04334-4

FINAL WORK PLANM E T A L S P E C I A T I O N A N DSOURCE C H A R A C T E R I Z A T I O NC A L I F O R N I A GULCH CERCLA S I T EL E A D V I L L E , COLORADO

September 24,1991

Prepared for:Resurrection Mining Company

Prepared by:Camp Dresser and McKee Inc.133117th StreetSuite 1200Denver, Colorado 80202

FINAL WORK PLANM E T A L S P E C I A T I O N A N D SOURCE C H A R A C T E R I Z A T I O N

C A L I F O R N I A GULCH CERCLA S I T EL E A D V I L L E , COLORADO

TABLE OF CONTENTS

Section____________________________________________Page1.0 INTRODUCTION ........................................... 1-11.1 Objectives ............................................ 1-11.2 Components of the Work Plan ............................... 1-22.0 SCOPE OF WORK ........................................... 2-13.0 SELECTION, HANDLING AND DISTRIBUTION OF SAMPLES FOR M E T A L

SPECIATION AND SOURCE CHARACTERIZATION STUDIES ............. 3-13.1 Protocol for Select ion, H a n d l i n g and Distribution ofSoil Sample s for Off-Site Laboratory Analysis andMetal Speciation ........................................ 3-23.1.1 Soil S a m p l e s for Off-Site Laboratory Analysis .............. 3-23.1.2 Soil Sampl e s for Metal Speciation ...................... 3-23.2 Protocol for Selection, H a n d l i n g and Distribution ofEnvironmental S a m p l e s for Off-Site Laboratory Analysisand Metal Speciat ion ..................................... 3-43.2.1 Environmental Sample s for Off-Site Analysis ............... 3-43.2.2 Environmental S a m p l e s for Metal Speciat ion ............... 3-53.3 Protocol for Select ion, H a n d l i n g and Distribution ofMine Waste Rock, Tail in t s , S l a g and Smelter Sample s forOff-Site Laboratory Analysis and Metal Speciat ion ................... 3-64.0 OFF-SITE LABORATORIES LEVEL f f l AND IV CHEMICAL ANALYSIS ....... 4-15.0 ELECTRON MICROPROBE ANALYSIS ............................. 5-16.0 X-RAY DIFFRACTION ANALYSIS ................................ 6-17.0 OPTICAL MICROSCOPY ...................................... 7-18.0 LEAD ISOTOPE ANALYSIS .................................... 8-19.0 DATA VALIDATION ......................................... 9-19.1 Overview ............................................ 9-19.2 Metal Analyses by Off-Site Laboratories ......................... 9-29.3 Electron Microprobe Analysis ............................... 9-39.4 X-Ray Dif f rac t i on ....................................... 9-39.5 Optical Microscopy ...................................... 9-39.6 Lead Iso t op e Analysis .................................... 9-3

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TABLE OF CONTENTS (CONTINUED)Section____________ ______ __ ______ ____ __________Page10.0 PRINCIPAL SCIENTISTS ..................................... 10-111.0 REFERENCES ............................................ 11-1

A P P E N D I C E SAPPENDIX A - Standard Operating Plan and Quality Assurance Project Plan for Silver Val l eyLaboratoriesAPPENDIX B - Standard Operating Plan and Quality Assurance Project Plan for Accu-LabsResearch, Inc.APPENDIX C - Standard Operating Plan and Quality Control for Electron Microprobe Analysisby Surface Science Western, the Surface Science Laboratory, the University ofWestern OntarioAPPENDIX D - Standard Operating Plan and Quality Control for X-Ray D i f f r a c t i o n Analysis by theMineral LabAPPENDK E - Standard Operating Plan for Optical Microscopy Analysis by Amax.APPENDK F - Standard Operating Plan and Quality Control for Lead Iso tope Analysis byDepartment of Geological Sciences, University of WashingtonAPPENDIX G - Curriculum Vitae for Principal Project Scienti s t s

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2.0 SCOPE OF WORK

The scope of work for the Metal Spec ia t ion and Source Characterization s tudy includes the f o l l o w i n gactivities:

3.4.5.6.7.

