0 0 .) 0 2 1

SSSSL,. 81983

MADISON

QUALITY ASSURANCE PLAN

FOR

THE ANALYSIS FOR HAZARDOUS SUBSTANCESLIST VOLATILE ORGANIC COMPOUNDS

IN AIR SAMPLES BY GC/MS

PREPARED BY:

RADIAN CORPORATIONP.O. BOX 13000

RESEARCH TRIANGLE PARK, NC 27709

January 21, 1988REVIM* *¥ AEGXON V, QA S ECU ON

OK Jttir 21, 1988

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2.0 TABLE OF CONTENTS

Paoe

I.0 TITLE .................................................. 12.0 TABLE OF CONTENTS....................................... 113.0 LIST OF TABLES.......................................... 1 i 14.0 INTRODUCTION............................................ 15.0 PROJECT DESCRIPTION..................................... 16.0 PROJECT ORGANIZATION AND RESPONSIBILITIES............... 17.0 QUALITY ASSURANCE OBJECTIVES............................ 38.0 SAMPLING PROCEDURES..................................... 79.0 SAMPLE CUSTODY DOCUMENTATION............................ 910.0 DELIVERABLES............................................ 10II.0 TUNING AND CALIBRATION PROCEDURE AND FREQUENCY.......... 1212.0 ANALYTICAL PROCEDURES................................... 1513.0 DATA REbUCTION, VALIDATION, AND REPORTING............... 2214.0 INTERNAL QUALITY CONTROL CHECKS......................... 2415.0 PERFORMANCE AND SYSTEM AUDITS........................... 2716.0 SPECIFIC ROUTINE PROCEDURES USED

TO ASSESS DATA PRECISION, ACCURACY,AND COMPLETENESS........................................ 2g

17.0 CORRECTIVE ACTION....................................... 2918.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT................. 3019.0 SAFETY.................................................. 30

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3.0 LIST OF TABLES

Number Page

p1 Inter!aboratory Tenax Performance Evaluation ............. 6Z. GC/MS Tuning and Mass Calibration ......................... 133. Scheme of QuantHation for Analytes ....................... 144. Analytical Conditions for Analysis of Sample

Cartridges .............................................. 175. Calibration Compounds for Air Toxics Analysis ............. 196. Limits of Detection of Compounds of Interest .............. 26

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QUALITY ASSURANCE PLANFOR

THE ANALYSIS FOR HAZARDOUS SUBSTANCES LIST VOLATILE ORGANIC COMPOUNDSIN AIR SAMPLES BY GC/MS

JANUARY 1988

Project Responsibility: Approved by:

Laboratory Project Director:

Laboratory Program Manager;

Laboratory QA Officer:

Denny Wagoner, jjalfian Corporation

/James Homolya, Radian Corporation

Joan Bursey, Radian Corporation

Project Manager:

Project QA Manager:

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4.0 INTRODUCTION

The purpose of this document 1s to describe the Quality Assurance Program forair toxic analytical measurements performed by the Radian Research TrianglePark (RTP) Analytical Laboratory. This plan outlines the policies,organization, functional responsibilities, and general operating proceduresdesigned to ensure that measurement efforts result in valid data, of knowndata quality. This plan 1s presented 1n the general format prescribed forQuality Assurance Project Plans for the Environmental Protection Agency (ERADocument QAMS-005/80).

5.0 PROJECT DESCRIPTION

The objective of this Quality Assurance Plan is to describe the procedureswhich are Implemented for the analysis of air toxics samples and to ensurethat data acceptability criteria are Imposed and obtained on a routine basis.

The aim of this Quality Assurance Plan is to provide timely delivery of dataof the highest possible quality. Samples of air are provided to RadianResearch Triangle Park Laboratory and analyzed for a given set of constituentswhich are of environmental concern. These analyses are performed to supportenvironmental sampling activities conducted by Radian or external clients.

6.0 PROJECT ORGANIZATION AND RESPONSIBILITY

In the Radian organization, Mr. James B. Homolya serves as Program Manager forair toxics analytical activities performed under contract. Mr. Homolyasupervises and administers all contractual requirements which Includesmonitoring Radian's budget and schedule of performance. He will:

I) keep the client Informed on all aspects of the programIncluding expenditures, problems, and recommended solutions;

2} be available to the client for action on any problem;

3} be available to the Project Director (Dr. D. E. Wagoner) forany action on any problem requiring additional management ortechnical support; and

4) keep Radian corporate management Informed on all mattersrelating to the program.

Dr. Denny E. Wagoner, Project Director, will work directly with Mr. Homolya,the Program Manager, to schedule and direct the analytical requests during theproject. Dr. Wagoner will be the technical manager with overallresponsibility for ensuring the technical quality of the air toxics analyticalprograms performed 1n the Radian RTP Laboratory. Dr. Joan T. Bursey, SeniorTechnical Advisor, is available to the Project Director for consultation on

^_. any technical problems arising from the analysis of samples and interpretationof data for this program. Dr. Bursey also provides final review of analyticaldata and review of data packages prior to delivery of the packages to theProject Director for final review and delivery to the client. Dr. Bursey alsoorganizes and coordinates the Quality Assurance efforts on the air toxicsanalytical program.

Mr. Randall L. Porch, Supervisor of the Gas Chromatography/Mass SpectrometryLaboratory, is responsible for the scheduling and supervision of day-to-dayanalytical activities for the sample analysis portion of this program.Working under Mr. Porch's supervision are the operators of the GC/MSInstrumentation, Mr. Mitchell Howell, Mr. James Carleton, Mr. Ron Harris, Ms.Marda McGinnity, and Mr. David Kusel. Mr. Porch is responsible for thescheduling of activities In the GC/MS laboratory and for the delivery ofquality analytical results In a timely manner. Mr. Porch supervises theanalyses and provides an initial review of data and organization of the datapackages. Mr. Tom Buedel works under Mr. Porch's supervision in thegeneration of components of the data packages and in the initial organizationof the data package. Mr. Porch and the system operators in collaborationprovide the primary level of quality control for the program: the analysts,under Mr. Porch's supervision, assure that quality criteria are tested and metprior to the initiation of any analyses in any given day and during continuinganalysis.

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Mr. Owes F. McGaughey, Operations Manager, Is responsible for thecoordination of efforts 1n the preparation of sampling cartridges. The tubesare packed, conditioned, and tested for cleanliness under Mr. McGaughey'ssupervision. Ns. Candace Blackley and Ms. Leslie Cooper work under Mr.McGaughey's supervision 1n the preparation and quality control for thesampling cartridges. Ns. Margaret Wilson, Sample Control Officer, Isresponsible for the shipping of prepared sampling cartridges to the fieldstaff for sampling. Ms. Ullson, assisted by Ms. L. McBHan, also logs insamples received Into the computerized Sample Analysis and Management (SAM)System used In the Radian laboratories. Ms. Wilson generates report formsthrough SAM which are Included as part of the data package ultimately

^ delivered to the client.

7.0 QUALITY ASSURANCE OBJECTIVES '

The analysis of air samples Is always subject to a matrix effect. Within theconstraints of this matrix effect, various observations may be made. Thelevel of moisture 1s always a primary consideration in analytical sampling ofair, since the presence of water has a deleterious effect upon most analyticalInstrumentation. The effects which are encountered range from a minordistortion of chromatographic peaks due to water entering the analyticalsystem to a complete shutdown of the entire analytical system because of avacuum surge resulting from the entrance of water into the instrument. Theexistence and extent of introduction of water Into the analytical system areoutside the control of the analyst. However, considering the matrix effects,the following Quality Assurance goals can be set for precision, accuracy, andcompleteness.

There 1s usually far more difficulty associated with producing truly replicateair samples than with producing replicate results. Precision is defined asthe numerical measure of the reproduc1b1l1ty of an analytical measurement, asexpressed by the coefficient of variation obtained when at least threereplicate analytical measurements are compared. When replicate samplingcartridges are spiked, precision as expressed by coefficient of variation ofreplicate (at least three) analyses 1s typically in the range of 15-30% and

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the precision Is compound-specific. For compounds such as toluene,chlorobenzene, ethylbenzene, hexane, heptane, and the xylenes, precision datawill tend toward the lower part of the range cited above. For other morepolar compounds such as chloromethane, bromomethane, chloroethane, vinylchloride, the dlchlorobenzenes, acetone, and 2-butanone, precision will tendtoward the higher part of the range and may, at times, extend above the higherpart of the range. A historical database Is the best predictor of the rangeof precision which should be attainable In any given set of circumstances.When the effects of matrix are overlaid with the effects ofcompound-to-compound variation, the range of precision may be expected to beat least £5-40%, chiefly due to the presence of water and the effects whichthe water has upon the analytical determination.

Accuracy 1s defined as the correspondence of observed values to true values,usually related to spiked samples. A1r toxics programs to date have not beencharacterized by the use of externally prepared audit samples because noorganized audit program making externally-prepared audit samples availableexists. Therefore, no historical database 1s available for prediction ofaccuracy or bias values. Two assessments of an expected value for accuracycan be given. In the analytical process, each sample 1s spiked with surrogatecompounds, which are 1sotop1cally labeled or fluorinated analogs of compoundsof Interest. The compounds used as surrogates are dlfl-ethy1benzene,perfluorotoluene, d--l,2-d1chloroethane, dg-toluene, and dg-benzene.Bromofluorobenzene, a compound which Is commonly used as a surrogate compoundas well as a tuning standard in many programs which require purge and trapanalysis of volatile organic compounds, has been proposed as a surrogatecompound. HMtver, the volatility of bromofluorobtnzene relative to the othercompounds ootfce target 11st 1s so low (the boiling point of.4-broaofluor«tMzene 1s 150°C) that Us stability In the static dilution bulbu,sed for calibration is questionable, and reproducible values for>4rottfluorobMZMt In even an initial calibration cannot be obtained.Bromofluorobenzene is therefore used only as a tuning standard in the airtoxics analytical program.

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A typical range of recoveries for the surrogate compounds presently in use Is20X, depending upon the moisture which 1s Introduced with the samples.

Use of a laboratory or field blank where the moisture problems are not sosevere as actual field samples will usually raise the lower part of the rangeto 75% or better.

An additional measure of accuracy can be provided by the analysis of auditp

samples. A series of spiked Tenax audit samples was provided by Mr. JohnSchwelss, EPA Region X, prior to the Initiation of the air toxics analyticalprogram at Radian. In December, 1986, Mr. Schwelss had organized aPround-robin study among laboratories which perform analysis of Tenaxcartridges, and spiked samples were supplied by Mr. Schwelss. The resultspshown 1n Table 1 were obtained for analysis of triplicate spiked Tenaxcartridges. There have been no subsequent audit programs.

Note that, 1n the audit samples analyzed, the difference between spiked valuesand observed values tends to Increase with decreasing volatility of thecompound of Interest. The Increase In this parameter reflects the decreasingpefficiency of the desorptlon from Tenax . The values can still be quitereproducible, however, even with decreasing efficiency of the desorption frompTenax . In this series of audit samples, specific values for accuracy ofspecific compounds range from -4% to -50% while the assay 1s performing withall analytical parameters in control. The accuracy expected for the assay iscompound-dependent, with the desorptlon efficiency of the more polar compoundsas well as the higher boiling (!.£., less volatile) compounds being lower andmore variable.

Completeness 1s a measure of the number of acceptable assays relative to thenumber of assays which can possibly be performed. The goal of 100%completeness can sometimes not be attained, however, because of instrument orpower failures and other circumstances, so a goal of 90% for completeness isreasonable and ought to be attainable in most circumstances, and 100% will beattainable In most circumstances.

