was designed to evaluate the performance of SW-846 analytical methods in different matrices for analytes of concern to the petroleum industry, particularly where performance data are inadequate in SW-846 (detection limits and recovery ranges). Twelve volatiles, 29 semivolatiles, and 7 metals identified as refinery analytes were evaluated in a dilute TCLP (Toxicity Characteristic Leaching Procedure) leachate solution3, a clean soil, an oily waste, and a treated waste.

Although the refinery analytes were APls primary focus, and this report emphasizes the method performance for these analytes, API did include many other hazardous constituents from the RCRA program. Method performance data are presented for an additional 41 volatiles and 99 semivolatiles.

Method performance data for recovery, precision, and method detection limits (MDLs) are presented. For semivolatiles, evaluations of different extraction and cleanup procedures were also part of this study. The effects on semivolatile recovery and precision using three extraction procedures (two SW-846 methods and another EPA handbook method) were compared. Alumina and gel-permeation as cleanup procedures were compared to see which semivolatile analytes were unintentionally removed during cleanup and whether or not precision was improved relative to the no-cleanup case.

TCLP extraction fluid no. 1 (as per SW-846 Method 131 1) diluted 1 5 with reagent water. Extraction fluid no. 1 is prepared by diluting 5.7 millileters (mL) of glacial acetic acid and 64.3 rnL of 1 N sodium hydroxide with reagent water to a volume of 1,000 mL.

1-1



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Section 2

STUDY DESIGN

SAMPLE MATRICES Four matrices relevant to the petroleum refining industry were used in this study: an oily waste mixture of separator sludge and slop oil emulsion, a treated waste from a solvent extraction process, a clean loamy soil, and TCLP extraction fluid4 no. 1 diluted 1 5 with reagent water. Data for a reagent water matrix are also presented in this report. The reagent water data are from a different study and were obtained at different spiking levels. In some cases, reagent water data could not be compared directly with the other matrices.

ANALYTES Analytes of concern to the petroleum refining industry include volatiles, semivolatiles, and metals. For this study, analytes specific to the industry were identified from the Ground Water Monitoring List for hazardous wastes in Appendix IX of 40 CFR 264 (Code of Federal Regulations) and the Skinner or Refinery List. The Skinner List is a subset of the list of hazardous constituents in Appendix VIII of 40 CFR 261 and has been used for refinery waste delistings, land treatment demonstrations, and site closures related to petroleum refinery hazardous waste programs.

Refinery analytes in this study included 12 volatiles, 29 semivolatiles, and 7 metal analytes (Table 2-1). In the volatile group, m-xylene and p-xylene were not differentiated and were counted as a single analyte. In the semivolatile group, 3-methylphenol (m-cresol) and 4-methylphenol (p-cresol) were not differentiated and were counted as a single analyte.

I -methylnaphthalene 2-methylnaphthalene 2-methylphenol 3-& 4-methylphenol naphthalene phenanthrene phenol pyrene

Table 2-1. Refinery Analytes Volatiles Sem ivolatiles

acetone benzene 2-butanone carbon disulfide 1,2-dibromoethane 1 ,Cdioxane et hylbenzene methylene chloride styrene toluene m+p xylenes o-xylene

antimony arsenic chromium cobalt lead

Metals

acenaphthene acenaphthylene anthracene benzenethiol benzo(a)anthracene benzo(b)fluoranthene benzo(k)fluoranthene benzo(g, h,i)perylene benzo(a)pyrene bis(2-ethylhexy1)phthalate chrysene dibenzo(a, h)anthracene dibenzofuran 7,12-dmethylbenzanthracene 2,Cdimethylphenol fluoranthene fluorene I h-indene

nickel indeno( 1,2,3-cd)pyrene selenium 3-methylcholanthrene

Extraction fluid no. 1 is prepared by diluting 5.7 millileters (mL) of glacial acetic acid and 64.3 mL of 1N sodium hydroxide with reagent water to a volume of 1,000 mL.

2-1



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Although the refinery analytes were the primary focus of this study, API expanded the organic analyte list to include other hazardous constituents in the RCRA program because the additional cost was small compared to the value of the data generated. In total, this study included 53 volatiles, 128 semivolatiles, and seven metals (same metals as the refinery analytes). Tables 2-2 and 2-3 show the entire list of organic analytes in this study and for convenience, divide them into groups by compound type. Refinery analytes are highlighted in these tables.

The volatile analytes are divided into five groups: aromatic volatiles; halogenated volatiles; non-halogenated volatiles; EDBIDBCP (1,2-dibromoethane and 1,2-dibromo-3-chloropropane); and a group consisting of acrolein, acrylonitrile, acetonitrile and related compounds. Volatile refinery analytes primarily belong to the aromatic and non-halogenated groups.

The semivolatile analytes are divided into eleven groups: benzidines and amines, chlorinated hydrocarbons, haloethers, heterocyclics, nitroaromatics/cyclic ketones, nitrosamines, organophosphorus pesticides, phenols, phthalate esters, polynuclear aromatic hydrocarbons (PNAs), and a group of miscellaneous analytes labelled "Other." Semivolatile refinery analytes primarily belong to the PNA and phenol groups.

Table 2-2. All Volatile Analvtes Acrolein, Acrylonitrile, Acetonitrile (and related compounds)

acetonitrile acrolein acrylonitrile ethylcyanide methacrylonitrile

Aromatic Volatile Organics t benzene t ethylbenzene t styrene t toluene t m+pxylenes t o-xylene

t 12-dibromoethane t acetone t 2-butanone t carbon disulfide t 1,4-dioxane

2-hexanone 4-methyl-2-pentanone vinyl acetate

bromodichloromethane bromoform bromomethane carbon tetrachloride

EDBIDBCP 1,2-di bromo-3-chloropropane

Non-halogenated Volatile Organics

Halogenated Volatile Organics

Halogenated Volatile Organics (continued)

chlorobenzene 2-chloro-I ,3-butadiene chloroethane 2-chloroethyl vinyl ether chloroform chloromethane 3-chloropropene di bromochloromethane dibromomethane t-l,4-dichloro-Z-butene dichlorodifluoromethane 1 ,I-dichloroethane 1 ,Zdichloroethane 1, I-dichloroethene trans-I ,Z-dichloroethene I ,2-dichloropropane cis-I ,3-dichloropropene trans-I ,3-dichloropropene iodomethane

t methylene chloride I ,I ,2,2-tetrachloroethane 1 ,I , I ,24etrachloroethane tetrachloroethene 1 ,I ,I-trichloroethane 1 ,I ,2-trichloroethane trichloroethene trichlorofluoromethane 1.2.3-trichloro~ro~ane

I . .

vinyl chloride

-f Refinery Analyte

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A P I PUBLZ4597 95 II 0732290 0549823 3 6 3 II

Because the reagent water data were generated from another study, they did not include all of the organic analytes. Fifteen analytes were not spiked in the reagent water matrix. They are: benzenethiol; quinoline; p-phenylenediamine; phorate; disulfoton; parathion; famphur; I h-indene; 1 -methylnaphthalene; o,o,o-triethylphosphorothioate; sulfotepp; dimethoate; methyl parathion; chlorobenzilate; and hexachlorophene. Pentachlorobenzene was spiked in reagent water, but not in any of the other four matrices.