Selection, handling and distribution of samples for metals analysis and metalsSpeciation.O f f - s i t e laboratory analysis using EPA approved analytical methods to determine totalmetal concentrations and Level III and IV quality assurance documentation comparableto that spec i f i ed in the EPA Contract Laboratory Program (CLP). (For purposes ofthis plan, such o f f - s i t e analyses will be referred to as "Level III and IV analyticaltechniques".)Electron microprobe analysisX-ray d i f f r a c t i o n analysisOptical microscopyLead isotope analysisData validation

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2-1

3 . 0 S E L E C T I O N , H A N D L I N G A N D D I S T R I B U T I O NOF SAMPLES FOR M E T A L SPECIATIONA N D SOURCE C H A R A C T E R I Z A T I O N S T U D I E S

Off- s i t e laboratory analysis and metal speciation will be carried out on s p a t i a l l y representative samplescollected during implementation of the f o l l o w i n g work plans for current investigations at theCali fornia Gulch site:

1. 'Final Work Plan, S o i l s Inves t igat ion, C a l i f o r n i a Gulch CERCLA S i t e , Leadvi l l e ,Colorado" (CDM, 1991).2. "Final Work Plan for S a m p l i n g and Analyses of Lead Occurrence in and Immediate lyAdjacent to Residential Areas" (Dept. of Env. H e a l t h , 1991).3. "Slag Pile Remedial Investigation at C a l i f o r n i a Gulch S i t e , Leadvi l l e , Colorado"(Woodward-Clyde, Inc., 1991a).4. "Mine Waste Pile Remedial Investigation Work Plan, Cal i f ornia Gulch Si t e , Leadville,Colorado" (Woodward-Clyde, Inc., 1991b).5. "Smelter Si t e Invest igation Work Plan, C a l i f o r n i a Gulch S i t e , Leadvi l l e , Colorado"(Woodward-Clyde, Inc., 1991c).6. "Tailing Disposal Area Remedial Investigation Work Plan, C a l i f o r n i a Gulch S i t e ,Leadvil l e , Colorado" (Woodward-Clyde, Inc., 1991d).7. "Soil Investigation Work Plan, C a l i f o r n i a Gulch S t u d y Area, Leadvi l l e , Colorado"(Woodward-Clyde, Inc., 1991).8. "Work Plan for Engineering Evaluation and Cost Analysis, Malta Gulch Tai l ing s ,Leadville , Colorado" (Adrian Brown Consultants, Inc., 1991).

Detailed citations for these plans may be found in the reference section of this document.

Between IS and 25% of all samples collected during implementation of the Final Work Plan, S o i l sInvestigation, and the work plan for S a m p l i n g and Analyses of Lead Occurrence in and ImmediatelyAdjacent to Residential Areas (the "environmental sampling program") will be analyzed by o f f - s i t elaboratories for correlation of results with on-site analytical results (see Section 4.0). Between ISOand 263 of the soils investigation samples collected in the course of the Final Work Plan, S o i l sInvestigation (item 1, cited in the preceding paragraph) and up to and 210 of the environmentalsamples (item 2, preceding paragraph) will be subsequently submitted for determination of metal

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speciation. A minimum of 75 samples collected during the investigations of waste rock pi l e s , tai l ings,slag and smelters (items 3-6, preceding paragraph) will be analyzed by o f f - s i t e metal analysis andsubjected to metal speciation. A maximum of 550 samples will be subjected to metal speciation. Allsamples subjected to metal speciation will be among those sent to an o f f - s i t e laboratory for metalanalysis.

3.1 PROTOCOL FOR S E L E C T I O N . HANDLING AND DISTRIBUTION OF SOILS A M P L E S F O R O F F - S I T E LABORATORY A N A L Y S I S A N D M E T A L S P E C ! A T I O N

This section details the methodology for sample collection, the protocol for sampl ing handling anddistribution and the criteria used for sample selection for metal speciation. Chain-of-custody recordswill be used when submitting all samples to o f f - s i t e laboratories for metal analysis and for metalspeciation.

3.1.1 SOIL S A M P L E S FOR OFF-SITE LABORATORY ANALYSIS

Between 15 and 25 percent of each of the <2 mm and <250 jim soil fractions will be prepared asdepicted in Figure 1 and submitted to o f f - s i t e laboratories for metals analysis for correlation with on-site analytical results. These samples will be selected on the basis of spatial representation. That is,they will be selected to achieve a relatively even dis tribution of sample points throughout the entirearea of the investigation (Final Work Plan, Soi l s Investigation; CDM, 1991; Figure 3-1).