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TABLE 1. INTERLABORATORY TENAX* PERFORMANCE EVALUATION

Compound

chloroform1,1,1-trlchloro-

ethanecarbon tetra-

chlorldebenzenel,2-d1chloro-

ethanetrlchloroethenel,2-d1chloro-

propanetoluenetetrachloroethenechlorobenzeneethyl benzeneo-xylenebrorooforra

Spiked Value

108293

233

384366

320168

441354483315384420

Observed Value11 12

111314

216

348356

285159

409329398261265266

100245

236

328311

262147

391294393279385371

#3

100251

204

312315

265135

317252153471635

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8.0 SAMPLING PROCEDURES

Sampling Is not an activity which has been conducted by Radian personnel inthe air toxics analytical program. The extent of Radian Involvement inpsampling has been to supply Tenax (Supelco, Inc., Bellefonte, PA} andpTenax /charcoal tubes to client field sampling teams. The procedures forpreparation of these tubes and the quality control associated with theprocedure are described below.

All tubes are prepared by packing and thermal desorption for a minimum of 24hours at 210°C. After desorption, the tubes are removed from the oven, storedIn Individual containers, and blanked using gas chromatography with flameionization detection with cryotrapplng. Every single tube prepared as part ofa batch 1s not analyzed by gas chromatography with flame ionization detection,but at least 50% of the tubes are blanked Individually. If the Individualanalyses of 50% of the tubes of a given batch are satisfactory, the entirebatch Is considered acceptable and ready for shipment to the field forsampling exposure. Tubes are then re-packaged and shipped to the field withChain of Custody forms, sample seals, and special Instructions for handling ofthe tubes.

The assembly and packing of sorbent cartridges 1s carried out In a laboratoryarea which 1s free of volatile organic material, in a laboratory in which noorganic solvents are handled or stored, and in which the laboratory air ispcharcoal-filtered. New Tenax Is Soxhlet-extracted for 24 hours with methanol(Burdick and Jackson, Pesticide Grade or equivalent), then dried for 6 hoursin a vacuum oven at 50°C prior to use. Cartridges packed with Tenax arethermally conditioned by flowing organic-free nitrogen at a rate of 30 mL/minthrough the resin while heating to 210°C for 24 hours. After thermalconditioning, the sorbent cartridges are stored for 24 hours at roomtemperature prior to monitoring the cartridges for residual organiccontamination. If the cartridges have collected high concentrations oforganic compounds in field use (mlcrogram levels of organic materials), the

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sorbent will require Soxhlet extraction prior to use for another fieldapplication. Because of problems with possible charcoal contamination,charcoal Is not reused. New charcoal (Calgon Corp., Pittsburgh, PA) 1s

Pprepared as Tenax 1s prepared.

Glass tubes and culture tubes for holding the tubes in shipment are cleanedwith a non-Ionic detergent In an ultrasonic bath, rinsed well withorganic-free water, and dried at 100°C. Metal parts (fittings to cap the endsof the sampling tubes and to make connections to the sampling apparatus andthe analytical Instrumentation) are cleaned In an ultrasonic cleaner with awarm non-Ionic detergent solution, rinsed with organic-free water, air dried,

^ and heated 1n a muffle furnace for 2 hours at 400°C. Glass wool used inpacking the sampling tubes Is Soxhlet-extracted using pentane for 8-16 hours,and oven-dried at 110°C before use. The glass wool is checked before use to besure that all residual pentane has been removed. Nitrogen gas used in thedrying and quality control of sampling tubes Is organic-free (Linde-UnionCarbide, 99.999% pure, hydrocarbon-free, or equivalent). Cryogenic traps areused to ensure purity.

DIn the preparation of the sampling cartridges, approximately 1.6 g Tenax isweighed and packed In a sorbent tube and held in place with glass wool. The

D DTenax tubes are stored and transported in culture tubes with Teflon -linedscrew caps, within a clean metal container which contains clean charcoal. Thestorage container 1s kept cold using Ice or cold pack storage.pTenax /charcoal tubes are packed with an approximately 3:1 volume ratio ofpTenax and charcoal. The cartridge 1s assembled so that the inlet side duringpsample collection Is Tenax , followed by a layer of charcoal at the outletside of the sorbent cartridge. The sorbents are held in place in thecartridge by glass wool. End caps are placed on the assembled cartridges andpthe Tenax /charcoal cartridges are packed and stored by the procedure used forpTenax cartridges.

The following Quality Control measures are used to ensure that the sorbentcartridges are free from background contamination prior to sample collection.Gas chromatograph with flame ionization detection is calibrated using direct

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Injection of propane standards. The chromatographic column Is 1.8 m x 0.25 cmID glass packed with IX SP-1000 on Carbopack (60/80 mesh). Following assemblyand leak-checking of the sampling cartridges, the cartridges are connected toa source of organic-free nitrogen. Nitrogen 1s passed through each samplingcartridge at a flow rate of at least 30 ml/rain, while the cartridges areheated to 200°C. Every sampling cartridge receives the conditioning withnitrogen under heat; 50% of the cartridges are checked by flame 1on1zat1on gaschromatography after the conditioning to ensure freedom from contamination.If In using this procedure, the background exceeds 10 ng, the batch ofcartridges must be recleaned and reanalyzed. Cleaned tubes are viable forfield sampling for up to six weeks 1f they are kept sealed in the shippingtubes. After sampling, exposed tubes must be analyzed within two weeks.

9.0 SAMPLE CUSTODY DOCUMENTATION

With every set of sampling tubes which leaves the Radian laboratory, a set ofChain of Custody forms and sample seals 1s furnished to the field samplingpersonnel. Upon receipt of exposed sampling tubes at the Radian laboratories,the Chain of Custody forms are signed and dated by the Sample Custodian. Thesampling tubes are then logged Into the computerized laboratory SampleAnalysis and Management (SAM) system. After the sampling tubes have beenlogged Into the SAM system, the tubes are relinquished to the MassSpectrometry Laboratory Supervisor (or his designee), to be placed into the

Rfreezer especially designated for Tenax tubes. When the samples areanalyzed, the analyst breaks the Sample Seal to remove the tubes from thecontainers In which they have been shipped. The sample seal 1s affixed to thechromatogram generated from the sample in the analyst's laboratory projectnotebook. This sample seal Is subsequently duplicated for inclusion in theultimate data package. After samples have been analyzed, the analyst obtainsthe Initial quantitative data. The project notebook with all data therein issubsequently relinquished to the Data Control Officer, who generates the otherInformation required for the complete data package which Is delivered to theclient. When a data package Is complete, the package is reviewed by the MassSpectrometry Laboratory Supervisor and by the Senior Technical Advisor, priorto delivery. The Project Director (Radian) also reviews the data package.

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The laboratory notebook is signed and dated by reviewing personnel, and thedata sheets produced by the Sample Analysis and Management system are signedby a reviewer.

10.0 OELIVERABLES

The documentation which Is supplied 1n a data package Includes:

1) a data summary table prepared from the Individual sample results2) a table which contains a summary of the surrogate recoveries for

all of the samples and blanks analyzed in a given batch ofsamples

3) a description of the experimental procedure, which typically isnot varied

4) a description of the analytical conditions, which are maintainedas nearly constant as possible

5) tabulated tuning data for every twelve-hour period of analysis

6) a table of limits of detection, which are determinedexperimentally •

7} a table which shows the response factor database(s), Includingthe mean of all of the calibration analyses, the standarddeviation, and the coefficient of variation. In addition, allof the reconstructed gas chromatograms and all of the hardcopiesof the computerized quantitation reports for each individualanalysis of standards are reported

8) twelve-hour calibration checks are tabulated for comparison tothe mean of the response factor database

9) reconstructed gas chromatograms and computerized quantitationreports of the analyses of all samples and blanks are reported

10) mass spectra of the compounds of Interest from each datafile(other than the calibration analyses) are reported; the massspectra of the compounds of Interest are plotted relative to thereference spectrum of the compound obtained on the sameInstrument (see Figure 1)

11) when additional compounds are Identified, copies of the massspectra and copies of the computerized library search aresupplied. In addition, estimated concentrations (using aresponse factor of 1 relative to the quantitation standard) aresupplied for the other compounds identified

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L1MMY SE/WCH•1/Jfat Hi 55i U » 3i2IWmii M HC STO 11293 I 11439CMS. i 33(4 HIM) TO 2M tEMWCCO <S 191 2N IT)

OfiTfli F880183 » 2*1CM.li F8a012fi I 3

BASERICi

Zi 42B4351.

StfffU

C4.HB.O FUtNN. TETMHyQRO-

1-ftOfOC, 1-fCTMOXY-

fl/Z

Figure 1. Presentation of the mass spectrum of the compound of interestplotted with the reference spectrum; lower display illustrates thedifference between the two mass spectra.

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12) report forms printed by the Sample Analysis and Managementsystem are supplied

13} Chain of Custody forms and copies of. the sample seals are alsosupplied with the report.

Thus, the entire history of the sample through the Radian Research TrianglePark laboratory Is documented through the data package.

11.0 TUNING AND CALIBRATION PROCEDURE AND FREQUENCY

The mass spectrometer Is Initially tuned using perfluorotrlbutyl amine (FC-43)according to the manufacturer's specifications. Prior to the analysis of anysamples, a 50 ng standard of 4-bromofluorobenzene prepared in methanol isInjected onto and purged from a cleaned stapling cartridge. The resultantmass spectrum for the bromofluorobenzene must meet all of the criteria shownIn Table 2 before sample analysis can be Initiated. These tuning criteria forbromofluorobenzene must be demonstrated each twelve-hour shift. The GC/HSsystem Is calibrated by analyzing calibration cartridges prepared by spikingBlank cartridges with internal standards, surrogate standards, 4-bromofluoro-ben««ne and conpounds of interest. For the initial database, a five-point

calibration 1s used, subject to acceptability of the coefficient of variation(percent coefficient of variation less than 20%). Target compounds arequantified according to the scheme shown in Table 3. If an acceptablecoefficient of variation is not observed after five injections, the dataset isexamined for errors of injection or calculation. If no mechanical errors aredetected, additional analysis at each concentration level are performed,deleting the original analysis at a given concentration and replacing the datafor the initial analysis with the values from the new analysis for all of thecompounds of Interest. The repeated analysis of calibration standards at eachconcentration level is continued until an acceptable coefficient of variation1s obtained, with five points in a response factor database. Response factorsare calculated according to equation (1).

TABLE 3. SCHEME OF QUANTITATION FOR ANALYTES

perfl uorobenzene (QS)ad4-l,2-d1ch1oroethine (S)dg- benzene (S)trlchlorofluoromethane1,1-dichloroetheneacetonemethylene chloridetrans-l,2-d1chloroethenehexaneI,l-d1chloroethane2-butanonechloroform1,1,1-trichloroethanecarbon tetrachlorldebenzenel,2-d1chloroethaneheptane

dg-chlorobenzene (QS)djQ-ethylbenzene (S)chlorobenzeneethyl benzenem-t g-xyleneo-xylenestyrenebromoformisopropylbenzene1,1,2,2-tetrachloroethanem-dichlorobenzeneg-dichlorobenzeneo-dichlorobenzene

l,4-d1fl uorobenzene (QS)perfl uorotoluehe (S)dg- toluene (S)trichloroethene1 , 2-d1 chl oropropanebromodl chl oromethane2-chloroethylv1nyl ether

trans-l,3-dichloropropenetolunec1s-l,3-dichloropropene1,1,2-trichloroethanetetrachloroethenedibromochloromethane

aQuantitation StandardSurrogate

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RF- (ACI x ngstd}/(Astd x ngci)where:

RF • response factorA£J » area of the quantltatlon Ion of the compound of interest

"9$td " nanograms of quantltatlon standardAstd " *rea of the quantltatlon Ion of the quantltatlon standard

* nanograms of compound of Interest

The calibration la checked every twelve hours, ual FV Weak "cartridge spikedwith calibration standard «AirtTWrm-«t 50 ng lewl of all coapounds ofinterest plus Internal standatda, ewrrogate standards and 4-bronof luorobenzene ,and check for acceptability uslAf'tto calibration cheek coapounds (CCC) as theyare discussed below:

o If the check of the calibration ehows that the calibration database isstill acceptable* samples ar* analysed.

o If the calibration check show* that the original database is not valid,a second check Is wade. If the seco»d check la not acceptable , the tuningcheck and generation of the response factor database are repeated. Thefreqtiettt!? of calibration ia ttms a variable depending on the length oftlae before the twelve hours check of the calibration fails to meet theepeciZieetlena for accepability. A calibration database has been observedto maintain acceptability for a week or longer, and recalibration hasalso been required after a single day. The determining factors are-usually external parameters such as power failures or other types ofinstrument failure and sample cleanliness.