Table 2-3. All Semivolatile Analytes ienzldenes (& Amines)

aniline azobenzene benzidine 4-chloroaniline 3,3'dichlorobenzidine pdimethy laminoazobenzene 3,3'dimethylbenzidine aadimethylphenethylamine 1 -naphthylamine 2-naphthylamine 5-nitro-o-toluidine 2-nitroaniline 3-nitroaniline 4-nitroaniline

o-toluidine * p-phenylene diamine

:hlorinated Hydrocarbons 2-chloronaphthalene 1,2dichlorobenzene 1,3dichlorobenzene 1,4dichlorobenzene hexachlorobenzene hexachlorobutadiene hexachlorocyclopentadiene hexachloroethane hexachloropropene

.t pentachlorobenzene pentachloroethane 1,2,4,5-tetrachlorobenzene 1,2,4-trichlorobenzene

4-bromophenyl-phenylether bis(2-chloroethoxy )methane bis(2-ch1oroethyl)ether bis(2chloroisopropyl)ether

laloethers

Heterocyclics t dibenzofuran

isosafrole (#I) isosafrole (#2) methapyrilene 4-nitroquinoline-l-oxide n-nitrosomorpholine n-nitrocopyrrolidine 2-picoline pyridine

* quinoline safrole

NitroaromaticslCyclic Ketones

4-aminobiphenyl mdinitrobenzene 2,4dinitrotoluene 2,6dinitrotoluene isophorone nitrobenzene n-nitrosopipendine pentachloronitrobenzene sym-trinitrobenzene

n-nitrocodi-n-butylamine n-nitrosodiethy lamine n-nitrosodimethy lamine n-nitrosodiphenylamine n-nitrosodi-n-propylamine

Nitrosamines

Polynuclear Aromatic Hydrocarbons (PNAs) (Cont'd.) t benzo(b)fluoranthene t benzo(k)fluoranthene t benzo( g, h, i)perylene t benzo(a)pyrene t chrysene t dibenz(a,h)anthracene t 7,12dimethylbenzanthracene t fluoranthene t fluorene *t lh-indene t indeno( 1,2,3-cd)pyrene t 3-methylcholanthrene *t l-methylnaphthalene t 2-methylnaphthalene t naphthalene t phenanthrene t pyrene

Organophosphorus Pesticides dimethoate disulfoton famphur methyl parathion

* parathion * phorate * sulfotepp * o,o,o-triethylphosphorothioate

Phenols (Cont'd.) 2,4dinitrophenol

t 2-methylphenol t 3 4 4-methylphenol

2-nitrophenol 4-nitrophenol pentachlorophenol

2,3,4,-tetrachlorophenol 2,4,5-tnchlorophenol 2,4,6-trichlorophenol

butylbenzylphthalate di-n-butylphthalate diethylphthalate dimethylphthalate di-n-octyl phthalate

t phenol

Phthalate Esters

t bis(2-ethylhexyl)phthalate

Other acetophenone 2-acetylaminofluorene aramite (#1) aramite (#2)

*t benzenethiol benzyl alcohol chlorobenzilate ethylmethacry late ethylmethane sulfonate

n-nitrosomethylethylamine Phenols * hexachlorophene Polynuclear Aromatic benzoic acid methylmethacry late Hydrocarbons (PNAs) 2-sec-buiyl4.6dinitrophenol( DNBP) methylmethanesulfonate t acenaphthene 4-chloro-3-methylphenol 1 ,Cnaphthoquinone t acenaphthylene 2-chlorophenol phenacetin t anthracene 2,4dichlorophenol pronamide t benzo(a)anthracene 2,6dichlorophenol

t 2,4dimethylphenol 4-chlorophenyl-phenylether 4,6-dinitro-2-methylphenol

t Refinery Analyte

Not spiked in reagent water Not spiked in TCLP leachate, clean soil, treated waste, or oily waste

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SPIKE LEVELS Spike levels used in this study are shown in Table 2-4 for organics and in Table 2-5 for metals. The oily and treated waste samples contained background levels of some analytes. All solid matrices contained background levels of the metals. Each sample matrix was analyzed before spiking to determine background concentrations and then spike levels were set accordingly. The spike levels for the metals were also based on the sensitivity of the analytical method.

Table 2-4. Spiking Levels (Organics) Spiking Levels

General Spiking Levels

Reagent Water TCLP Leachate Clean Soil Treated Waste Oily Waste

Semivolatiles 5

1 O0 1,000 5,000

25,000

AnalyteSpecific Spiking Levels Volatiles

* 1 ,4-Dioxane spiked at 20 times the general spike level in all matrices shown above. Spiking levels (pg/L) for specific volatiles in reagent water that differ from the above general levels are shown below.

Volatiles acetone 25 acrolein 1 O0 acrylonitrile I O0 2-butanone 25 2-chloroethyl vinyl ether 25 vinyl acetate 25

** Spiking levels (pg/L) for specific semivolatiles in reagent water that differ from the above general levels are shown below.

aramite (#I) 2.5 aramite (#2) 2.5 benzidine 50 33-dichlorobenzidene 40 3,3-dimethyl benzidene 40 4,6-dinitro-2-methylphenol 40 2,4-dinitrophenol 40 isosafrole (#I) 10 isosafrole (#2) 10

3-methylcholanthrene 10 1,4-naphthoquinone 1 O0

Semivolatiles

Semivolatiles

methapyrilene 40

2-nitroaniline 40 3-nitroaniline 40 4-nitroaniline 40 4-nitrophenol 40 4-nitroquinoline 1 O0 5-nitro-o-toluidine 20 pentachloronitrobenzene 40 pronamide 10 2,4,5-trichlorophenol 40

2-4



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Table 2-5. Spiking Levels - (Metals) Spiking Levels (pg1L)

ICP antimony arsenic chromium cobalt lead nickel selenium

antimony arsenic selenium

GFAA

0.05 0.05 0.05 0.05 0.05 0.05 0.5

0.02 0.01 0.02

0.5 0.5 0.2 0.2 0.5 0.5 2

0.5 0.5 0.2

50 50 20 20 50 50 200

50 5 2

50 50

20 50 50 200

50 50 2

t

50 50

20 50 50 200

50 50 2

t

* Chromium not spiked due to high levels in sample

ANALYTICAL METHODS With the exception of one cleanup method, sample preparation and analytical methods used in this study were from the United States Environmental Protection Agencys (EPAs) Test Methods for Evaluating Solid Waste, SW-846, third edition (SW-846) [USEPA 19861.

Volatiles were analyzed by SW-846 Method 8240, Gas Chromatography/Mass Spectrometry for Volatile Organics [USEPA i 986il. Semivolatiles were analyzed by SW-846 Method 8270, Gas Chromatography/Mass Spectrometry for Semivolatile Organics: Capillary Column Technique [USEPA 1986jl.

Three extraction procedures for semivolatiles were compared in this study. The first procedure was SW-846 Method 3550, Sonication Extraction, using a one-to-one ( I :I) mixture of methylene chloride and acetone for the extraction solvent [USEPA 1986bl. The second procedure also used the sonication extraction procedure in SW-846 Method 3550, but with 100% methylene chloride. Method 3550 states that the 1:l mixture of methylene chloride and acetone provides a more rigorous extraction procedure. However, it is well documented that acetone reacts with itself during the extraction process to form aldol condensation products such as diacetone alcohol. The reaction products are manifested as a series of early eluting interfering compounds. The third extraction procedure was taken from EPAs guidance manual, Handbook for the Analysis of Petroleum Refinery Residuals and Wastes (Handbook) [Radian 19841. This procedure is a simultaneous extractiodacid-base partition preparation which includes the sonication and phase separation with methylene chloride and aqueous sodium hydroxide for baseheutral analytes, followed by extraction of the acidified aqueous layer for the acid analytes. For the oily waste, only the Handbook method and Method 3550 with 100% methylene chloride were evaluated.