3.1.2 SOIL S A M P L E S FOR M E T A L SPECIATION

To obtain spa t i a l ly representative samples for o f f - s i t e laboratory analysis f rom samples collectedduring the soils investigation, every tenth point within the popula t ed area of the C a l i f o r n i a gulch siteon the 500 foot sampling grid described in the Final Work Plan, S o i l s Inves t igat ion (CDM, 1991;Figure 3-2) will be designated as a site for collection of a sample for metal speciation. Each dep thinterval for each grid point selected will be metal speciated, if that sample meets the selection criteriadescribed below. Figure 1 illustrates the protocol for the handling and distribution of samplescollected under the Final Work Plan, S o i l s Investigation.

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V s p t H1 — — - ^ — ' • ' 1 Remaining Samples unman , T1 ......̂ ^ AUSampIes yEPA FDEEDBASB ARCHIVE

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| XRP SPLTT| S p G tRcnmfuim!U p l O l Q Q If Samples , r !5-25%

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COM SOIL PROCESSING PROTOCOL 1

For the metals speciation program the f o l l o w i n g criteria will be used for selection of samplescollected during implementation of the Final Work Plan, S o i l s Investigation (CDM, 1991):

1. Only samples for the populated area of the C a l i f o r n i a Gulch RI/FS site will be selected,i.e., that area included within the 500-foot sample grid space (CDM, 1991; Figure 3-2).2. Only samples with a concentration of lead greater than 1,000 m g / k g will be selected.3. To meet the objective of selecting metal speciation samples s p a t i a l l y representative of thesite (i.e., evenly distributed), every tenth grid point will be selected as a sample locationfor metal speciation (i.e., all locations that end in a "0"). All "K" series samples(samples that are sp l i t in order to undergo both XRF and o f f - s i t e CLP analysis) andexposure point locations (EP) samples will also be tentatively selected for metalspeciation.4. For source samples (e.g., tailings, waste rock, slag, etc.) that are collected during thesoils investigation (CDM, 1991) sampl ing will be conducted from 0 to 1 inch, 1 to 2inches, 2 to 6 inches, 6 to 12 inches and 12 to 18 inches. Splits proportionate in weightto the thickness of the interval from which they were taken, from each of the f ive depthintervals, will be composited to generate the sample that will be metal speciated. T h i sprocedure is expected to provide a sample representative of both near surface materialsand less weathered materials that may occur to a depth of 18 inches.5. Metal speciation will be conducted on the <250 / t i n fraction.

Using these criteria, it is estimated that 10 percent of all samples collected hi the popu la t ed area ofthe Cali fornia Gulch RI/FS site will be subjected to in-depth metal speciation analysis.

3.2 PROTOCOL FOR S E L E C T I O N . HANDLING AND DISTRIBUTION OFE N V I R O N M E N T A L S A M P L E S F O R O F F - S I T E L A B O R A T O R Y A N A L Y S T S A N DM E T A L S P E C I A T I O N

3.2.1 ENVIRONMENTAL SAMPLES FOR OFF-SITE ANALYSIS

Between 15 and 25 percent s p a t i a l l y representative environmental samples obtained from the"Sampling and Analyses of Lead Occurrence in and Immedia t e ly A d j a c e n t to Residential Areas"(Department of Environmental H e a l t h , 1991) and screened to obtain the <250 /tm fraction will besubjected to o f f - s i t e laboratory metal analysis for correlation with on-site analytical results. Sample swill be selected to achieve even spatial representation of the approx imate ly 300 homes that will be

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sampled under this program. From each of the 45 to 75 homes that are s p a t i a l l y selected, each of theseven matrices that are sampled will be analyzed by o f f - s i t e metal analyses:

1. Attic dust2. Interior household dust3. Exterior house dust (e.g., porch dus t)4. Composited soil sample from the yard5. Street dust6. Interior paint chip sample7. Exterior paint chip sample

Off- s i t e metal analysis is contingent on the avai lab i l i ty of s u f f i c i e n t sample for the analysis. Metalspeciation determination, pursuant' to Section 3.2.2, wil l take precedence, if a l imited amount of anysample is available.