12.0 ANALYTICAL PROCEDURES

The procedures for sample analysis are adapted from ERA Method T01("Compendium of Methods for the Determination of Toxic Organic Compounds inAmbient A1r," R. M. Riggin, ERA- 600/4-84-041, April, 1984). Method T01 aswritten allows considerable flexibility in Instrument configuration andoperating conditions; the procedures used by Radian are described below.Field samples taken on TenaxR and/or TenaxR/charcoal are analyzed by thermaldesorption into a gas chromatograph/mass spectrometer/data system. The actualcartridges used for sampling are glass, in the same configuration as the tubesused in the analysis of emissions samples taken by the Volatile Organic

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Sampling Train (VOST) (EPA Method 5040, SW-846, Third Edition, September,D

1986). Sampling cartridges are analyzed either singly or as a Tenax /charcoalpair according to client request. The analysis of each individual tube of thepair doubles the number of analyses required but provides a laboratory checkon the occurrence of breakthrough. Breakthrough or specific retention volumeIs the sample volume required to elute a compound which is Introduced onto asorbent bed. Before breakthrough occurs, the amount of spiked materialadsorbed on the sorbent bed 1s directly proportional to the volume sampled.Moreover, the adsorbate-sample volume relationship must pass through theorigin. After the breakthrough volume has been reached, the amount ofadsorbate 1s no longer proportional to the sample volume, but approaches ahorizontal asymptotic value equal to the equilibrium loading. Individualanalysis of both sampling tubes is the only measure which the analyticallaboratory can take to demonstrate that breakthrough may be occurring.Occurrence of breakthrough can be controlled only by controlling the volumesampled. Retention volumes for a given sorbent are compound dependent. It ispossible to experimentally determine these retention volumes for each of thecompounds of interest and regulate the volumes sampled so that these retentionvolumes are not exceeded. Some data on compound retention volumes on TenaxD

GC are available, but the information in the literature is by no meanscomplete for all of the compounds of interest. In general, a compromise issought in the field between a sample volume sufficiently small that nobreakthrough volume for any of the compounds of interst will be exceeded and asample volume sufficiently large to adsorb quantities of compounds largeenough to achieve successful analysis if the compounds are present in the air.

The analytical conditions are shown in Table 4. In the analytical procedureR Rfor the sample cartridges, Tenax and Tenax /charcoal tubes are heated to

180°C and purged with 40 mL/min of helium for 10 minutes, thus directingorganic constituents through a heated 5 ml purge flask (90°C) onto ananalytical trap which is the same as the analytical trap used for EPA Method601. Quantitation standards and surrogate compounds from a static dilutionbulb are spiked through a side arm of the purge flask at the beginning of thepurge cycle. The trap is then backflushed with helium for 4 minutes and the

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TABLE 4. ANALYTICAL CONDITIONS FOR ANALYSIS OF SAMPLE CARTRIDGES

InstrumentGC Column

Carrier GasCarrier Gas Flow Rate

GC Program

Electron EnergyIonizer TemperatureInterface Oven TemperatureInjector TemperatureManifold Temperature

Finnigan-MAT 4500 or OWADB-624 megabore fused

silica capillary, 30m, I u filmthickness

Heli urn15 mL/min, 15 mL/minmakeup

5°C for 2 min, then6°C/min to 200°C, hold

for 10 min70 eV, nominal150°C200°C100°C100°C

Analytical Trap, Tekmar LSC2 EPA 601: 1.0 cm 3% OV-1on Chrom W (60/80 mesh),p7.7 cm Tenax (60/80 mesh7.7 cm silica gel,7.7 cm charcoal

Cartridge Purge TimePurge GasCartridge Purge Gas FlowAnalytical Trap Desorb TimeAnalytical Trap Desorb TemperatureTrap Bakeout TimeTrap Bakeout Temperature

10 minutesHeli urn40 mL/min4 minutes180°C15 minutes200°C

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organic compounds directed to the head of a 30m 08-624 megabore fused silicacapillary column with a helium flow rate of 15 raL/min, with 15 ml/min makeupthrough a glass jet separator. The megabore column Is Interfaced to a glassJet separator 1n the GC/MS Interface oven, using a helium makeup flow of 15ml/mln in order to optimize both column flow and separator efficiency.

After the tune has been established, a five-point calibration is performed bygaseous injection from a static dilution bulb. The compounds shown in Table 5are in gaseous solution in the heated bulb.

The five-point calibration typically covers a range of approximately 10 ng to300 ng, but the exact range Is flexible according to client request. A commonrange is 20, SO, 100,200 «nd 300 ng. The method of relative response factorsis used, with the coefficients of variation of the calibration check compoundsover this concentration range required to have a value of 20% or less. Ifthis coefficient of variation 1s not attained with the original five datapoints, additional calibration data points at each concentration are addeduntil an acceptable calibration curve is obtained consisting of a single datapoint at each concentration. This initial calibration curve provides theoriginal database prior to the initiation of sample analysis. The first sampleanalysis is a laboratory blank. The laboratory blank consists of a set oftubes which was prepared with the field samples but which was reserved in thelaboratory for analysis with the field samples. Since laboratory blanks arestored in the same freezer with samples, the laboratory blanks also serve asfreezer storage blanks. Laboratory and field blanks are checked prior to theInitiation of sample analyses. If contamination is encountered at this point(observation of any of the compounds of Interest at a level five times thedetection limit is considered contamination at an unacceptable level), theclient is advised of the extent and nature of the contamination and a jointdecision Is made as to whether or not to continue analysis. If nocontamination is observed (no compounds of Interest are present at a level offive times the detection limit), sample analysis is initiated. The bulbthrough which the gaseous desorbed compounds- pass is both heated andcontinuously flushed with helium. However, if high compound levels areencountered in an analysis, a blank sample is analyzed to demonstrate theabsence of compound carryover prior to the analysis of further field samples.

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TABLE 5. CALIBRATION COMPOUNDS FOR AIR TOXICS ANALYSIS

trlchlorofluororoethane (101}aroethylene chloride (84)1,1-dichloroethene (61)1.1.1-trlchloroethane (97)benzene (78)trichloroethene (130)bromochloromethane (83)toluene (92)1.1.2-trichloroethane (97)dibromochloromethane (129)ethyl benzene (106)p.-xylene (106)1,1,2,2-tetrachloroethane (83)fl-dichlorobenzene (146)chloromethane (50)chloroethane (64)heptane (57)styrene (104)2-butanone (72)

1,1-dichloroethane (63)1-1,2-dichloroethene (61)chloroform (83)carbon tetrachloride (117)1,2-dichloroethane (62)1,2-dichloropropane (63)l-l,3-d1chloropropene (75)£-l,3-d1chloropropene (75)tetrachloroethene (164)chlorobenzene (112)ffl-» fl-xylene (106)bromoform (173)nj-dichlorobenzene (146)fl-dichlorobenzene (146)bromomethane (94)vinyl chloride (62)isopropylbenzene (105)acetone (58)hexane (57)

Surrogates:dlfl-ethylbenzene (98, 116)perfluorotoluene (217)dd-l,2-dichloroethane (65)dg-toluene (98)dS-benzene (84)

Quantitation Standards:perfluorobenzene (117)1,4-difluorobenzene (114)dg-chlorobenzene (117)

alon used for quantitation is presented in parentheses.

can.004 19

If sample analyses span a period of several days or weeks, the initiation ofanalysis for each twelve-hour period requires that an acceptable tune bedemonstrated. After a tuning check, a calibration check is performed. Acalibration sample 1s analyzed, and quality criteria are imposed on thiscalibration check before sample analysis 1s Initiated. The quality criteriafor the twelve-hour calibration check are:

1} Gaseous components (chloromethane, bromomethane, chloroethane,and vinyl chloride) must be observed with a response factor of0.10 or better. Closer criteria for these compounds on aday-to-day basis cannot be Imposed because of their lack ofstability In the static dilution bulb. The stability of thegaseous components under the conditions of sample storage anddelivery for the calibration sample tends to be variable.However, if the gases cannot be observed at all, the calibrationstandard must be re-prepared and the calibration processrepeated.

2) The calibration check compounds (chloroform, carbontetrachlorlde, trichloroethene, toluene, tetrachloroethene,chlorobenzene, fl-xylene, and isopropylbenzene) are checked toverify that the response factors obtained for these compoundsare within 20% of the value obtained for the mean of thedatabase.

3) The other calibration compounds are checked to be surethat no more than 3 compounds other than the calibration checkcompounds have a value which is more than 50% different from themean of the response factor database. If these criteria cannotbe met, the calibration sample is re-analyzed. If thecriteria still cannot be met, the calibration standard isprepared and analyzed again and the analytical system isrecalibrated, if necessary, prior to the initiation of sampleanalysis. If the acceptance criteria are met, sample analysisIs Initiated and the values for response factors obtained fromthe analysis of the dally calibration sample are used forquantitative calculations for the samples analyzed on that day.

4} The compounds listed in Table 5 shall be identified byan analyst competent in the interpretation of massspectra, by comparison of the mass spectrum of thesuspected compound of Interest to a mass spectrum of astandard reference mass spectrum of the same compound.Two criteria must be satisfied to verify the identification:

a) elution of the sample component at the samegas chromatographic retention time as thestandard component: The sample componentrelative retention time must compare within

can.004 20

0.06 relative retention time units of thestandard components. The standard will berun within the same twelve hours as thesample; and

b) correspondence of the sample component andthe reference mass spectrum of thecomponent. The requirements for qualitativeverification are:

1) all Ions present in the standard massspectrum at a relative Intensity greaterthan 10% (where the most abundant Ion ofthe mass spectrum equals 100%) must bepresent in the sample spectrum;

2) the relative Intensities of ionsspecified above must agree within 20%between the standard and the samplespectrum;

3) ions greater than 10% in the samplespectrum but not present in thestandard spectrum must be consideredand accounted for by the analystmaking the comparison. If a compoundcannot be verified by all of the abovecriteria but in the technical judgmentof the mass spectral interpretationspecialist 1s correctly identified asa compound of Interest, Radian willreport the identification and proceedwith the quantitation.

Samples received at the Radian Research Triangle Park laboratory are loggedinto the Sample and Analysis Management (SAM) system by the Sample ControlOfficer. Custody of the samples is then relinquished to the Supervisor of theMass Spectrometry Laboratory, who places the samples in a locked limited

Qaccess freezer which is reserved exclusively for Tenax samples. The samplesand blanks are stored in this freezer until analysis. When the instrumentoperator is ready to analyze the samples, one container of samples is removedfrom the freezer and allowed to come to room temperature (to prevent crackingof the glass tubes during analysis). Samples are then placed into thedesorption apparatus as rapidly as possible, to minimize the handling time.The possibility for contamination of the samples in the mass Spectrometrylaboratory is extremely limited, since no bulk solvents are handled in thislaboratory and sample exposure time is extremely limited.

can.004 21

13.0 DATA REDUCTION, VALIDATION, AND REPORTING

The steps of data review described above are always Included for any datapackage delivered to a client. In addition, the contents of a data packageInclude:

1) a summary data table containing all the values obtained foranalytes 1n all of the blanks and samples analyzed,appropriately qualified

2) a summary of surrogate recoveries for all blanks and samplesanalyzed

3) a description of the experimental procedure

4) a summary of the analytical conditions

5) a summary of the tuning data obtained for every twelve-hourperiod during which analysis of a given series of samples wasperformed

6) a table of the limits of detection

7} response factor database(s) (the response factor databaseobtained in the Initial calibration, as well as any responsefactor databases generated by subsequent recalibration, aretabulated and reported)

8) calibration standards (all calibration standards analyzed togenerate response factor databases are reported, includingchromatograms and raw data reports generated by the data systemof the mass spectrometer)

9} calibration check standards (all raw data associated with theanalysis of calibration check standards are reported)

10) reconstructed gas chromatograms and quantitation reportsgenerated by the mass spectrometer data system for all samplesand blanks are reported

11) mass spectra for the target compounds observed in each sampleand blank analysis are supplied, plotted against referencespectra of the same compound

12) if Identifications of additional compounds are requested by theclient, the data for compounds identified and semi- quantitativecalculated quantities are reported, with mass spectra of thecompounds and the output of the computerized library search

cah.004 22

13) forms generated by the Radian Sample and Analysis ManagementSystem are supplied

14) chain of custody forms and sample seals.