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Two cleanup procedures to remove interferences for semivolatiles were evaluated. The first procedure was SW-846 Method 3640, Gel-Permeation Cleanup, (GPC) [USEPA 1986dl. The second procedure was SW-846 Method 361 1, Alumina Column Cleanup and Separation of Petroleum Wastes [USEPA 1986~1. Alumina column cleanup has been widely used to remove interferences from aliphatic hydrocarbons in oily wastes for the determination of a select list of semivolatile analytes. The application of this cleanup technique to a broader suite of analytes, for example, the Appendix IX Ground Water Monitoring List, has not been studied.

The GPC Method 3640 was developed in EPAs Contract Laboratory Program (CLP) for a limited suite of analytes and its use for Appendix VIII analytes has been discussed [Marsden and Longbottom 19871; however, its utility for samples containing aliphatic hydrocarbons has not been thoroughly evaluated. Furthermore, whether alumina or GPC cleanup provides improved reliability as relative to the no-cleanup case has not been studied.

Metals were analyzed by two SW-846 methods. SW-846 Method 601 O, Inductively Coupled Plasma Atomic Emission Spectroscopy, (ICP) was used for all 7 metals [USEPA 1986el. Three of these 7 metals were also analyzed by SW-846 graphite furnace atomic absorption (GFAA) methods: antimony (Method 7041) [USEPA 1986f1, arsenic (Method 7060) [USEPA 198691, and selenium (Method 7740) [USEPA 1986hl. Prior to analysis, solid samples were digested using SW-846 Method 3050, Acid Digestion of Sediments, Sludges, and Soils [USEPA 1986al.

NUMBER OF SAMPLES Analytical method performance (recovery, precision, MDL) was based on seven to eight replicate samples from each matrix; the exact number used for each matrix is discussed in the next chapter, Method Performance. Two replicate samples from both the treated and oily waste were extracted by each of the three extraction procedures. For the evaluation of cleanup procedures, alumina column cleanup was used on seven replicate samples of both the treated and oily waste. These same samples were then analyzed for semivolatile recovery, precision, and MDLs. GPC was used on four treated waste and three oily waste replicate samples. Three replicate samples of treated waste and four replicate samples of oily waste were extracted with no followup cleanup.

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Section 3 METHOD PERFORMANCE

Method performance in recovery, precision, and method detection limits is presented for volatiles, semivolatiles, and metals. In addition to these basic performance data, the section on semivolatiles includes a comparison of three different extraction procedures and a comparison between GPC and alumina column cleanup.

VOLATILES Reco - verv and P recision Seven samples of each of the five matrices were used for recovery and precision evaluation of volatiles. The average recoveries for each analyte are listed in Appendix A by analyte group along with the median average recovery among all analytes within the group.

. .

A summary of these median recoveries for each analyte group is shown in Table 3-1. The ranges in median recoveries were:

Reagent water 96-1 23% Treated waste 76*-103% TCLP leachate 90-1 03% Oily waste 63-1 15% Clean soil 86111% * Not including the 4% recovery for the acrolein, acrylonitrile, acetonitrile group

Table 3-1. Volatile Recovery (Analyte Groups) Median Recovery ("h)

Analyte Group r*] Reagent TCLP Clean Treated Oily Water Leachate Soil Waste Waste

Spike Level' 5 pglL 100 pglL 20 pgikg 1,250 pglkg 5,000 pgikg

Acrolein, Acrylonitrile, Acetonitrile [5] 102 90 105 4 87 (and related anaIfles)***

Aromatic Volatile Organics [6] 103 103 103 103 115

EDB/DBCP*"* [2] 123 94 84 84 63

Halogenated Volatile Organics [33] 96 95 94 84 95

Non-halogenated Volatile Organics m 96 1 O0 111 76 82 Most analytes in reagent water spiked at 5 VgiL, some at higher levels (see Chapter 2, "Study Design," for specific spike levels). Number in brackets is number of analytes in each group.

-* Methacrylonitrile and ethylcyanide - 1,Z-Dibromoethane and 1,2dibromo-3-chloropropane 3- 1



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Reagent water, TCLP leachate, and clean soil had similar recovery performances. Treated and oily wastes recoveries were similar and overall were lower than the other three matrices. The median recovery of the acrolein, acrylonitrile, and acetonitrile group in treated waste was particularly poor (4%). Of the five analytes in this group, only acrylonitrile and methacrylonitrile had reasonable recoveries in treated waste (69% and 89%, respectively); acetonitrile and acrolein were not recovered and ethylcyanide had only an average 4% recovery. The aromatic volatile organic group consistently had recoveries greater than 100% in all five matrices.

Average recoveries for the 12 volatile refinery analytes are shown in Table 3-2. Some problems were encountered with several of these analytes as seen by the abnormally low and high recoveries in the table. Calibration problems were experienced with the xylenes and blank contamination was suspected with acetone and methylene chloride analyses. Outlier analyses identified 2-butanone; carbon disulfide; and I ,Cdioxane with recovery outside the normal performance for some matrices. Median recoveries for the refinery analytes, however, were similar to the entire set of volatiles shown previously in Table 3-1 except in the oily waste matrix. For this matrix, the median recovery of refinery volatiles was significantly higher (1 05%) than the median recovery shown for all analytes (87%).

Table 3-2. Volatile Recovery (Refinery Analytes) I Recovery ("YO)

Reagent TCLP Clean Treated Oily Water Leachate Soil Waste Waste

Spike Level' 5 PgI i 100 pgl i 20 pglkg 1,250 pglkg 5,000 pglkg

acetone" benzene 2-buianondt carbon disulfide# 1,2-dibromoethane 1 ,4-dioxane# ethyl benzene methylene chloride" styrene toluene m+p xylenes** &xylene**

Median

104 83 21 5 76 160 110 96 97 93 105 104 119 137 70 48 86 68 103 60 79 98 105 88 79 92 86 71 116 54 92 99 1 o9 104 111 124

108 I O0 138 307 1 o9 83 91 85 a2 103

107 95 I 02 94 106 119 160 151 155 178 97 122 1 o9 115 128

1 o1 98 1 06 88 105 I I

Most anaiytes in reagent water spiked at 5 YglL, some at higher levels (see Chapter 2,

** Calibration problems *** Possible blank contamination # Statistical outlier in one or more matrices

"Study Design," for specific spike levels.

Matrix effects on recovery and precision for refinery volatiles were analyzed only with the five analytes that did not have calibration, blank, or outlier problems. These five analytes were

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benzene; 1,Zdibromoethane; ethylbenzene; styrene; and toluene. A summary of the recovery and within-analyte precision for each matrix is shown in Table 3-3. The within-analyte precision is the pooled estimate from the standard deviations of individual analytes (the individual standard deviations based on the replicate samples).

Statistical tests on recovery and precision indicated matrix effects on precision, but not on recovery. With two exceptions, significant differences in precision were shown among all matrices. No matrix effects on precision were shown between TCLP leachate and oily waste and between clean soil and oily waste. Precision for reagent water was notably worse than the other matrices, however, this was not surprising since the spiking levels in this matrix were near the method detection limit; at these concentrations performance typically worsens.