3 .2 .2 ENVIRONMENTAL S A M P L E S FOR M E T A L SPECIATION

Metal speciation of environmental samples will be conducted at 30 homes sampled under the program"Sampling and Analyses of Lead Occurrence in and Immed ia t e ly A d j a c e n t to Residential Areas"(Department of Environmental H e a l t h , 1991). All samples subjected to metal speciation will beamong those sent to an o f f - s i t e laboratory for metal analysis. The homes will be selected on the basisof spatial representativeness of the homes located in the popu la t ed area of the Cal i f o rn ia Gulch RI/FSsite. From each of the 30 homes the f o l l o w i n g seven types of samples will be subjected to metalspeciation as described in Sections 5.0, 6.0, 7.0, 8.0 and 9.0:

1. Att i c dust2. Interior household dust3. Exterior residential dust4. Composited soil sample from the yard5. Street dust

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6. Interior paint chip sample7. Exterior paint chip sample

Metal speciation will be carried out on the <250 /on fraction of the seven sample types, and willonly be performed on samples with a lead concentration of greater than 1,000 mg/kg.

33 PROTOCOL FOR S E L E C T I O N . HANDLING AND DISTRIBUTION OF MINEW A S T E ROCK. T A I L I N G S . S L A G A N D S M E L T E R S A M P L E S F O R O F F - S I T ELABORATORY A N A L Y S I S A N D M E T A L S P E C I A T I O N

Up to 75 samples collected during the sampling of mine waste rock, tail ings, slag, and smelters asdescribed in the previously cited work plans (Woodward-Clyde, Inc., 1991a, b, c & d) will be sent too f f - s i t e laboratories for metal analyses to be correlated with on-site analytical results, as described inSection 4.0, and for metal speciation as described in Sections 5.0, 6.0,7.0, 8.0 and 9.0. Thesamples for o f f - s i t e laboratory analysis and metal speciation will be spa t ia l ly representative of thesampling area and will also be representative of all of the types of mine waste and smelter waste inthe sampling area. The collection, handling and preparation of these samples are described in therespective work plans for these source area types , to be performed by other PRPs under separateOrders. The timing of metal speciation of these samples is contingent upon the timing of receipt ofprepared samples from these other investigations. The <250 /tm fraction will be obtained and a sp l i treserved for electron microprobe analysis, XRD, and optical microscopy. The remaining <250fraction will be ground and submitted for o f f - s i t e chemical analysis and metal speciation by leadisotope analysis and sequential extraction analysis as shown in Figure 2.

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MINE WASTE ROCK T A I L I N G S S L A G S M E L T E R

ANALYSIS PERFORMED AS PER INDIVIDUAL RI PROGRAMS.SPLITS PROVIDED BY PRPs IMPLEMENTING WORK PLAN(S)

Minimum of, r 75 S a m p l e s Minimum ofi r 75 S a m p l e sSCREENED <250 urn(PROVIDED BY OTHER PRP) GROUND S A M P L E S P L I T(PROVIDED BY OTHER PRP)

1M E T A L S P E O A T I O N :• Election Microprobe• XRD• Optical Mineralogy

M E T A L S P E O A T I O N :• Lead Isotopes

A R C H I V E A R C H I V E

C a m p , Dresser & M c K e e Inc.C O M

C A L I F O R N I A G U L C H C E R C L A S I T E S O I L S I N V E S T I G A T I O NO T H E R RI P R O G R A M S

Figure2

7.0 OPTICAL M I C R O S C O P Y

The microscopic investigation of soils, stream sediments, mine waste rock, ta i l ing s , slag, smelterdust, interior household dust, exterior house dust, attic dust and paint chip samples will be conductedby:

AMAX Research & Development Center5950 Mclntyre StreetGolden, Colorado 80403-7499

T h i s work will be under the direction of Mr. Ron Corbet t , Mineralogis t (see A p p e n d i x H forcurriculum vitae for resumes of AMAX Research & Development). All samples submitted for opticalmicroscopy analysis will be accompanied by a chain-of-custody record form. The objective of thiswork is to i d e n t i f y rock-forming minerals, determine morphology, grain size, mineral associations,textures and alteration features. Both transmit ted-l ight microscopic analysis using standardpetrographic procedures and incident-l ight, pol i shed-sect ion analysis will be performed using high-quality research Leitz optical microscopes. The Standard Operating Procedure for the microscopicinvestigation is included hi A p p e n d i x E.