Mass spectrometrlc data are reduced In a semi-automated mode; that is, theanalyst verifies the Identification of every target compound prior to thesubsequent automated generation of quantitative data for that compound. Whenquantitative data are generated, the report from the computer is entered intothe project notebook and archived permanently in this notebook. Then, eitherthe analyst or the Data Control Officer generates the additional informationwhich 1s to be Incorporated Into the deliverable data package. Thequantitative calculations and qualitative Identifications are verified by theLaboratory Supervisor, with a subsequent review by the Senior TechnicalAdvisor.

Immediately after completion of analysis of a sample lot, data are summarizedin tabular form. Any deviations from the protocol are documented. Thestability of the response factors 1s reported in tabular form, to show thatInstrumental parameters were in control when the assay was performed. A tableof surrogate recoveries Is also provided to document the reproducibility ofthe overall sample preparation and analysis procedures.

Field blanks (or trip blanks, as provided by the client) are analyzed for thepurpose of providing blank correction. The results of the analysis of allblanks are reported, but no blank correction 1s reported, except in the casewhere the amount of a compound reported on the blank is greater than 25% ofthe sample amount. In that case, values for the compound in the samples areflagged, since the values are suspect. In addition, laboratory blanks arealso analyzed. The number of blanks analyzed is one blank per ten sampleanalyses. If sufficient trip blanks are not available, laboratory blanks willbe substituted. If a compound Is observed with an identifiable mass spectrumat a level below the method detection limit, the value will be reported andflagged with the code J. If a compound is observed in a blank analysis, thevalue reported for that compound in a sample analysis will be flagged with thecode B.

can.004 23

14.0 INTERNAL QUALITY CONTROL CHECKS

Quality control procedures have been discussed In detail in the description ofthe analytical procedures, since the quality control measures are an integralpart of the analytical methods. However, the quality control procedures aresummarized below:

1} chromatographic check of 50% of all sampling cartridges preparedto monitor for contamination prior to sending the sampling tubesto the field

2) analysis of at least one laboratory or field (trip) blank foreach ten field samples analyzed

3) twelve-hour tuning checks for stability of the mass spectrometer

4) twelve-hour calibration checks for stability of the massspectrometric calibration

5) continuous monitoring of surrogate recoveries for every sampleand blank analyzed

6) continuous monitoring of signal level for the quantitationstandard In every.sample and blank analyzed.

7} Initial quality check of the data by the analyst, withsubsequent review by the Laboratory Supervisor, and anotherlevel of review by the Senior Technical Advisor. Final reviewof the data is provided by the Project Director.

The following criteria are applied for rejection of data:

1} if an analyte 1s observed in a blank at a level which is 25% or moreof the level at which that compound is observed in a sample,quantitative data reported for that compound in the sample areflagged.

2) if none of the quantitation standards are observed in the analysisof a sample, the data for that sample are rejected.

3} if all surrogate recoveries are below 30%, the data for that sampleare rejected.

4) If the level of compound observed in a sample is below the limit ofdetection calculated for the compound, the value reported for thatcompound is flagged with the code J. A decision to reject data willbe made by the Project Director and the Quality Assurance Officerafter complete review of the entire data package.

cah.004 24

The Units of detection to be expected 1n the program are compound specific.The chief factor Influencing limits of detection in a specific sample Is theamount of water which enters the analytical system, a parameter which 1scompletely out of the control of the analyst. Water entering the analyticalsystem causes several types of problems:

1) a quantity of water which is sufficiently large will cause ashutdown of the entire analytical system because of the failure ofthe system vacuum and electronics.

2) lower amounts of water will cause distortion of the chromatography,with consequent spreading of the chromatographic peaks and loweringof observed peak areas for analytes. A sharp chromatographic peakwith well-defined baseline provides far more reproducible and largervalues for quantltatlon than a peak which 1s highly asymmetric andwide.

3} an amount of water which is not sufficient to cause visibledistortion of the chromatographic peaks can still cause areas ofpeaks to be lowered from the values observed for the same quantityof compound spiked onto a dry sampling cartridge. This effect isdemonstrated daily on the analytical system when field samples(which contain varying amounts of water) are analyzed after theIntroduction of standards from an almost completely dry staticdilution bulb.

An additional factor which influences the limits of detection is the amount ofinterference encountered from the sample matrix. For example, a sample which1s taken near the side of a busy road (and which, therefore, shows high levelsof hydrocarbons) will exhibit a proportionately higher detection limit forcompounds of Interest which elute in the midst of the hydrocarbons. Again,the background matrix 1s completely out of the control of the analyst.

Under conditions in which no water is Introduced into the analytical systemand the matrix background level is minimal, the limits of detection shown inTable 6 will be attainable, as demonstrated by analysis of low-levelcalibration standards. In the presence of water in a reasonable range on thesample tubes and not allowing for any interferences from the background, thedetection limits within a factor of 1-3 times the experimentally determineddetection limits should be attainable. In a situation where the amount ofwater 1s large and/or there is extensive contribution from the sample matrix,

can.004 25

TABLE 6. LIMITS OF DETECTION OF COMPOUNDS OF INTEREST

Compound Detection Limit,9 ngtrichlorofluoro-nethane

1,1-dichloroethenemethylene chlorideJt- 1 , 2-d1 chl oroethene1,1-dichloroethanechloroform1,1,1-trichloroethanecarbon tetrachloridebenzene1,2-dichloroethanetri chl oroethene1,2-dichloropropanebromodlchloromethanei- 1 , 2-dichl oropropenetoluene£-1, 3 -di chl oropropene1,1,2-trlchloroethanetetrachl oroethenedibromochloromethanechlorobenzeneethyl benzeneffl*t fl-xylene2-xylenebromoform1,1,2 , 2-tetrachl oroethaneaj-dichlorobenzenefl-dichlorobenzenefl-dichlorobenzenestyreneacetone2-butanoneheptaneisopropyl benzenehexanechloromethanevinyl chloridebromomethanechl oroethane

1.1

3.21.43.93.91.42.41.83.83.21.24.11.44.82.26.92.92.01.41.23.81.81.92.63.56.16.37.92.54.18.06.71.6.7.052604550

PracticalQuantitationLimit, ng°

3

104121247511104124147

219644115681018192481224205

21160180140150

ng/mLEPA 624

_ _ _

2.82.81.64.71.63.82.84.42.81.96.02.2...6.05.05.04.13.16.07.2......4.76.9.__------...-_..._......._..._...

- - -

*. — , —— , —— —_ — _ —— _ ———— , ———— „ ———— „, — ^ — , —— m — , ____________'Detection limits determined according to SOP 327-MS-027 (Appendix 2).'practical Quantitation Limits are provided as a guide and may not beachievable in wet samples or matrices which have high levels of organiccompounds.

cah.004 26

limits of detection will meet or exceed the higher portion of the rangeslisted above, If Indeed the samples can provide Identifications andquantitative data at all.

Detection Units from EPA Method 624 (calculated as ng/mL, since the sample ispurged from water) are Included for comparison with the detection limits whichpcan be expected from Tenax cartridges. The comparison Is made with EPAMethod 624 since there should likewise be water present when the compounds ofInterest are purged from water, and these numbers show that, 1n most cases,detection limits from thermal desorption and analysis of compounds of interestpfrom Tenax which contains some amount of water are comparable to thedetection limits from EPA Method 624. The permanent gases, in particular, arevery strongly influenced by the presence of water. Chloroethane, for example,responds poorly In the best of circumstances and, being one of theearllest-elutlng compounds, shows a very severe effect in the presence ofwater. The values tabulated above should be reasonably attainable in thepresence of the amounts of water which might be anticipated from sampling on ahumid day. If sampling occurs on a rainy day, however, the values may well gosubstantially above the top of the range listed 1n the Table, if the samplescan be analyzed at all.

15.0. PERFORMANCE/SYSTEM AUDITS

Prior to the initiation of analysis of air toxics samples, the RadianLaboratory participated in the analysis of a series of Performance Evaluationsamples. Radian will participate in such an evaluation again, if auditsamples are available. In the ongoing analytical program, the analysis of thecalibration check samples serves as a system control, and no external auditshave been initiated, since the size of the sample batches is less than 75-100samples.

Some programs which can be cited to show Radian familiarity with QualityControl/Quality Assurance procedures and participation in programs whichprovide audit samples are discussed below: Participation in the ContractLaboratories Program (CLP) of the Environmental Protection Agency is projectedfor the Radian Research Triangle Park laboratory for late spring of 1988. At

cah.004 27

that tine, Radian will follow established CLP protocols with regard to theregular analysis of audit samples. At present, the Radian laboratories allover the country are regular participants In the Office of Solid Waste (OSW)Performance Evaluation Sample analysis program, In which samples are sentquarterly to participating laboratories. The sample analyses in this programencompass both organic* analysis and metals analysis. The Radian ResearchTriangle Park laboratory has also participated in the analysis of organics andmetals through the Environmental Protection Agency's wastewater analysisprogram as a prerequisite to the analysis of wastewater samples. RadianPerimeter Park laboratory has also participated 1n the analysis of performanceevaluation samples for certification as an analytical laboratory for the stateof North Carolina, and for those states with which North Carolina hasreciprocal agreements to accept certification.

16.0 SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATAPRECISION, ACCURACY, AND COMPLETENESS

Data precision Is assessed most reliably by the analysis of replicate samples,which must be supplied by the field personnel. In general, duplicate ortriplicate samples are not supplied with a given batch of samples, butreplicates are analyzed as supplied and as per client request. Results froman analysis of replicate spiked samples, supplied as Performance Evaluationsamples, are discussed elsewhere in this Quality Assurance Plan. At any time,by request of the client, if problems with reproducibility are suspected, aset of replicate sampling tubes can be prepared and analyzed, using any or allof the compounds of Interest. The only other indirect assessment of precisionIs the recovery of surrogates for a given batch of samples, where conditionssuch as background and level of water observed on the sampling tubes mightreasonably be expected to be constant. However, this assumption of constantconditions for a given site is only an approximation, since conditions mayvary in the course of a day and will almost certainly vary over a period ofseveral days.

Data accuracy is evaluated by analysis of spiked samples to determine thecorrespondence between found and true values. This type of experiment has beenperformed only once, with results discussed above.

can.004 28

A scheme of analysis of Matrix Spike (MS) Samples and Matrix Spike Duplicates(MSD) would be a desirable addition to the air toxics analytical program. Thepreparation of reproducible matrix spike samples Is not an establishedprocess, nor are all clients willing to supply the additional samples requiredto prepare and analyze an appropriate level of MS/MSD samples. Radian willdevelop the techniques for preparation of MS/MSD samples and will request fromclients the requisite field samples so that appropriate numbers of MS/MSDsamples can be prepared and analyzed.