Table 3-3. Volatile Performance by Matrix (Refinery Analytes**)

Matrix RecoveryfStandard Deviation (%)*

Reagent water 99YoI21 Yo

TCLP leachate 99%*1 I %

Clean soil 95%i6%

Treated waste 92%*3%

Oily waste 106%*8%

* RecoveryIStandard Deviation (%) Based on seven samples for each matrix. The standard deviations are pooled estimates of the within analyte precision.

c1 Refinery Analytes Includes only these five of the twelve refinery volatile analytes: benzene;

The other seven refinery volatile analytes were omitted from the calculations for the following reasons:

1,2-dibromoethane; ethylbenzene; styrene; toluene.

Calibration problems: m- & pxylenes, o-xylene. Possible blank contamination: acetone; methylene chloride. Outliers: 2-butanone; carbon disulfide; I ,4-dioxane.

- Precision for reagent water appears worse than the other matrices because the spike levels were near the detection limit where performance typically worsens.

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Method Detection Limits (MDLs) MDLs were calculated from the replicate samples for the five matrices for all analytes in accordance with procedures at 40 CFR 136, Appendix B. MDLs for the individual volatile analytes are listed by analyte group in Appendix B of this report. Table 3-4 is a summary of the median MDLs based on all of the volatile analytes for each analyte group. MDL ranges of the median values are shown below:

Reagent water 3-1 1 pg/L Treated waste 110-700 pg/kg TCLP leachate 33-51 pg/L Oily waste 830-9,500 pg/kg Clean soil 3-1 2 pg/kg

Table 3-4. Volatile MDLs (Analyte Groups)

I Method Detection Limits (MDLsbMedians by Group Anaiyte Group y]

Spike Level

Acrolein, Acrylonitrile, Acetonitrile [5] (and related analytes)

Aromatic Volatile Organics [6]

EDBIDBCP [2]

Halogenated Volatile Organics [33]

Non-halogenated Volatile Organics [A

Reagent Water 5 PglL

Il

3

7

4

7

TCLP Leachate 100 pglL

51

35

35

33

46

Clean Treated Soil Waste

20 pglkg 1,250 pglkg

12 400

4 I i o

5 400

5 140

8 700

Oily Waste

5,000 pglkg

6200

830

4500

1500

9500

I

* Most analytes in reagent water spiked at 5 pg/L, some at higher levels (see Chapter 2, Study Design, for specific spike levels). Number in brackets is number of anaiytes in each group. - Methacrylonitrile and ethylcyanide

MDLs for the volatile refinery anaiytes are shown in Table 3-5. MDLs for Il4-dioxane were much higher than for the other analytes because it was spiked at 20 times the level of the others. Ranges in MDLs, excluding I ,4-dioxane, were:

Reagent water 2-9 pg/L Treated waste 69-1,600 pg/kg TCLP leachate 30-87 pg/L Oily waste 390-9,500 vg/kg Clean soil 3-13 pg/kg

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Table 3-5. Volatile MDLs (Refinery Analytes) Method Detection Limits (MDLs)

Note different units for liquids and solids->

Spike Level*

acetone" 3enzene 2-butanone# xrbon disulfide# 1 ,Zdibromoethane 1,4-dioxane## 2thylbenzene nethylene chloride*** styrene :oluene n+p xylenes** >-xylene**

Reagent Water (IJglL)

5 IJglL

7 2 9 3 4

220 4 3 3 3 4 3

TCLP Leachate

( IJgU

100 pg/L

87 33 51 30 34

2600 36 45 34 32 54 43

Clean Soil

( I J g W

20 IJgm

8 5

12 13 4

460 5 4 3 4 8 4

Treated Waste (IJiglkg)

1,250 W k g

700 I10

1100 69

130 14000

150 1600

89 120 230 I10

Oily Waste (IJglkg)

5,000 vdkg

3400 830

9500 1800 2500

47000 620

2800 850 390 830 930

Median 3 40 5 140 1400

Most analytes in reagent water spiked at 5 pg/L, some at higher levels (see Chapter 2,

** Calibration problems *** Possible blank contamination

# Statistical outlier in one or more matrices

"Study Design," for specific spike levels.

According to SW-846 Method 8240, the MDL for an oily waste should be about 500 times the MDL for a clean soil5. In this study, 9 of the 12 volatile refinery analytes met this criterion. The refinery analytes that did not meet this criterion were, with their oily waste to clean soil ratios: 2-butanone (81 8); 1,2-dibromoethane (683); and methylene chloride (656). Of the 53 volatile analytes in this study, only 34 were able to meet the criterion; however, all aromatic volatiles met the criterion. MDL ratios between oily waste and clean soil for each of the volatile analytes are found in Appendix B.

SEM IVOLATI LES Extraction The performance of the three sample extraction methods for clean soil, treated waste, and oily waste for refinery analytes is compared in Table 3-6. Overall performance in recovery for SW-846 Method 3550 with a 1: l solution of methylene chloride and acetone was 77%, for Method 3550 with 100% methylene chloride alone was 73%, and for the EPA handbook method

The ratio is actually iven in the method for Practical Quantitatjon Levels (PQLs); however, since the PQL is a multiple of the MDL, t\is ratio holds true for the MDL as well. It is assumed that the oily waste and clean soil in this study are comparable to the non-water miscible waste and low soillsediment, respectively, in SW-846.

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recovery was 79%. An analysis of variance on the recoveries, however, showed no difference in recovery among methods or matrices.

Table 3-6. Comparison of Extraction Procedures for Semivolatiles (Refinery Analytes***) Extraction Method*

3550 3550 Handbook MC:AC MC AcidlBase

RecoveryfStandard Deviation ('%O)**

Clean soil 82%f3% 74%110% 73%f3%

Treated waste 71 %I1 1 % 80%*5% 84%f9%

Oily waste - 63%*4% 79%118%

All matrices 77%18% 73%f7% 79%fl2%

* Description of Methods SW-46 Method 3550 (Sonication Extraction) MC:AC-extraction with methylene ch1oride:acetone (1 :I), normally used where

concentrations of individual analytes are < 20 mglKg MC-extraction with 100% methylene chloride, normally used where concentrations of

individual analytes are > 20 mgiKg, like for the oily waste Extracts from treated and oily wastes were cleaned using SW-846 Methods 3650 (Acid-

base Partition Cleanup) and 361 1 (Alumina Column Cleanup and Separation of Petroleum Wastes)

and Wastes," extraction with acid-base partitioning Handbook, AcidiBase: "Handbook for the Analysis of Petroleum Refinery Residuals

* RecoveryIStandard Deviation (%) Based on two samples for each methodmatrix. The standard deviations are pooled estimates of the within analyie precision.

*** Refinery Analytes Of the 28 refinery sernivolatiles, only 23 are included in this table. Five anaiytes were omitted from this comparison because of calibration problems (acenaphthylene, benzenethiol) or because they were statistical outliers (bis(2ethylhexyl)phthalate; 7,lZdirnethylbenzanthracene; naphthalene).

Precision (within-analyte) ranged from 3% to 18%. Statistical tests on the data suggest that the handbook method was less precise than SW-846 Method 3550; however, because the tests were based on only two samples for each combination, this was not considered confirmatory.