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9.0 DATA VALIDATION

Data validation on the o f f - s i t e laboratory metal analyses will be conducted by:

Camp Dresser & McKee Inc.1331 17th Street, Suite 1200Denver, Colorado 80202Telephone: 303/298-1311FAX: 303/293-8236

9.1 OVERVIEW

The term "data validation" used in the strictest sense refers only to data assessment performedaccording to the procedures set f o r th in the "Laboratory Data V a l i d a t i o n Functional Guidel ines ForEvaluating Inorganic (organic) Analyses" (EPA Doc. No. HQ-8410-01, 1988). Data validationperformed according to the Functional Guide l ine s is a step-by-step process whereby a rigid set ofquality control (QC) requirements is checked against the QC sample results associated with a batch ofanalytical samples. QC samples are analyzed with analytical samples to serve as a means ofquantising the i n s t r u m e n t ' s and m e t h o d o l o g y ' s performance, s t a b i l i t y , and variability. They alsoprovide data to track any biases in the f inal sample data. Calibrat ion standards, calibration checksamples, surrogate and analytical spikes, and performance evaluation standard materials can all beused to assess instrument and method performance. S a m p l e d u p l i c a t e s , matrix spikes and matrixspike duplicates result hi information concerning the precision and accuracy of the methodology aswell as the variability introduced by the sample matrix. Field blanks, travel blanks, and methodblanks are used to pin-point contamination from f i e l d sampl ing , sample transportation and laboratorysources, respectively.

The analyses described hi this work plan are not all standard inorganic analyses performed as part ofthe routine contract laboratory program (CLP). T h e r e f o r e , not all of the standard QC requirements(QC sample types, numbers and control l imi t s) are a p p l i c a b l e to the methodologies to be employedfor metal speciation. The term "data validation" will be used throughout this section to refer to theactivity of reviewing sample and QC data and assessing the data's quality and usability. However, itis understood that the guidelines for data val idat ion will be developed and be unique to the particularanalytical method and the intended uses of the data.

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Determination of appropriate control limits for QC samples associated with the various analysesspec i f i ed in this work plan is not a clearly d e f i n e d process. W h i l e the control l imi t s for the Level mand IV metal analyses can either be taken dire c t ly from the Funct ional Guide l ine s or modi f i ed basedon the Functional Guidel ines , the remaining analyses (electron microprobe, X-ray d i f f r a c t i o n , opticalmicroscopy, and lead isotope analysis) will necessitate the development of a QC scheme thataddresses the spe c i f i c methodology. One approach may be to per form a statistical analysis on eachset of QC samples. Values which fall within the 95 percent confidence level would be considered tobe acceptable (within control l imit s) and values outside the range would require some qual i f i ca t ion ofthe data.

The data validation for the o f f - s i t e laboratory metal analyses will be performed by Camp Dresser andMcKee Inc. (CDM) and a subcontractor to CDM that will be determined. The subcontractor will bef u l l y qual i f i ed in the areas of concern.

The level of data validation to be performed on the o f f - s i t e laboratory metal analyses as well as theextent of validation that will occur has not yet been determined. All of the laboratories, regardless ofthe analytical methodology, will be required to submit s u f f i c i e n t documentation of the actualprocedures, calculations, results, QC activities and suppor t ing raw data for an evaluation of the data'squality and usability to be completed.

9.2 M E T A L ANALYSES BY OFF-SITE L A B O R A T O R I E S

The work will be carried out hi accordance with the Contract Laboratory Program (CLP) Statement ofWork (SOW) 7/88. It is understood that Roy F. Weston (EPA's contractor) will be per forming datavalidation on these data. In the event that EPA's data va l ida t i on cannot be completed within thetimeframe necessary for preparation of the f inal report of this investigation, CDM will perform anoversight data validation. T h i s data val idat ion process may range from an electronic screening of thedata for QC violations and an assessment of their a c c e p t a b i l i t y in consideration of the samplematrices, to a validation performed in strict accordance with the Functional Guidelines.

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9.3 ELECTRON MTCROPROBE ANALYSIS

The accuracy of the electron microprobe analysis is monitored by checking the magnification barusing a micrometer scale. A calibration is performed prior to each analytical run. Precision isdetermined from the random variation in the calibration samples. A check standard will be analyzedonce a month as an internal laboratory check. The results of activities may be veri f ied during datavalidation. Consistency of the results with the stated procedures may be assessed as part ofvalidation.

9.4 X-RAY DIFFRACTION

The X-ray d i f f r a c t i o n data may be reviewed to ensure that the sample preparation and analyticalprocedures were carried out as sp e c i f i ed in the SOP. The raw data may be checked for calculationsand consistency with the f inal reported results.