Completeness 1s evaluated by comparing the number of analyses for which validdata are generated to the number of sampling tubes supplied for analysis.Completeness is typically 95% or better. The usual reasons for obtainingcompleteness less than 100% are samples broken in shipment which thelaboratory is subsequently unable to analyze or external factors such as powerfailure or instrument failure.

17.0 CORRECTIVE ACTIONS

Corrective actions are Initiated whenever any of the parameters monitored inthe program shows a value which 1s outside the limits for acceptability. Thecorrective action requires the determination of the source of the problem:some of the possible sources of problems include instrument failure andcontamination. The appropriate corrective actions include repair of theinstrumentation, where pertinent, and removal of the sources of contamination.It 1s the responsibility of the analyst to identify problems while theLaboratory Supervisor has the responsibility for initiating and completingcorrective actions and advising the Project Director of the nature of theproblem and the action taken to resolve it. The Project Director approves allcorrective actions and, if necessary, advises the client.

A specific illustration of the occurrence of a Corrective Action was thecontamination of sampling cartridges with styrene and related compounds. Assoon as the analyst observed a blank with a high level of one of the compoundsof Interest, the analyst notified the Laboratory Supervisor, who in turnnotified the Project Director (Dr. Wagoner) and the QA Officer/Senior

cah.004 29

Technical Advisor (Dr. Bursey). Since there was no possibility of re-samplingor re-preparation of the samples, the samples were analyzed with appropriatequalification or failure to report suspect compounds in the samples based onthe results of the blanks. However, cartridge preparation procedures werereviewed by Dr. Wagoner and Mr. McGaughey, the cause of the problem wasdetermined, the cartridge preparation procedure was revised to eliminate theproblem, and testing procedures far more stringent than the standardprocedures used for preparation of sampling tubes for field sampling were useduntil cognizant project personnel were confident that the problem had beeneliminated.

18.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT

The Laboratory Supervisor is responsible for evaluating measurement accuracy,precision, and completeness on a routine basis. The Project Director isresponsible for reporting the evaluation of these results to the client and tothe Laboratory Technical Director if Quality Assurance Plan criteria are notbeing met. Reports on corrective actions and their resolution are prepared bythe responsible individual and submitted to the Laboratory Supervisor.Appropriate Quality Assurance and Quality Control data are an integral part ofevery analytical report which is delivered by the laboratory.

19.0 SAFETY

The safety considerations listed below will be adhered to during any plannedlaboratory activities. Laboratory activities will be performed under theguidance of the Radian Corporate Health and Safety manual and the currentlaboratory procedures at Radian's Research Triangle Park analytical laboratoryfacility.

The Radian Project Director is responsible for the health and safety of Radianproject personnel . All work practices shall comply with the safetyrequirements prescribed by the Occupational Safety and Health Act of 1970, asamended (29 CFR Part 1910), and all employees will be expected to performtheir duties in a responsible, professional, and safe manner. All Radian

can.004 30

personnel will be required to read the Radian Corporate Health and Safetyplan, and have all their questions answered prior to the start of thelaboratory activities.

can.004 31

Appendix 1. Standard Operating Procedure for the Analysis of Air SamplesUsing Gas Chromatography/Hass Spectrometry

cah.004 32

e a mmom ATI OH

CONFIDENTIAL

RESEARCH & ENGINEERINGSTANDARDOPERATINGPROCEDURE

GROUP OR LABORATORY:Perimeter Park

TITLE:[Standard Operating Procedure For The Analysis

Of Air Samples Using Gas Chromatography/Mass

PROCEDURE NO: PAGE:327-MS-005 1

REVISION NO: EFFECTIVE DATE:

SUPERCEOES:

REFERENCES

SATELLITE Fll ES,

REASON FOR REVISION:

1.0 PURPOSE

1.1 This method provides a standard operating procedure for theoperation of a Tekmar LSC-2 sample concentrator system modified

R Rfor the analysis of Tenax and/or Tenax /charcoal sampling tubeson a gas chromatograph/mass spectrometer/data system (GC/MS/DS)using a megabore fused silica capillary column.

2.0 MATERIALS

2.1 The following materials are needed to perform the analysis ofR RTenax and/or Tenax /charcoal sampling tubes:

a. Variable autotransformerb. Type K thermocouple wirec. Supelco gas purifier (clamshell oven) {Supelco, Inc.

Bellefonte, PA)d. 0.125 inch TeflonR tubinge. Swagelok fittings: 0.25 - 0.125 inch stainless steel

reducing unions; 0.25 - 0.25 inch stainless steel unions;0.25 - 0.25 inch TeflonR union,

f. Tekmar LSC-2 purge-and-trap unit with a three-armed purgeflask (Tekmar Co., Cincinnati, OH). Heat the purge flask to90°C by wrapping with heating tape and controlling thetemperature with a variac.

VRITER NAME/DATE

CTIVITY MGR NAME/DATE NAME,'DATE NAME/DATE

CONFIDENTIAL ~TAH«. anC..»«..T.,~ «___ STANDARDRESEARCH & ENGINEERING SSSSS&

(CONTINUATION PAGE PROCEDURE

PROCEDURE NO: PAGE:2

g. DB-624 Megabore Column: 0.50 mm by 30 m, 5 u film thickness(J&U Scientific, Rancho Cordova, CA)

h. 500 uL syringes.1. 9.5 mm Thermogreen septa (Supelco, Inc., Bellefonte, PA).J. Temperature controller (Omega Engineering, Inc.,

Stanford, CT).k. Static dilution bulbs.

Note: The calibration, quantitation static dilution bulbcontains the compounds of interest, the quantitationstandards, and the surrogate compounds. This staticdilution bulb is used only to create the response factordatabase and is not used with the analytical samples.

The quantitation, surrogate static dilution bulbcontains the quantitation standards and the surrogatecompounds. This standard is coinjected with the samplefor quantitative analysis.

1. Analytical trap, EPA Method 601. The trap must be at least2 cm long and have an inside diameter of at least 0.105inches. The trap must be packed to contain the followingminimum lengths of adsorbents: 1.0 cm of methyl siliconecoated packing (3% OV-1 on Chromosorb W'(60/80 mesh)), 7.7 cm

Dof diphenylene oxide polymer (Tenax GC , 60/80 mesh), 7.7 cmof silica gel, 7.7 cm of coconut charcoal (Supelco, Inc.,Bellefonte, PA).

m. Gas Chromatograph/Mass Spectrometer/Data System. The gaschromatgraph is an analytical system capable of temperatureprogramming through a subambient range, with all requiredaccessories such as gases. The mass spectrometer is capableof scanning from 35-60 amu every second or less, using 70 eV(nominal) electron energy in the electron ionization mode andproducing a mass spectrum that meets all of the criteria inTable 1 when 50 ng of 4-bromofluorobenzene (BFB) isintroduced through the gas chromatograph inlet. The GC/MSinterface is a glass jet separator. The computer system

CONRDENT1AL

RESEARCH & ENGINEERING(CONTINUATION PAOO

STANDARDOPERATINGPROCEDURE

n.

allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout theduration of the chromatographlc program: this data system isinterfaced to the mass spectrometer. The computer has softwarewhich allows searching any GC/MS datafile for Ions of aspecified mass and plotting such ion abundances versus time orscan number. This type of plot is defined as an Extracted IonCurrent Profile. Software is available to allow integratingthe ion abundance signal levels In any Extracted Ion CurrentProfile between specified time or scan-number limits. The mostrecent version of the EPA/NIH Mass Spectral library is alsoavailable (42,222 compounds).

Reagents. The analytez have been purchased individually at thehighest possible level of purity and are added individually toprepare the calibration mixture. The internal standards areperfluorobenzene, 1,4-difluorobeneene, and d^-chlorobenzene.The surrogate conpounds are dg-benzene, d^-l^-dichloroethane,perfluorotoluene. d^-toluene, and d^Q-ethylbenzene, Calibrationstandards solutions are prepared monthly or as often as necessarywhen degradation of the standard mixture is noted. Calibrationstandards are analyzed at a minimum of five concentration levels.Methanol used to prepare the standard solutions is of pesticidequality.

The following solutions are needed for calibration and tuning:

o Stock Standard Mixture Solutions containing all compounds ofinterest at the concentration of 200 ng/ul in methanol.

o Working Standard Mixture Solutions at concentrations of 10 ng/uland 50 ng/ul, prepared by dilution of the Stock StandardMixture Solutions.

o Standard solution containing 25 ng/ul of 4-bromofluorobenzenein methanol.

o Internal/Surrogate/Tuning solution containing 25 ng/ul ofinternal standard compounds, surrogate compounds and 4-bromo-fluorobeneene (BFB) in methanol.

CONFIDENTIAL

RESEARCH ft ENGINEERING(CONTINUATION PAGE)

STANDARD

NO: PAGE:

3.0 SAMPLE PREPARATION

Precleaned TenaxR/TenaxR-charcoal tubes are sent to the field forsampling; sampling procedures are usually not performed by Radianpersonnel. Upon receipt at the Radian Research Triangle ParkLaboratory, sampling tubes are logged into the Laboratory SampleAnalysis and Management (SAM) system.

After the samples are logged into the SAM system, the tubes are releasedto the custody of the Mass Spectrometry Laboratory Supervisor, whoplaces them in a locked restricted access freezer used solely for thepurpose of storing sorbent tubes and located in the Mass SpectrometryLaboratory. The exposed sampling tubes are released to the analystwhen the instrument 1s calibrated and prepared for analysis.

Th* blank cartridge, calibration cartridges and sample cartridges willbe prepared , prior to analyfil*, a* following:

o Preparation of blank cartridge for analyeiaA clean , blank cartridge is spiked, from the carrier gas inlet endwith 2 ul of the Internal/Surrogate/Tuning Solution.

Preparation of Calibration Cartridges -The calibration cartridges will be prepared only when the GC/MS systemla ftWMMl and r*ady *«r PM*1* analysis j , Clean, blank cartridges arespiked, from the carrier gas inlet end. , with 2 ul of Internal/Surrogate/Tuning Solution, and variOM volume of working standard solutionsas they are shown below:

Amount of Analyte

20 «850 ng100 ng200 ng300 ng

Vol. of 10 ng/ul

2 «15 ul

Vol. of 50 ng/ul

2 ul4 ul6 ul

Preparation of Calibration Check Cartridge -A clean, blank cartridge is spiked, fro» th* *Accl«r ««* tftlfct end1,with 5 ul of the 90 3g/«d.,£U&iag standard mixture solution, and2 ul of Internal/3urffifSliTTOalng Solution.

CONFIDENTIAL STANDARDRESEARCH & ENGINEERING

(CONTINUATION PAGE)WUCHXJHENO: PAGE:

5

Preparation of Sample Cartridges for analysis -

Spike each Maple cartridge** fron the carrier gas inlet end >with2 ul of the Internal/Surrogate/Tuning Solution, prior to theconnection of the sample cartridges to the purge train.

Note: 1. The end of the cartrUtf* aplked withbe Marked. When the c*rt*ldg* !• connectf^TW^Sffl^k train,the spiked end should be connected to the carrier gas Inlet.

4.0 ANALYTICAL METHODOLOGY

4.1 Preparation of the Instrument.

Check the helium gas cylinder for purity, cylinder pressure, andappropriate settings of all valves.

Note: If the pressure of gas remaining in the cylinder is not atleast 500 psig, introduction of impurities is extremely likely.If extensive contamination is introduced, bakeout and possiblyreplacement of the analytical trap will be required.

4.2 Connect the "Desorb" line located on the back panel of the Tekmarpurge-and-trap apparatus to the outlet of the capillary pressureregulator on the panel of the gas chromatograph. This connectiondirectly controls the flow of the carrier gas through the Megaborecapillary column as well as the flow of the desorption gasthrough the analytical trap on the Tekmar unit.