Five of the refinery analytes were excluded in the comparison of extraction methods. Acenapthylene and benzenethiol were excluded because of calibration problems and three other analytes were excluded because they were outliers (bis(2-ethylhexy1)phthalate; 7,12-dirnethylbenzanthracene; naphthalene). Naphthalene was an outlier because it was not detected due to aldol condensate interference in the methylene ch1oride:acetone extractions.

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Since none of the extraction methods was found significantly better than the others, Method 3550 with 100% methylene chloride was selected for the rest of the semivolatile analyses because it did not produce aldol condensate interferences like the methylene ch1oride:acetone method and it was less labor intensive than the handbook method.

Cleanur, Cleanup procedures for semivolatile analysis using GPC and alumina columns were compared for treated and oily wastes. One of the objectives of this comparison was to see which analytes were not recovered by each column. A second objective was to see if cleanup procedures could improve recovery and precision without a deterioration in analyte detection.

Baseline performance of the GPC and alumina columns without matrix interferences was first determined with a standard solution. The average recoveries for GPC and alumina were 83% and 78%, respectively and were not found to be statistically different. As noted in Table 3-7, the phenolic refinery analytes (2,4-dimethylphenol; 2-methylphenol; 3-&4-methylphenol; phenol) were not included in this comparison because acid/base partitioning was not done prior to running the sample through the alumina column. One other analyte was excluded from the comparison because it was a statistical outlier (7,12-dimethylbenzanthracene). As discussed before, the two refinery analytes that had calibration problems (acenaphthylene; benzenethiol) were also left out of the comparison.

Table 3-7 shows that nine analytes in the standard solution were not recovered after cleanup by GPC while twelve analytes were not recovered after alumina cleanup. None of the unrecovered analytes were refinery analytes. Five analytes were not recovered due to GPC or alumina cleanup: benzidene; hexachlorocyclopentadiene; hexachlorophene; methylmethacrylate; and p-phenylene diamine. The analytes that were not recovered were from four analytical groups: benzidenes and amines; chlorinated hydrocarbons; nitroarornatics/cyclic ketones; and other. The only notable difference between GPC and alumina columns appeared in the chlorinated hydrocarbons group where five analytes were not recovered by alumina as opposed to only one analyte not recovered by GPC. This difference in the chlorinated hydrocarbons group, however, was not seen in the treated and oily wastes.

Recovery performance after GPC and alumina column cleanup for refinery analytes is shown in Table 3-8 for treated and oily wastes. Phenolic analytes were included in the comparison because acid/base partitioning was used before the alumina column. Neither GPC nor alumina column cleanup showed a statistical difference in overall recovery for treated and oily wastes when compared to no cleanup. With treated waste, recovery with no cleanup was 83%; recovery was 87% and 78% after GPC and alumina column cleanup, respectively. With oily waste, no cleanup recovery was 61 % while GPC was 48% and alumina was 52%.

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Table 3-7. Nondetects after Cleanup for Semivolatiles Standard Solution (All Analytes)

Cleanup Method GPC Alumina"

Benzidines (a Amines) aniline benzidine 3,3'-dimethylbenzidine aa-dimethylphenethylamine 2-na ph t hylamine 4-nitroaniline p-phenylene diamine

X X X X

X X

X X X

Chlorinated Hydrocarbons hexachlorobutadiene X hexachlorocyclopentadiene X X hexachloroethane X hexachloropropene X pentachloroethane X

NitroaromaticslCyclic Ketones

Other

4-aminobiphenyl

hexachlorophene methylmethacrylate 1,4naphthoquinone

I X X X X X

X

I Number of analytes 9 12 x Not detected after cleanup

Phenolic compounds are not included in comparison because acidbase partitioning was not done prior to using the alumina column

Table 3-8. Comparison of Cleanup Procedures for Semivolatiles Treated and Oily Wastes (Refinery Analytes **)

Cleanup Method* No

Cleanup GPC Al um na

Recovery (%)

Treated waste 83% 87% 78% (number of samples) 3 4 7

Oily waste 61% 48% 52% (number of samples) 4 3 7

Description of Methods No cleanupsamples were analyzed at dilutions due to matrix interferences. Consequently,

GPC-Gel Permeation Chromatography, SW-846 Method 3640 (Gel-Perneation Cleanup)

AluminbSW-846 3650 (Add-Base Partition Cleanup) and SW-846 Method 361 1 (Alumina

Column Cleanup and Separation of Petroleum Wastes)

all values were below reporting limits and therefore, are only estimated values.

Both treated and oily wastes were extracted with 100% methylene chloride

using SW-846 Method 3550 (Sonic Extraction).

Refinery Analytes Of the 28 refinery semivolatiles. only 21 are included in this table. Seven anaiytes were omitted from this comparison

because they either had calibration problems (acenaphthylene, benzenethiol) or because they were statistical-

outliers (benzo(b)iumnthene; benro(g,h,i)perylene; bis(2ethylhexyl)phthalate; 3-methylcholanthrene; 2- methylphenol).

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Table 3-9 shows the analytes that were not recovered before or after cleanup. At the bottom of the table is an overall performance summary that shows the number of analytes that were not detected using no cleanup, GPC cleanup, and alumina column cleanup. It also shows the percentage of nondetects in the total number of analyses.

GPC recovered substantially more analytes from the treated waste than either no cleanup or alumina column cleanup. After GPC, only 18 of the semivolatiles were never recovered, compared to 33 nondetects after alumina column cleanup and 51 with no cleanup. GPC performance for the oily waste was also better than no cleanup or alumina. After GPC, only 36 of the semivolatiles were never recovered, compared to 40 nondetects after alumina column cleanup and 43 with no cleanup.

Overall analyte recovery from the treated waste was improved after alumina column cleanup although performance among analyte groups was mixed. In particular, alumina column cleanup of the treated waste substantially improved recovery of phenolic analytes, however, recovery was worse with nitrosamines and phthalate esters. Performance among analyte groups was also mixed for the oily waste and on average, alumina column cleanup did not improve recovery. Substantial improvement was shown in the recovery of phenolic analytes from the oily waste, however, recovery after cleanup was worse with phthalate esters and PNAs.

Except for several PNAs in the oily waste, detection was improved after both GPC and alumina column cleanup for nearly all of the refinery analytes. Detection in the treated waste was improved for acenaphthylene; benzenethiol; benzo(g, h,i)perylene; bis(2-ethylhexy1)phthalate; chrysene; 7,12-dimethylbenzanthracene; and 3-&4-methylphenol. Detection in the oily waste was improved after cleanup for acenaphthylene, benzenethiol, and 2-methylphenol. Recovery of PNAs 7,12-dimethylbenzanthracene; 1 -methylnapthalene; phenanthrene; and pyrene from the oily waste was worse after GPC and alumina column cleanup.

A comparison of precision before and after column cleanup is shown in Table 3-10. In this comparison, analytes are listed where cleanup improved precision as well as where cleanup degraded precision. Differences in precision in this table were tested for statistical significance by an F-test instead of judging if the precision merely increased or decreased. Those analytes that were not recovered or recovered infrequently were not included in the comparison.