9.5 OPTICAL M I C R O S C O P Y

Optical microscopy does not lend i t s e l f to quali ty control samples. The f inal data report may beassessed for consistency with the SOPs.

9.6 LEAD I S O T O P E ANALYSIS

The final report may be reviewed for consistency with the SOP. Each set of eight samples analyzedwill have an associated blank and standard sample. Contamination from sources other man sampleswill be monitored by the blank. Precision, r e p r o d u c i b i l i t y and accuracy are monitored by thestandard. Fractionation-corrected standard value deviations > 0.5 percent are considered to be out ofcontrol. All calculations may be checked during the va l ida t i on process.

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10.0 PRINCIPAL SCIENTISTS

Each element of the metal speciation program will be directed by a principal scientist. Thecurriculum vitae of these scientists are included in A p p e n d i x H. The resumes of other scientists thatwill participate in implementation of this work plan are also included hi A p p e n d i x H.

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APPENDIX CSTANDARD OPERATING PLAN AND QUALITY CONTROL FOR ELECTRON

MICROPROBE A N A L Y S I S B Y S U R F A C E S C I E N C E W E S T E R , T H E S U R F A C E S C I E N C ELABORATORY, THE UNIVERSITY OF W E S T E R N ONTARIO

263VCA O U L C H \ M C T A L S P E C \ A P P E N D . T X T08/01/91 mlb

SPECIAT10N OF LEADI N S O I L , I N T E R I O R H O U S E H O L D D U S T , E X T E R I O R H O U S E D U S T ,A T T I C D U S T , S T R E E T O U S T , F L U E D U S T , M I N E W A S T E , T A I L I N G SA N D S L A G S A M P L E S B Y ELECTRON M1CROBEAM T E C H N I Q U E S

1. OBJECTIVEThe objective of this work Is to Identify the lead species, their size and associationand attempt a lead mineralogies! distribution in camples of soil, intertori householddust, exterior house dust, attic dust, street dust, f l u e dust, mine waste rQck, ta i l ingsand slag using electron mlcrobeam techniques.

2 . S A M P L E S A N D S C H E D U L EThe maximum anticipated number of samples is 550 and the tima. frame forcompletion of the study te 6 • 6 months.

3 . I N S T R U M E N T A T I O NIn order to analyze the quoted nurnber of samples within the sp e cMled l t ime frameit Is proposed to use the f o l l o w i n g three instruments:(a) Scanning electron microscope (ISIDS-130) equipped with l ight element EDSdetector (Tracor Northern Z/MAX/30), TN-5500 data procesang systemwith image processing software, and a Robinson backscatterfcd electrondetector. This instrument is located at the S u r f a c e Science Westernlaboratory.(b) Electron microprobe (JEOL 8600) equipped with four Wavelengthspectrometers, EDS detector and the TN-5600 data processingRystem. ALDEC crystal for C and a LDE1 crystal for O analyses will be Used. Thisequipment is located in the University of Western Ontario Department ofGeology.(c) Electron microprobe (JEOL 733) equipped with four Wavelengthspectrometers, EDS detector, controlled by TN-5500 and TM5600 dataprocessing systems and image analyzer with TN-850Q series f o f tware . ALDEC crystal for C end a LDE1 crystal for O analyses win be used. Thisequipment is located at the Mineral Sciences Laboratories, Canada Centrefor Mineral and Energy Technology (CANMET), Ottawa.