4.3 Connect the purge line located on the back panel of the Tekmarpurge-and-trap unit directly to the carrier gas supply by using a

pstainless steel Swagelok tee. The head pressure on the trap ofthe Tekmar is controlled by a pressure regulator located on thefront panel of the Tekmar. This pressure regulator should be setat 20 psig +/• 5 psig.

CONFIDENTIAL STANDARD

RESEARCH & ENGINEERING SSSSSS&(CONT.NUAT.ON PAGE) PROCEDURE

PROCEDURE NO: PAGE:

4.4 Test the flow of gas through the purge of the analytical trap onthe Tekmar by the use of a soap bubble meter. The flow should beapproximately 30 mL/min. If an adjustment is required, a finemetering valve located on the front panel of the Tekmar willadjust the flow to the correct measurement.

4.5 Connect the heated transfer line from the Tekmar to the Megaborecolumn by the use of a 0.0625 inch to 0.0625 inch stainless steelpSwage!ok union. A graphite (0.8 mm ID} polyimide ferrule must beused on the column side of the union and a stainless steel ferrulemust be used for the connection of the heated trace line from theTekmar to the union.

4.6 Check the flow of the carrier gas through the Megabore CapillaryColumn by using a soap bubble meter or a mass flow measuring device.The flow through the Megabore Column must be 10-15 mL/min.

4.7 After flow through the column has been established and verified,condition the column according to the manufacturer's directions, ifnecessary. After the column is conditioned, connect the back of theMegabore column to a tee located in the oven of the gas chromatographthrough which a make-up flow of 15 mL/min of helium is supplied.Connect the column to the tee withwith a graph1te-polyim1de ferrule.

DConnect the column to the tee with a 0.0625 inch Swagelok fitting

4.8 Install the separator in the transfer line oven according to themanufacturer's instructions, if necessary.

5.0 ANALYTICAL PROCEDURE

5.1 To initiate analysis, tune the mass spectrometer using perfluoro-tributylamine (FC-43) according to the criteria recommended by theinstrument manufacturer. Tuning mass 131 and 219 to a ratio of 1:1(35% abundance relative to m/z 69} will usually obtain an

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acceptable tune so that the tuning criteria for bromofluoro-benzene will be met successfully (Table 1). Prepare a masscalibration table so that the computer will assign massescorrectly.

5.2 After a mass calibration table has been prepared, analyze SO ngof 4-bromofluorobenzene and demonstrate that the criteria inTable 1 are met successfully. If the criteria are not met,adjust the tuning parameters until the bromofluorobenzene tuningcriteria are met successfully. No analysis can be performed untiltuning criteria are met successfully.

5.3 the tcalibration by100. ,200 «nd 300 vgfri ofThe analTtea, ••rroaatetogether with yriairy •neatitetlon

perform a five-pointcartridges containing 20, 50,

• of Interest respectively.Internal (quantltatlon) standards,. are shown In Table 2.

5.4 Calculate relative response factors according to the equationbelow:

RF * <Acpd x <Astd xwhere:

RF « response factorACpd • area of primary quantltatlon ion of compound of interest

ngstd " nan°9ranis of standardAstd " area of Pr1mary quantltatlon ion of standard compoundngcpd * na"ograms of compound of interest

.......... CONFIDENTIAL STANDARDRESEARCH & ENGINEERING

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Follow the scheme of quantltatlon for the compounds of interestshown 1n Table 2; There are three quantltatlon standards,perfluorobenzene, 1,4-difluorobenzene, and dj-chlorobenzene.

5.5 Calculate response factors for each compound relative to one of thequantltatlon standards. The quantltation standard selected forthe calculation of the response factor for a compound is thequantltation standard which has a retention time closest to thecompound being measured.

5.6 Calculate an average response factor for each compound.

5.7 Using the response factors from the initial calibration, calculate thepercent relative standard deviation for the Calibration CheckCompounds according to the following equation:

SDZRSD - -=— X 100

mwhere:RSO • relative standard deviation

x - mean of five initial response factor determinations for acompound

SO • stan,aup deviation of average response factors for acompound

SD __

N-l

The % Relative Standard Deviation for each individual CalibrationCheck Compound should be less than 20%. This criterion must bemet in order for the original calibration to be valid. The

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Calibration Check Compounds are: chloroform, carbontetrachlorlde, trlchloroethene, toluene, tetrachloroethene,chlorobenzene, o-xylene, and isopropyl benzene.

5.8 Verify that the gaseous components (chloromethane, bromomethane,vinyl chloride, chloroethane) are observed with a response factor

notstandard aoiatiCMrepeated .

ared and ti* calibration process

5.9 To perform analysis of blanks and samples, connect the sampleanalysis train to the purge flask and proceed as follows:

5.9.1 Heat sample cartridges (TenaxR and/or Tenax /charcoal to180°C with the aid of a temperature control device connectedto the clamshell oven. Desorb the tubes by backflushingwith helium so that the charcoal end of the Tenax /charcoaltube is exposed to the carrier gas first.

5.9.2 When the sample tubes have reached the final desorptiontemperature of 180°C, start the flow of purge gas and injectthe quantltation and surrogate standards from the staticdilution bulb into the aide-arm of the purge flask using agas-tight syringe.

5.9.3 When the sample tube(s) is purging and the correct standardshave been injected, set up the program on the gaschromatograph and the data acquisition for the INCOSsoftware. Follow the Applications Software Manual for thecorrect setup of the data system.

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5.14

PROCEDURE NO: PAGE:

and the analytical system 1s recalibrated, 1f necessary,prior to the Initiation of sample analysis. If theacceptance criteria are met, sample analysis Is Initiatedand the values for response factors obtained from theanalysis of the dally calibration sample are used forquantitative calculations for the samples analyzed onthat day.

5.12 Analytical conditions are shown In Table 4.

5.13 Evaluate quantltatlon standard responses and retention times1n the check calibration standard immediately after or duringacquisition of the data. If the retention time for any quan-tltatlon standard changes by more than 30 sec from the last checkcalibration (12 hr), Inspect the chromatographic system formalfunction and make corrections, as required. If the ExtractedIon Current Profile area for any of the quantitation standardschanges by a factor of two (-50% to +100%) from the last dailystandard calibration check, Inspect the mass spectrometer formalfunctions and make corrections, as appropriate.

ifany

\n in a field bleak ( observation ofat a level above the detection

limit), advise the Laboratory Supervisor of the occur-rence of the contamination. The client will be advised of theextent and nature of the contamination and a joint decision can bemade as to whether or not to continue the analysis of samples.

5.15 If high compound levels are observed 1n a sample, analyze a blankas the next sample in the sequence in order to demonstrate that nocarryover of components Is being observed. The criteria for asuccessful blank analysis are failure to observe any of thecompounds of interest at a level higher than five times thedetection limit,

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PAGE;11

Analyze a laboratory blank, and verify that no target coopoundsare present at a level above the detection Unite (Table 6) exceptra*tfa?**?e chloride» acetopa, toluene and 2-btttanone. Tf targetcoBpowwle «« observed at a level above the detection Units orthe lab cowm .olvents such aa nethylene i«wt*4«u J^luene,ac«toaa and 2-but«none are obaerved at a iiWW iHPvinesdetection limit«, b«fce tlie analytical trap £*rlM'1mmm andanalyze anotoac blank cartridge. If the pr«blm rrriftiiiri traceche source of tba contamination and corra Mtlflrtl HHt&ltiationof sainple analysis.

the

5.11 Check and verify the initial calibration curve for each compoundof interest once for every twelve hours of analysis. Analyse a blankcartridge apiked with 50 ng of calibration standards and verify thefollowing criteria:

a) gaseous components (chloromethane, bromomethane, vinylchloride, and chloroethane) must be observed with aresponse factor of 0.10 or better.

b) Calibration Check Compounds (chloroform, carbon tetra-chloride, trlchloroethene, toluene, tetrachloroethene,chlorobenzene, o-xylene, and isopropylbenzene) must showa response factor within 20% of the value obtained forthe mean of the database.

c) check the other calibration compounds to be sure that nomore than three compounds other than the CalibrationCheck Compounds have a value which is more than 50%different from the mean of the response factor database.If these criteria cannot be met, re-analyze thecalibration sample. If the criteria still cannot be met,the calibration standard is prepared and analyzed again

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6.0 DATA INTERPRETATION

6.1 Qualitative Analysis

6.1.1 Identify an analyte by comparison of the sample massspectrum with the mass spectrum of a standard of thecompound (standard reference spectrum). The mass spectrafor standard reference are obtained on the gas chromatograph/mass spectrometer/data system within the sametwelve hours as the sample analysis by analysis of thecalibration standards. Two criteria must be satisfied toverify identification:

a) the sample component must elute at the same gaschromatographlc relative retention time as thestandard component;

b) the sample component must correspond to the standardmass spectrum.

6.1.2 The Relative Retention Time of the sample component mustcompare within 0.06 Relative Retention Time units of thestandard component. For reference, the standard must beanalyzed within the same twelve hours as the sample. Ifcoelutlon of Interfering components prohibits accurateassignment of the relative retention time of the samplecomponent from the total ion chromatogram, the relativeretention time 1s assigned by using extracted ion currentprofiles for ions which are unique to the component ofinterest.

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6.1.3 All Ions present in the standard mass spectra at arelative intensity greater than 10% (where the mostabundant ion of the mass spectrum has a relativeintensity of 100%) must be present In the sample massspectrum.

6.1.4 The relative intensities of Ions at a relative intensitygreater than 10% must agree within plus or minus 20%between the standard and sample mass spectra.

6.1.5 When sample components other than the target compoundsare identified, a library search is made for the purposeof tentative Identification. The guidelines for makingan Identification are:

a) The relative intensities of major ions in thereference mass spectrum (ions >10% of the mostabundant ion) should be present in the sample massspectrum.

b) The relative intensities of the major ions shouldagree within plus or minus 20%.

c) Molecular ions present in the reference mass spectrumshould be present in the sample mass spectrum.

d) Ions present in the sample mass spectrum but not inthe reference mass spectrum are reviewed for possiblebackground contamination or presence of coelutingcompounds.

e) Ions present in the reference mass spectrum but notin the sample mass spectrum are reviewed for possible

........... CONF.DENT.AL STANDARDRESEARCH & ENGINEERING

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subtraction from the sample mass spectrum because ofbackground contamination or coeluting peaks. (These.discrepancies can sometimes be created by data systemlibrary reduction programs).

7,0 QUANTITATIVE ANALYSIS

7.1 When a compound has been Identified, use the Integrated abundanceof the primary ion from the extracted 1on current profile and theappropriate relative response factor to perform quantitativecalculations. Perform quantitative calculations according tothe following equation:

concentration (total ng) - (Acpd x ng$td) / (Astd x RF)

where:A d - area of primary quantitation ion for the compound of

Interestng_td - amount of quantitation standard injected, in nanogramsA td - response factor for the compound of interest

RF « response factor for the compound of interest.

7.2 Make an estimate of concentration for noncalibrated componentsof the sample using the equation above with the followingmodifications:

a) the area for primary quantitation ions should be from the totalIon chromatogram, if possible;

b) assume a response factor of 1 for the compound. Report theconcentration indicating that the value is an estimate andindicate which quantitation standard was used to determinethe concentration. Use the nearest quantitation standardwhich is free of interferences.

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8.0 PROJECT NOTEBOOK

8.1 Maintain a project notebook for each batch of samples. Theproject notebook must contain the following Information:

a) analytical conditions,

b) signed and dated pages (black Ink) for all samples,

c) tuning data: mass spectra, lists of mass spectra, andtables of tuning criteria,

d) hardcopy of the library created for the analysis,

e) hardcopy of the procedures used in the quantitation,

f) sample traveler forms,

g) copies of the quantitation reports generated by the datasystem,

h) reconstructed gas chromatograms for every sample,

i) copies of all calculations, Including any correctionfactors or unit changes required,

j) response factor database, including the summary of allfiles making up the database and a list of the samplesquantitated with each database; be sure that allInformation Is complete if multiple databases have beenrequired,

k) copies of all documentation supplied with the standardsto document traceability of all standards,

1) enter explanations of any problems observed with thesamples and any other pertinent observations, and

PAGE:15

m) enter Control Charts for appropriate parameters.