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Table 3-9. Nondetects after Cleanup for Semivolati les Treated and Oily Wastes (All Analyte: Key Treated Waste Oily Waste O Not detected in at least one replicate No No = Not detected in any replicate Cleanup GPC Alumina Cleanup GPC Alumina t Refinery analyte

Number of samples 3 4 7 4 3 7 Benzidines (a Amines)

aniline rn O w benzidine rn

4-chloroanaline O rn O 3,3-dichlorobenzidine

W 3,3-dimethylbenzidine W rn rn rn w aa-dimethylphenethylamine W W

1 -naphthylamine rn 2-naphthylamine O O W 2-nitroaniline O W

~

3-nitroaniline O w w 4-nitroaniline W rn W 1 W 5-nitro-o-toluidine O p-phenylene diamine W W w rn o-toluidine W m

Chlorinated Hydrocarbons hexachlorobutadiene O O

w hexachlorocyclopentadine W rn W W hexachloroethane rn O hexachloropropene O O O P pentachloroethane W rn

Haloethers

I iccafroie # ~ W O rn methapyrilene O W rn O rn

w 4-nitroquinoline-I-oxide w rn W n-nitrosomorpholine O O n-nitrocopyrrolidine rn U rn 2-picoline rn W Dvridine O O w W

I auinoline O = I Nitrosamines

n-nitrocodi-n-butylamine rn O W n-nitrosodiethylamine O O n-nitroso-di-n-propylamine n-nitrosomethvlethvlamine O

NitroaromaticslCyclic Ketones 4-aminobiphenyl rn W rn m-dinitrobenzene W rn 2,4-dinitrotoluene O 2,b-dinitrotoluene rn

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Table 3-9. Nondetects after Cleanup for Semivolatiles Treated and Oily Wastes (All Analytes)

Key Treated Waste Oily Waste O Not detected in at least one replicate No No rn Not detected in any replicate Cleanup GPC Alumina Cleanup GPC Alumina t Refinery analyte

(Continued)

henanthrene O

acetophenone O 2-acetylaminofluorene rn rn O rn aramite (#I) rn rn rn rn

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Table 3-9. Nondetects after Cleanup for Semivolatiles Treated and Oily Wastes (All Analytes) (Continued)

Key Treated Waste Oily Waste O Not detected in at least one replicate No No rn Not detected in any replicate Cleanup GPC Alumina Cleanup GPC Alumina t Refinery analyte

Number of samples 3 4 7 4 3 7

aramite (#2) rn rn rn rn

benzyl alcohol rn O H O chlorobenzilate rn 1 ethylmethacrylate O hexachlorophene rn rn rn rn O methylmethacwlate H methylmethanesulfonate rn O O

rn 1,4-naphthoquinone rn rn rn rn phenacetin rn O H rn

Other (Continued)

t benzenethiol rn rn

pronamide rn rn

Total number of anaiytes 127 127 127 127 127 127

Number of analytes not detected at least once 58 22 57 55 43 61

Number of analytes not detected in any replicate 51 18 33 43 36 40

Percent of all analyses not detected 42% 15% 35% 39% 31% 39%

At the bottom of Table 3-10 are the total number of analytes with improved precision, poorer precision, and no difference in precision after cleanup. Overall, these numbers show that cleanup had little effect on the treated waste precision and tended to degrade the oily waste precision.

Table 3-1 O. Precision After Cleanup, Treated and Oily Wastes (All Analytes) Treated Waste Oily Waste

GPC Alumina GPC Alumina Benzidines (i% Amines)

Chlorinated Hydrocarbons azobenzene X

2-chloronaphthalene X X 1,2-dichlorobenzene X 1,3-dichlorobenzene X I ,4-dichlorobenzene hexachlorobenzene 1,2,4,5-tetrachIorobenzene X X X 1,2,4-trichIorobenzene X X X

bis(2-ch1oroethoxy)methane - X X Haloethes

bis~2-chloroethvl~ether X

I 4-bromophenyl-phenylether X X I I I

0 Improved precision after cleanup x Poorer precision after cleanup t Refinery analyte

- No difference in precision after cleanup

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Table 3-1 O. Precision After Cleanup, Treated and Oily Wastes (All Analytes) (continued)

I t fluoranthene I t fluorene t 1 h-indene t indeno(l,2,3-cd)pyrene X X t 3-methylcholanthrene X X t I-methylnaphthalene t 2-methylnaphthalene X X X t naphthalene X X t phenanthrene X t pyrene X X

Analyies with improved precision 1 2 O 1 Analytes with poorer precision 2 7 16 15 Analytes with no difference 33 27 20 20

0 Improved precision after cleanup x Poorer precision after cleanup

- t Refinery analyte

No difference in precision after cleanup

Although cleanup does not appear to offer any advantages in precision, it does offer other advantages. For example, practical quantitation levels (PQLs) will be lower with cleaned samples. In this study, the oily waste samples were analyzed at the following final sample volume/sample weight ratios: uncleaned samples, 10 mL per gram (mug); GPC, 2 mug; and alumina, 1 mug. Consequently, the uncleaned samples had higher PQLs than the cleaned samples and results for the uncleaned samples were reported below the PQL which was not necessary for the cleaned samples. In general, the spectra obtained below the PQL are poor quality and at times, technically questionable.

Cleanup also helps to remove analytical interferences..GPC removes high molecular weight interference while alumina removes interference from high concentrations of aliphatic hydrocarbons. Both cleanup techniques are useful for their intended purpose and both may be necessary based on the materials in the sample.

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The constant introduction of contaminants into the measurement system will eventually degrade the performance of the system. As discussed in SW-846 Method 3600, "Cleanup", cleanups are designed to purify extracts to prevent deterioration of column efficiency and loss of detector sensitivity and as such, can increase the useful life of expensive columns.

Recovery and Precision Method performance for semivolatiles was based on eight samples for the TCLP leachate and seven samples for the other four matrices. The solid samples, clean soil, treated waste, and oily waste, were extracted with 100% methylene chloride using the sonic extraction technique in SW-846 Method 3550. Following extraction, the treated and oily waste samples were cleaned using acid-base partitioning and alumina column cleanup.

Average recovery for each analyte and median recovery for each analyte group are found in Appendix C while median values by analyte group are summarized in Table 3-1 1. Median recovery ranges were:

Reagent water 73*-97% Treated waste O-87%

Clean soil 72-1 19% TCLP leachate 72-1 08% Oily waste 0 4 4 %

Not including the 48% recovery for the phthalate esters group. The low recovery of phthalate esters in reagent water was believed to be a result of sample contamination.

Table 3-1 1. Semivolatile Median Recovery (All Analytes) Median Recovery (%)

Analyte Group r y Reagent TCLP Clean Treated Oily Water Leachate Soil Waste Waste

Spike Level' 5 pglL 100 pgiL 1,000 pglkg 5,000 pglkg 25,000 pglkg

Benzidines (8 Amines) [I61 96 85 74 O O

Chlorinated Hydrocarbons [ I 31 73 72 79 59 50

Haloethers [5] 94 80 86 87 64

Heterocyclics [I I] 88 99 72 10 O

NitroaromaticslCyclic Ketones [9] 97 87 78 67 61

Nitrosamines [6] 93 1 O0 78 6 9

Organophosphorus Pesticides [8] **

Phenols [I81 90 79 79 68 55

Phthalate Esters [6] 48 73 86 46 11

108 119 50 31

Polynuclear Aromatic 87 72 84 80 50 Hydrocarbons (PNAs) [21]

Other [15] 73 86 77 O 9 Most Analytes in reagent water spiked at 5 pglL. some at higher levels (see Chapter 2, "Study Design," for specific spike levels).

Not spiked ** Number in brackets is number of anaiytes in each group.