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"V

Table 1. GC/MS TUNING AND MASS CALIBRATION

m/z

50

75

95

96

173

174

175

176

177

Ion Abundance Criteria

15 to 40% of mass 95

30 to 60% of mass 95

base peak, 100%

5 to 9% of mass

less than 1% of

relative abundance

95

mass 95

greater than 50% of mass 95

5 to 9% of mass

between 95% and

5 to 9% of mass

174

101% of mass 174

176

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TABLE 2. ANAIYTES, SURROGATE COMPOUNDS, AND QUANTITATION STANDARDS

perfluorobenzenedg-benzenedl-1,2-dlchloroethanetrlchlorofluoromethane1,1-dlchloroetheneacetonemethylene chloridetrans-l,2-d1chloroethenehexane1,1-dlchloroetbane2-butanonechloroform1,1,1-trlchloroethinecarbon tetrachlorldebenzenel,2-d1chloroethaneheptanechloromethanebromomethanechloroethanevinyl chloride

l,4-d1fluorobenzeneperfluorotoluenedg-toluenetrichloroethene1,2-dichloropropanebromod1ch1oromethane2-chloroethylv1nyl ethertrans-1,3-di chloropropenetolueneCls-l,3-d1chloropropene1,1,2-trlchloroethanetetrachloroethenedlbromochloromethane

(QSI1) (117)(S) (84)(S) (65)(101)(96)(43)(84)(96)(57)(63)(72)(83)(97)(117)(78)(62)(57)(50)(94)(64)(62)

(QS #2) (114)(S) (117)(S) (98)(130)(63)(83)(63)(75)(91)(75)(97)(164)(129)

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TABLE 2. ANALYTES, SURROGATE COMPOUNDS, AND QUANTITATION STANDARDS(Continued)

dc-chlorobenzene (QS 03) (117)d?Q-ethylbenzene (S) (98)cAYorobenzene (112)ethylbenzene (106)«-, p-xylene (106)o-xyTene (106)styrene (104)bromoform (173)1sopropylbenzene (91)1,1,2,2-tetrachloroethane (83)m-dichlorobenzene (146)£-d1chlorobenzene (146)o-d1chlorobenzene (146)aThe number listed in parentheses Is the primary quantitation ion for thecompound. Quantitation standards are Indicated as QS; surrogate compoundsare Indicated as S.

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TABLE 4. ANALYTICAL CONDITIONS

Tekmar LSC-2Purge timeOesorb timeBakeout timePurge temperatureDesorb temperatureBakeout temperaturePurge flask temperaturePurge gas:

10 minutes04 minutes12jninutes30°C200°C21§°C90°CHelium (ultrapure grade)

Gas Chromatograph

Injection portInitial oven temperature

holdOven program rateFinal oven temperature

holdCarrier gasColumn

Mass Spectrometer

Separator oven temperatureTransfer line temperatureManifold temperatureIonizer temperatureElectron energy

100°C58C2 minutes6 C/minute200°C5 minutesHelium (ultrapure grade)J&W 30 meter Megabore DB-624

250°C250°C100°C150°C70 eV

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TABLE 3. DETECTION LIMITS

Compound

trichlorofluoro-nethane

1,1-dichloroethenemethylene chloridet-l,2-d1ch1oroetheneT, 1-dichloroethanechloroform1,1,1-trichloroethanecarbon tetrachloridebenzene1,2-dichloroethanetrlchloroethene1,2-dichloropropanebromodlchloromethanet-lt3-dichloropropanetoluenec-l,3-dichloropropeneT,l,2-tricnloroethaentetrachloroethenedl bromochl oromethanechlorobenzeneethyl benzene0!"» P-xyleneo-xyleneEromoform1,1,2 , 2-tetrachl oroethanem-dichlorobenzene2-d1chlorobenzeneo-dichlorobenzeneItyreneacetone2-butanoneheptaneisopropyl benzenehexanechloromethanevinyl chloridebromomethanechl oroethane

Detection Limit*, ng PracticalQuantitation

Limits

1.1 3

3.2 101.4 43.9 123.9 121.4 42.4 71.8 * 53.8 113.2 101.2 44.1 121.4 44.8 142.2 76.9 212.9 92.0 61.4 41.2 43.8 111.8 51.9 62.6 83.5 106.1 186.3 197.9 242.5 84.1 128.0 246.7 201.6 57.0 2152 16060 18045 14050 150

^Detection limits determined according to SOP 327-MS-027 (Appendix 2).Practical Quantitation Limits are provided as a guide and may not beachievable in wet samples or matrices which have high levels of organiccompounds.

Appendix 2. Standard Operating Procedure for the Determination ofMethod Detection Limits in the GC/HS Laboratory

cah.004 33

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GROUP OR LABORATORY:Mass Soectrometrv. PFK

TITLE:Standard Operating ProcedureOf M«chod Deteccion Limits In

For The DeterminacionTh* GC/MS Laboratory.

PROCEDURE NO:327-MS-027

REVISION NO:

SUPERCEDES.

IPAQE1 1 Of 2

EFFECTIVE DATE

N/ASATELLITE RLES.

REASON FOR REVISION:

rVRPOSE

The purpose of this scandard operacing procedure is co determine mechoddececcion limits (HDD for che analyses which are performed in che GC/MSLaboratory.

2.0 DEFINITION

che2.1 According co che Federal Register, Mechod Dececcion Limit (HDD isminimus concencracion of a compound, determined from analysis of aparcicular matrix, that can be measured and reported with 99% confidencethat the analyce concencracion is greater than zero.

3 . 0 PROCEDURE

1 Sample Matrix: Reagent Vater

3.1.1 Estimate a dececcion limit by determining che concentracion valuethat corresponds co an inscrumenc signal/noise ratio between2.5-5.0.

3.1.2 Prepare interference -free reagent water (no analyte can bedetected at che HDD by boiling HPLC grade water for 1 hour andmaintaining purge with high purity nitrogen at all times.

3.1.3 Prepare a laboratory scandard containing the analytes of interestat a concencracion between 1-5 times the estimated deteccionlimit.

3.1.4 Proceed co 3.2.4.

WRITER: NAME/DATE"/*/

40

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3.2 Other Sample Matrices

3.2.1 Analyze che sample and decernine if an analyce is present becween1-5 tines the estimated detection Limit.

3.2.2 Proceed Co 3.2.4 if the analyta is present bacvaan 1-5 ciaaa chaestimated detection llaic.

3.2.3 Obtain anochar sampla with a lower concentration of analycas incha sane matrix if 3.2.2 limits ara axcaadad.

3.2.4 Process 7 aliquots of tha sanpla through the encire analyticalmethod.

3.2.5 Follow the procedures in the specific method for calculationsand finai reporting units.

3.2.6 Obtain a separata blank measurement for each aliquot analyzed ifblank measurement is required to measure an analyse.

3.2.7 Calculate cha MDL as specified on page 198 of the FederalRegister.

4.0 REPORTING/FREQUENCY OF MDL

4.1 Specify the analytical method.

4.2 Express che result in tha correct reporting units for che method.

•+.2 Report tha sample matrix involved in the MDL determination.

4.4 Report cha mean analyte level with the MDL.

4.5 Indicate if cha MDL procedure was repeated.

4.6 Report a mean recovery if a laboratory standard was used.

4.7 Do noc raporc cha MDL value if an analyce is < MDL or < 10 times the MDL inreagent water.

4.8 Repeat tha MDL study once a year for each analytical method used in chelaboratory.

4.9 Report cha calculated MDL for each method to che Sample Control Group.

4.10 Update all MDLs in che SAM system annually.

190 F«daMl / Vol. 49. No. 209 / Friday. October 26. 1984 / Rules and Regulations

B to Part DaJiiM for tfaa Dafammutioa of tfaa

visHhod DntactBOji Limit — Rmtiaa Lll

(b) If the MDL u to be determined inanother sample matrix anaJyta the sample. Iftba measured level of tbe analyte LB in tberarnmmana'eii ranee of ona to five times the

Tba Bwtbod dataettoa bout (MDU Uleaned u tba mmiaiiim concentration of ••ubaianea tbat can ba measured and reponadvith 09* confidence that tba analyte:oocantratMn is greater ibaa wo and isletennmed from analysis of a sample in a,iven nutru cantamDf tha enalyta.icone otto jipn/icoDon

This procadtm ta rlaaignad for applicabilityo a wide variety at sample typas rangingran reagent (blank) watar caedaimnguuiyte to weaiawaiar contamias; analyte.fba MDL for an analytical procadnra may^ary aa a function of sample type. Tba

rmtfura* m

estimated dataction limit proceed to Step 4.If me measured level of analyta is leas than

the ettimjted detection limit add a known•mount of anaJyta to brinf tbe level ofanaryta between one and fire tunas theeanatattd da lection mnjt

If tbe measured level of analyta is greaterthan five time* tba estimated dataction Unitthere are two options.

(11 Obtain another sample with a lowerlaweJ of anaJyta m tha same matrix if

a ••)•/•]

.'•U dafinad analytical method. It is aaaanoal

it ail saapla procecaing staps of tbamatbod ba included in the

latanrunatooii of tba matbod dataction UnutTha MDL obtained by this procaoura is

ised to iudaa tha signineanca of • nngtenaasuramant of a farara sampla.

Tha MDL procadnra was designed foripplicabilily to a broad variety of physicalind chemical methods. To accomplish this.ha procadura was nuda device- or

i natnunaat-indapandaBL

1. Make an estimate of the detection limittisttg one of tfaa following:

(a) Tha concentration value that•nrraaponds to an instrument ngnai/notse inbe range of 2J US.

(b) Tba concentration equivalent of threetunas tba standard deviation of replicateinstrumental measurements of the analyta inaaaant watar.

(c) That region of tha standard curve wherev ts a significant change m sensitivity,s break in the slope of the standard

-urve.(d) Instrumental limitations.It is recognized that the experience of the

analyst is important to this process.i lowever. the analyst most include the aboveonaidaraoons in tha initial estimate of thaetocnon limit.Z. Prepare reagent (blank) watar tbat is as

free of anaJyta aa posmbls. Ranamn or"Uarnvanca free water is dafinad aa a waterenmie in which analyta and intarrarentancana-anona are not detected at tba

matbod dataction hart of each analyte ofinterest Interferences are dafinad aafBtomadc errors in tba maaantad anaryttealgnai of an astahnahari procedure risnil by

.ja praaanea of interfering spaoaa(tatarferant). Tba tatarnmnt rnnranuailuu is" raaappoaad to be normally distributed in•nraeentaave sanmtee of a grvan matrix.1 (a) If tha MDL U u ba detenmaed in

reagent (blank) watar. prepare a laboratorystandard (analyta in reagent watar) at a

•BflBtttraooa wasefa is at laaat equal to or in• same concentration range aa tba

t method detscooa bauL

(2) The sample may ba need as is fordetenmmnf tba method detection limit if theinalyia levei doaa not txceed 10 times theMDL df tba analyta in reaeent watar. Theranaaca of tba anarrticaj matbod coanaas astbe analyte conontntton inereasas from tbeMDL. hence tha MDL determined under theseorcumstancai may not truly reflect methodvariance at lower snaiyte concantratron*.

4. (a) Take • minimum of seven aiiquots oftbe sample to be used to calculate the methoddatacuon limit and process each through theenure analytical method. Make allcampoUttons according to tha definedmatbod with final results in tba methodrtporUBf units. If a blank measurement istaauirad to caiculata tha measured level ofanaJyta. obtain a separate blankmaejsasiamsmi for each Tf^rft alioBOt•iiaryiad. Tba averaae blank measurement israbtractad from the respective sample

j between I and S tone* (he•ttaatad method detection limn.) Proceed to•P*

(b) It may ba economically and tactancallydesirable to evaluate tba estimated methoddetection fimil before proceeding with 4*.This will: (1) Prevent repeating this ennnprocedure whan th* coats of analyses arthigh and (2) insure that tha procedure n beingconducted at the correct concentration. It nquue poswbie that an inflated MDL will becalculated from data obtained st many tunestba real MDL even though tha level of analyteis leas than five tunas tha calculated methoddetection limit To mean that tha estimate ofthe matbod detection limit is a good estimate.it ia necessary to determine that a lowerconcantraoon of analyta will not raault in •sauBncntiy lower method detection bnut.Take two aUoBOO of the sample to ba used toeakulata tba method dataction limit andpracasa each tbrouga tba entire method.

above ia 4*. Evanwte tbaae data:(1) If tbata measurements indicate the

saaapia is in daairable range fordavsrmtnaaon of tba MDL take fiveaihUnrmal auqaots and proceed. Use allatvan inaaaonmanni for etlcalanon of the~MDL

ffl If tfaaaa niaaiiinmsiiii indicste thesensala ia not in correct ranaa. naamiits tbeMDL obttav new laaipli a* m J and repeataHnar4aor4b.

5. Cakalata tha vananca (S^ and standarddanaoon (S) of the repbcataaafooowa:

X* i -1 to n- * are the analytical results intbe final matbod reporting units obtainedfrom tha a sample aiiquots and I rcf anto the sum of tba X vabaa from t-l ton.

1 (el Compote tha MDL a* follows:

MDL. •»», (S)

wberrMDL - (he matbod detection limitU.-U . . t*t » tbe students t value

appropnata for s WK confidence leveiand s standard deviation estimate withn-l degrees of freedom. See Table.

S * itandard deviation of the rvpiicattanalyses.

(b) The 95% confidence interval estimateifor the MDL derived in fie are computedaccordine. to the following equations derivedfrom pemnales of the chi square overdegree* of freedom distribution |,'/df).

LO.-QJ4MDLUO. - ZJD MDLwhere LCL and UCL are the lower and

upper 98% confidence limits respecnveiybased on seven aiiquots.

7. Optional iterative procedure to verify theraaaonablanaas of tba estimate of the MDLand subsequent MDL determinations.

(a) If this is tbe initial attempt io computeMDL baaed on tfaa estimate of MDLformulated in Step 1. lake the MDL <*calculated in Step & spike in the matrix «t thecalculated MDL and proceed through theprocedure starting mth Step 4.

(b| If this is the second or liter iteration ofthe MDL calculation, use S1 from uie currentMDL calculation and S'from the prmoiuMDL fgknilaf*"" to compute the F-rtOo. TheP-ratx> ts calculated by substituting the largerS'mto the numerator SN and the others mtotbe denominator S V The computed F-raoo isthan compared with the f-rabo found in thetable wmcfa is X05 u follow* if 5V3%<X01 then compute the pooled itandarddeviation by tba following equation:

12

if SVS'^UJS. raapike at tbe most recentcalculated MDL and process the samplestbrooeh tbe mutadura itarong with Step 4. Ifthe moat recant calculated MDL does notparam qualitative "^tiftfaHoa whan

are apikad at that lawL report theMDL as a coooantrauuu batnaeii tha cttrraatand pievmua MDL which pamno) qualitative

defoJofdii

i

14

(e)Use tba u^ M calculated in 7b toconmnte tba final MDL according to tbefollowing equation:

tbe«pp

afie

tbe'vasiMDIi tarethai

Ifbek,excereaaMDi

AppCou.SP-AMl.Sc

LIdetertotalwatewast.

1-2/Ulanstopsthairaccu.diaao.

*Pproparrbrincrae

/ Vol 49. No. 209 / Fridjv. October 2B. 19S4 / Raiet tod R g f o J a t i o n i 1 M

waan 2J« Is eaaai to in. i^ - Jft(d) The 99V confidence bants for MDL

derived te 7e an oaapuiad accentine to thefbUowmi tqaaoan* derived from preceaalesof the cat squared over deerees of freedomdtetnoatiott.

LCL-Q-r2UDLUO.-l.a8 MDL

when LCL and UCL an the lower and upper9K confidence limits retpec&vi^ (Mead onUaUqtwu.

TAKES OF STUMMTT t VALUKS AT THK 99PBMCBBfT COmOKMCK LF*.

•••M

Si-ll ..,00-,

tfl I»lIS IJO Isot

iiii

The analytical method used most bespecifically identified by number or title andthe MDL for seen analyte sxptasstd in thtappropriate method repot one, onto. If theanalytical method permits options whichaffect tnt method detection limit theseconditions matt be speeded with tfat MDLvesss. TM sampk matrix used to dtianniuethe MDL mast also be identified with MDLvawa. Report the mean analyte level with thtMDL and indicate if the MDL procedure wasiterated. If s laboratory standard or • samplethat contained a known amoant saaiyte wasused for this detemnaanoa. also report the

[f tht level of aaaiyte m tbt sample WMbatow tht dtianmnad MDL or does notexceed 10 times tbt MDL of tht anaiytt mraaaent water, do not rvport t vame for thtMDL.Appendix C to Pert tmCoviniedSpectromeoric MMbod for Tract QawjaotAMlrw of Water and W

L Sap* and ApplicationU TM< Mtbod may 6« Mad far th«

total eleBMBti m dnbddaf water, •arfectWVMT. and doa>etoc and iadaatnai

iampin, appropriate itepn onwt bt taken tocomet for potential imarterenc* tffeeta. (See•ecnona.)

U Table 1 liats tiatneoti for which thiimethod appoat aioni with recommendedwmeteoftht and typical ettmaiadiaatnanentai ijeiacuoii limits aatnfoamnoaoal pneanaOc nvboiixatMo, Actualweriomj detoctton hmiu an ia«p4tijaptnritnl and ai the sampit matnx vane*.theee coDcantraOona may alao vary, la ttme.oomr tlementt may be added u more(•formation, baoomet avaiiable fitd at

abet*LA Beeaaaa of the difievtfioae mafcat and mooeis of sanaactarymatnaaaata. no detailed instrumentaloperadnf matracnoas can be wuvidenInstead, the analyst is referred to theinagacnoa provided by tht manufacturer ofthe pwtfcalar lastntmenL

"•f tSuauaarrofMfthodU The method describes • ttchmoue for

the ffmfff 11 ninut or seonennaJ mulbdenMBtdetarmdiatton of trace eleaienu in soutnon,The basts of the method is tht meastwmeniof ttoanc tmttsion by an opticalipectroscopic tecbmgua. Sampits sxtnebalized and the aerosol that is produced istransported tothepiaama torch whentadtation ocean. Charactanefic stonuc-Une•aveana apactn en prodaced by s radio*fraqatiiLT tndacCvrty coapied plasma (ICP1The specm an dispersed by • snoafl

an saonftond by peotomalttpoer tabes- ThtpBosocscraats from the pbotomaitfpiier tabesan preososod aad coairaUad by s cnninater

. A backs? uond correction technique isGO ODmoanaate for vartabia

baacaRMnd contribuQon to tht determtnatiaiiof trace •iamenu. Backfraund nm»t fatmeteared adtacem to anaiytt line* onsampwt dnrtnf anaiymis. The poaaonitterted for the backmnmd intenattyBwaeBnment. on tidier or both udte of thtanaryttcmi Una, wUJ be determmed by thtrnmpiuuty of the apectram adjacent to theaanryte Uae. The pomtion need anut be freeof apecml intartewaot and reflect the sameCMmmi in backframMi inienejty u ocean atThi mil j ii mriiainili mi •••mlBaacmwa convctUm it not remand incneet oftimt braadnmnf when •

dtarede the eatlyrt'al mulL The poambiiity<rf additional mMrtemcM named m M (andttea far their pnaaaet at daacnbed in ii|inaeid alao he mcnmiiied and appropriate

rat* wtocfaIDtftatOom

lien.U Dffoolved tiamaaci an ntitniiiiiad in

Stared aad aodinarf uapiee. AppropriateMeat mart be taken m all tniiyaai ueneonthat potential imaiftieucei art taaan mtoacoDent Thii u eapecuUr trae when

oeed 1500 a^/L. (SeeS.)

LJ Total eiemaan an detammed after

of the

wi peat rhmeeji • O4B urn meabrant filter.U StMpenoW—Those dementi which

an retmaed by • O4S turn inemleeiM filter.U Totat—The ooncentraOon det

oa an eaftltend aampn faUowint vmoralljiinut (Sacamt ajfc or tbe MM of thtdteaanvd ntmj i

pernymed. Since dmeeomiincnaee the dieaotved tottdi

[Section ai phm ait.3.4 TotaJ naarueotitf- Tha concentre POP

I on an enflltarad Mmple foUowmjwith hot dihite mmenl aod

U inftnmmtaJ asmcaon limit ThtcoocentraOon eqatvaamt to a samel dae totheanalyta. which Is eaaal to three tuaas tatstandard dmatton of a series of tea npttcsttmteturementi of s raaaaat blank stanel atthe same M.r.ttn«rh

U Saowovrty—Tat slope of thtuMlytkal carve. LS. ftmcdoeal relationship

i mnmatty andIOOO.

frin unaaii enact smiokij^-AmattleiesaeBt standard of kiaiwnooanBBtnttoae prepared by the soalysl toasssaear aad verify Instrument performancean a daily basm. (See 74U J

U tot^ftnuLt coses: aoeaWe—A

eaatyts sUmeats of known concentndonthai can be aaed to vattfy beckfroand andlamnssaauu catrecnoa iacaoo

obtained from aa oatttoe auuice havnmkaown. conceinratioe vamea to be vaed tovtn/y tbe caubratton Maadarda. (See 7JU|

3.10 Caiibroooa «umuuju> A stnts ofknown standard soninons used by thtaaalysi for cmiibrsoon of tht instrument (i.t_preparation of tht analytical currtt. (Stt 7.4!

111 Lauar tfynaoue roagf—Thtroacsntreoon ransje over which thsanalytical corvt nmauai linear.

112 Aaoytet 6fane A votant ofJaiiauied. distilled wear cnmatmnf thtsame aad matrn as the cahonoon standardscanted tluousjb the enttn aaalytical i

HId w dified with

ftHQi and HO. [Set 7ii)U4 Mithod of ttaadard addition— The

Handard addioaa tafchuajae mvofves tht useaf the unknown and the ankaown piosakaown amonnt of Maadard. (Set 10AI.]4-Saffty

4.1 The toxaaty of caranogeniaty of tectoftaamnt tiaed in this method has not btcnpncMely defined: however, each chtancalooamoand shoaid be tnatad u t potamtalhealth hazard. From tms vitwpomt czpotartto these rhf*™1" maet be ndaced to thelowest poatibli leva! by whatever meant•vauabla. The iahocaawy tt repeomitae far

avnatawanaawObofOSHA rtfataoane reaardtef the tanibaadhav of tht cnamsoaii apactfled in thismethod. A lefereace file of material datahaadttnf abeett sonasd atea be madetvauabM to all penanisal inrolred ta thechemical analysts. Additional reference* tolaboratory sanity an evaaabie and havebeen idaattfled '•** -*•—-*• for theiasonaaooa of the maWyat

SJ Several types of tamafeieuut tffsctimay contribute to tnaccvaoea in thtckiamuaaoon of trace liieiieU They can bt

1U Sptetra/iatmfmmum can bei lamuiliiil as (1) ovetasp of a spectral tintfrom another siemeac W uuiaeuliad overiapof aaaacalar bend epeuin. (31 bacfcareandtuacibanoe from oaiUuaaai or

paaaamaaa: and (4)d oaunoanan from ttny Uaat from