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Average recoveries for the each refinery analyte and overall median recoveries are listed in Table 3-12. Average recoveries for each matrix are shown in Table 3-13. Averages were calculated after deleting those analytes with calibration problems (acenaphthylene; benzenethiol), those that were not spiked in reagent water (1 h-indene; 1 -methylnaphthalene), and those that were statistical outliers (bis(2-ethylhexy1)phthalate; 3-methylcholanthrene; benzo(b)fluoranthene; benzo(g,h,i)perylene).

Statistical differences were found among matrices in both recovery and precision. The recovery for oily waste was significantly lower than the other four matrices. The recoveries for TCLP leachate, clean soil, and treated waste were statistically the same. The significant differences among matrices are summarized in the chart below. Each value in the chart represents the average difference between two matrices. Where there was no statistically significant difference between matrices, the chart contains a - . I For example, the recovery for the treated waste was 12 percentage points less than the recovery for reagent water, but no difference was found between the treated waste and TCLP leachate or clean soil.

Summary of Significant Difference in Recovery by Matrix Semivolatile Refinery Analytes

~~~

RW TCLP CLN TRT OILY

Numbers In table are average differences in recovery. Example: Reagent Water - TCLP = 1 P ! average difference (-) No significant diffemn found

Precision petformance was best with TCLP leachate, then clean soil. Reagent water precision tested equivalent to treated and oily wastes. As noted in the discussion of volatile performance, the poor precision in the reagent water matrix was related to low, near MDL spiking levels.

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Table 3-1 2. Semivolatile Median Recovery (Refinery Analytes) Recovery (%)

Spike Level'

acenaphthene acenaphthylene anthracene ienzenethiol ienzo(a)anthracene ienzo( b)fluoranthene ienzo(k)fluoranthene ienzo(g, h,i)perylene ienzo(a)pyrene iis(2-ethyl hexy1)phthalate :hrysene iibenzo(a,h)anthracene iibenzofuran I , 12-dimethylbenzanthracene !,4-dimethylphenol luoranthene luorene I h-indene ndeno(l,2,3-cd)pyrene i-methylcholanthrene I -methylnaphthalene !-methylnaphthalene i-& 4-methylphenol !-methyl phenol iaphthaiene ihenanthrene ihenol jyrene

Reagent TCLP Water 5 PBIL

96 1 O0 1 O0

95 86 87 75 83

29 1 107 73 96 77 81 97 93

67 53

87 102 86 86 103 95 104

H

H

CI

Leachate 1 O0 pg1L

73 18 68 147 73 68 78 70 65 87 83 73 85 60 57 75 75 68 73 46 59 78 78 76 64 72 80 74

Clean Treated Oily Soil

1,000 pglkg Waste Waste

5,000 pglkg 25,000 pgkg

83 83 26 20 84 78 159 219 89 81 1 O0 97 83 1 O0 86 78 82 80 90 78 91 89 87 76 83 89 69 45 79 81 87 81 83 85 I O0 88 86 71 61 51 82 39 83 77 80 73 77 76 79 76 a7 88 77 62 94 91

45 20 52

226 58 62 72 17 50 73 49 67 76 43 50 55 40 77 60 36 24 56 55 57 52 20 47 38

Median 93 73 83 79 52

* Most analytes in reagent water spiked at 5 pg/L, some at higher levels (see Chapter 2, "Study

** Not spiked Design," for specific spike levels).

. . Method Detectio n I imits IMDLsl MDLs were calculated from the replicate samples for the five matrices for all analytes except those for which recovery was always zero. MDLs were calculated in accordance with procedures at 40 CFR 136, Appendix B. MDLs for the individual analytes are listed in Appendix D.

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3ily waste 52%*15% ,

Table 3-1 3. Semivolatile Performance by Matrix * (Refinery AnalSes***)

Matrix RecoveryfStandard Deviation (%)* Descrintion of Methods

Reagent water 91 %II 3%

TCLP leachate 73%*5%

:lean soil 83%*8%

rreated waste 79%*11%

xtractio&W-46 Method 3550 (Sonication Extraction) with 100% methylene chloride for clean soil. treated waste, and oily waste.

CleanuHW-846 Methods 3650 (Acid-base Partition Cleanup) and 361 1 (Alumina Column Cleanup and Separation of Petroleum Wastes) for treated and oily wastes.

. . "RecovervIStandard Deviation Based on seven samples for each matrix (eight for TCLP leachate). The standard deviations are pooled estimates of the within anaiyte precision.

"Refinery Analvtes

Eight analytes were omitted from this comparison because they either had calibration problems (acenaphthylene, benzenethiol) or because they were not spiked in reagent water (1 h-indene; I-methylnaphthalene) or because they were statistical outliers (bis(2ethylhexyl)phthalate; 3-methylcholanthrene; benzo(b)fiuoranthene; benzo(g,h,i)perylene).

Of the 28 refinery analytes, only 20 are included in this table:

Table 3-14 is a summary of the median MDLs for each analyte group. The MDLs for the less complex matrices varied little among the analyte groups; however, MDLs for the treated and oily wastes were quite variable as shown below.

Reagent water 2-7 pg/L Treated waste 3904,200 pg/kg TCLP leachate 14-21 pg/L Oily waste 2,400-1 8,000 pg/kg Clean soi I 240-390 pg/kg

Table 3-1 4. Semivolatile MDLs (Analyte Groups) Method Detection Limits (MDLsbMedians by Group

Analyte Group r"] Reagent TCLP Clean Treated Oily

Note different units for liquids and solids-> (pglL) (pglL) (pglkg) (pglkg) (IJglkg) Water Leachate Soil Waste Waste

Spike Levels' 5 pglL 100 pglL 1,000 pgikg 5,000 pglkg 25,000 pgikg

Benzidines (8, Amines) [ I 61 7 15 240 830 5900

Chlorinated Hydrocarbons [13]

Haloethers [5]

2 15 290 1500 6800

2 15 280 1400 8700

* Most analytes in reagent water spiked at 5 pglL, some at higher levels (see Chapter 2, "Study Design," for specific spike levels). Not spiked

*** Number in brackets is number of analytes in each group.

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Method Detection Limits (MDLs)-Medians by Group

Analyte Group r"] Reagent TCLP Clean Treated Oily

Note different units for liquids and s o l i d s a (pglL) (pglL) (pglkg) (pglkg) (Ciglkg) Water Leachate Soil Waste Waste

Spike Levels*

Heterocyclics [I 11

5 pglL 100 pglL 1,000 pglkg 5,000 pglkg 25,000 pglkg

5 20 260 1 O00 6300

Nitroaromatics/Cyclic Ketones [9] 2 16 240 1200 7800

Nitrosamines [6] 2 18 270 390 2400

20 390 1900 15000 Organophosphorus Pesticides [8] **

Phenols [I81 3 21 260 1200 12000

Phthalate Esters [6] 2 16 250 5200 18000

Polynuclear Aromatic Hydrocarbons (PNAs) [21]

2 14 250 1600 1 1 O00

Other [15] 2 18 260 510 4500

* Most analytes in reagent water spiked at 5 pg/L, some at higher levels (see Chapter 2, "Study Design," for specific spike levels). Not spiked - Number in brackets is number of analytes in each group.

MDLs for the refinery analytes are shown in Table 3-15. Ranges in MDLs from the table are shown below:

Reagent water 1-1 I pg/L Treated waste 330-1 6,000 pg/kg TCLP leachate 4-54 pg/L Oily waste 2,800-59,000 pg/kg Clean soil 94-830 pg/kg

According to SW-846 Method 8270, the MDL for an oily waste should be about 75 times the MDL for a clean soil6. In this study, 26 of the 29 semivolatile refinery analytes met this criterion. The three refinery analytes that did not meet this criterion were, with their oily waste to clean soil ratios: benzo(g,h,i)perylene (1 24); bis(2-ethylhexy1)phthalate (238); and phenanthrene (87). Of the 128 semivolatiles in this study, the MDL ratio between oily waste and clean soil could not be calculated for 42 analytes because of poor recoveries. Of the remaining 86 semivolatiles where the ratio could be calculated, 79 were able to met the SW-846 criterion. In addition to the three refinery analytes already identified, those analytes that did not meet the criterion, with their ratios were: 4,6-dinitro-2-methylphenol (81); di-n-octyl phthalate (87); 4-nitrophenol (92);

The ratio is actually given in the method for Practical Quantitation Levels (PQLs); however, since the PQL is a multiple of the MDL, this ratio holds true for the MDL as well. It is assumed that the oily waste and clean soil in this study are comparable to the non-water miscible waste and low soil/sediment, respectively, in SW-846.

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and pentachlorophenol (135). The MDL ratios between oily waste and clean soil for each analyte are found in Appendix D.

METALS Recovery and Precision Recovery and precision performance for ICP and GFAA are summarized in Tables 3-16 and 3-1 7. Chromium was not spiked in treated and oily wastes because of high background levels of this metal; therefore, chromium recoveries could not be determined for these matrices.

Table 3-1 5. Semivolatile MDLs (Refinery Analytes) Reagent TCLP Clean Treated Oily

Waste Water Leachate Soil Waste Note different units for liquids and s o l i d s a (pglL) (pglL) ( P S W (Ccglkg) (ciglkg)

Spike Levels' 5 pg1L 100 pg/L 1,000 pglkg 5,000 pglkg 25,000 pglkg

scenaphthene scenaphthylene anthracene benzenethiol 3enzo(a)anthracene Denzo(b)fluoranthene Denzo(k)fluoranthene )enzo(g, h, i)perylene Denzo(a)pyrene h(2-ethylhexy1)phthalate :hrysene Ji benzo(a, h)anthracene jibenzofuran 7,12-dimethylbentanthracene 2,4-dimethylphenol iluoranthene luorene 1 h-indene ndeno(l,2,3-cd)pyrene 3-methylcholanthrene l-methylnaphthalene 2-methylnaphthalene 2-methyl phenol 3-& 4-methylphenol i a phthalene Dhenanthrene Dhenol

2 3 2

2 2 2 1 1

11 2 2 2 1 3 1 2

2 4

2 2 3 2 2 2

**

H

H

13 4

12 51 16 17 12 11 14 54 19 22 14 13

9 15 14 17 15 9

10 16 19 31 15 15 18

240 94

230 830 240 340 260 21 o 250 250 250 250 220 31 O 360 250 220 360 240 180 260 300 260 530 290 260 260

920 330 1 O00 16000 1300 6400 2900 4000 1200 6200 1600 2300

790 2800 1400 1400 I O00 1100 2300 2300 1200 2800 1200 1900 1800 I600 1 O00

12000 2800 I O000 36000 1 O000

9700 13000 27000 1 1 O00 59000 15000

7900 8600

17000 7000

1 1 O00 16000

91 O0 7000 61 O0

17000 1 O000 9600

21 O00 8600

23000 9500

Dyrene 2 13 250 2600 18000 Median 2 15 250 1600 10500

*

** Not spiked in sample

Most analytes in reagent water spiked at 5 pg/L, some at higher levels (see Chapter 2, "Study Design," for specific spike levels).

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Table 3-16. Comparison of Metal Recoveries by ICP Metals Analyzed by ICP*

All Metals Matrix Antimony Arsenic Chromium Cobalt Lead Nickel Selenium Exceot

'Reagent water

TCLP Leachate

Clean soil

"average "standard deviation

average standard deviation



average

Treated waste

Oily waste

(Sb)

89% 7%

108% 3%

0% 0%

8% 16%

5%

120% 96% 12% 4%

108% 107% 8% 4%

109% 109% 4% 6%

113% NA 11% NA

125% NA

(Co) (Pb) (Ni) (Se) Sb, Cr

98% 93% 98% 103% 102% 2% 7% 3% 3% 7%

97% 98% 100% 107% 102% 4% 5% 4% 6% 6%

96% 98% 100% 111% 103% 3% 7% 2% 2% 4%

110% 98% 126% 116% 113% 14% 6% 7% 6% 9%

90% 58% 102% 118% 99% I standard deviation 3% 7% NA 4% 5% 5% 4% 5%( * SW-846 Method 6010 (Inductively Coupled Plasma-Atomic Emission Spectroscopy) * Averages and standard deviations for each metal are based on seven samples (eight for

reagent water). The overall standard deviation for all metals is the pooled standard deviation. NA Not calculated because chromium not spiked in matrix because of high background levels of

chromium.

Antimony was recovered poorly or not at all in the solid matrices because of limitations of the sample digestion procedure (SW-846 Method 3050). An EPA study of Method 3050 for antimony concluded that this method does not recover antimony from solid matrices very well, a finding that is confirmed by the present study. SW-846 Method 7041, the GFAA method used for antimony in this study, states that there is currently no approved digestion procedure for antimony in solids.

Aside from antimony, recoveries were generally in expected ranges (85% to 1 15%). Recoveries higher than normal were seen in the analyses of arsenic in reagent water by ICP and GFAA and oily waste by ICP; in the analyses of nickel and selenium in treated waste by ICP; and in the analysis of selenium in oily waste by ICP. Low recoveries were seen in the analysis of lead in oily waste by ICP, and in the analyses of arsenic and selenium in oily waste and clean soil by GFAA.

There were a number of statistically significant differences in metal recoveries among matrices. In general, a difference of 10 percentage points between any of the recoveries shown in Tables 3-16 and 3-17 tested significant.

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Matrix

Reagent water it average

standard deviation




average standard

TCLP leachate

Clean soil

Treated waste

Oily waste

Table 3-17. Comparison of Metal Recoveries by GFAA I Metals Analyzed by GFAA*

Average excluding Antimony Arsenic Selenium

(Sb) (As) (Se) Sb

105% 5%

100% 4%

0% 0%

70% 21 %

59% 6%

120% 8%

98% 3%

76% 5%

93% 3%

82% 3%

86% 6%

91 % 5%

61% 3%

94% 16%

54% 10%

103% 7%

94% 4%

68% 4%

94% 11%

68% 7%

I deviation * SW-846 Atomic Absorption, Graphite Furnace Technique Methods 7041

(Antimony), 7060 (Arsenic), and 7740 (Selenium) ** Averages and standard deviations for each metal are based on seven samples

(eight for reagent water). The overall standard deviation for all metals is the pooled standard deviation.

Standard deviations (within-analyte precisions) for the ICP metals ranged from 2% to 16%; GFAA performance was similar with a range of 3% to 21%. Pooled estimates across all metals except antimony and chromium are shown in the last column of each table. For the ICP metals included in these estimates-arsenic, cobalt, lead, nickel, and selenium-the range was 49% among matrices, with a difference greater than two percentage points between matrices bei

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