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4. M E T H O D O L O G Y

4.1 S a m l e P r e a r a t i o nThe minus 250 pm size fract ion of soil, interior household dust, exterior housedust, attic dust, street dust, mine waste rock, tai l ings and slag sarriples, eachweighing not more than 5 grams, will be received for lead spedatton. The 250 pmsize c u t o f f was selected because this particle eize reportedly sticks to children'shands, becoming more readily available for ingestton (Bomscneln, R.U., personalcommunication) and thus represents a potential health hazard. Grain mounts, oneinch in diameter, of each sample will be prepared using air-cured epoxy The grainmounting procedure involves: (a) covering with releasing agent (ebehler) thep l e x i g l a s s surface used as base and the t e f l o n rings, (b) using vas t f ine on theTeflon base to prevent leakage of the epoxy resin, (c) placing 0,1 • 0.2 g of thesample In each "mold", (d) pouring the epoxy into the mount, (e) gent ly 1 mixing thesample and the epoxy with a toothpick to cover the entire base and then (f) curingfor 12 - 18 hours. The mounts then are ground with 1000 grit silicon carbide,sonicated in methanol and mechanically polished on paper cloth using 6, 3 and 1Mm diamond paste (Hyprez Diamond Compounds). Each mount wV! contain apiece of standardized cerussite obtained from the Geological Survey of Canada orother sources of cert i f ied standards. A blank mount and a duplicate mfcunt will beprepared for every twenty mounts to check for contamination during samplepreparation and for precision. The samples will be carbon coated for) analysis.Airborne part iculate samples are much smaller In volume end particle fifee, Theywill be provided on air-f i l ters . The sample preparation procedure is morecomplicated, end will have to be worked out. Alternative preparation schemesunder consideration are: (a) impregnation of f l a t - l y i n g loaded air-fitters with epoxy,air-curing, increasing thickness by adding more epoxy resin to produce a block,which, a f t e r curing, is polished with one micron diamond paste only; (b)emplacement of airborne particulates on Indium foil by bringing in Contact theloaded air-fitter with the indium foil. Indium is a pre f erab l e substrate to f e t i cky tapebecause tt is conductive, thus eliminating the Hying' of the particles wtien placedunder the electron beam, even af t e r carbon coating. I n d i u m is particularly suitablefor this as it possesses "sticky* qualities.Three pol i shed mounts containing a 1 • 2 mm crystal of each galena angles l te ,cerussite and pos s ib ly plumbobarite (if homogeneous) will be p r e p a r e d j t o be usedas In-house secondary standards.

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4,2 A n a l y t i c a l Procedure and Data PresentationThe analytical procedure will vary s l igh t ly with the Instrument used '•• scanningelectron microscope (SEM) and electron microprobe (EPMA) - to matfmize eachi n s t r u m e n t ' s capabilities. Quality control will be maintained by analyzing at regularintervals three f l o a t i n g standards (see next section).The backscattered electron images will be examined using two settings: one forllght-element-dominated matrices (slag-phases) and the second for heavy-element-dominated matrices (galena, ang l e s f t e , etc.) Thus, no Pb-carrier minerals will bemissed or mislabelled during the scanning of the polished grain mpunt. Thescanning will be done manually. Typically the magnif icat ion used for scanning allsamples except for airborne samples will be 40 - 50X and 400 - $OOX. Forairborne samples the magnification used for searching Pb-carrter; phases isexpected to be a maximum of 1000X. Once a candidate particle Is Identified, thenthe backscattered image will be optimized to discriminate any d i f f e r e n t phases thatmay be maklng-up the particle. I d e n t i f i c a t i o n of the Pb-bearing phases will bedone by WDS, end in the case of the electron probes, the spectrometers peakedat s, Pb, O and C, or by EDS In the case of SEM. The £iz§ of eacn Pb-carrierphase wDl be determined by measuring In jim the longest dimension. If areameasurements are made using Image analysis software, the longest dimension willbe obtained from the automated area measurement. A maximum of f hours willbe spent in scanning end analyzing each mount. For samples with abundant Pb-carrier phases It is expected that less time will be spent.Quantitative analyses are required to establish the average Pb conterv of the Pb-carrying minerals, which have variable Pb content as: jaro s l t e , f e rr t t e , barite endthe slag grains. These determinations are important e sp e c ia l ly In the case of s lagswhich are expected to nave considerable variation In their dissolved PD content.Results will be analyzed s tat i s t i cal ly to establish mean values and the confidenceinterval of the mean at the 85% significance level. They win also be deple t ed ashistograms to show the range of Pb concentrations measured as \jvetl as thepresence of one or more populations in terms of Pb content In the latter casenon-parametric statistics may have to be used or the median value, has to beestablished.The association of the Pb carrier phases wilt be established from the badkscatteredelectron images. Particular attention will be paid in e s tabl i shing whether the grainsare to ta l ly enclosed, encapsulated or liberated. The rinds on Pb-carrier grains willbe Identified. Representative photographs es tablishing the association of theprincipal Pb-carriers will be obtained for demonstration purposes. In bddl t ion, aqualitative assessment of the association of the principal Pb carriers w^ be madeon the sample proforma sheets (attached).

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As described earlier, the longest dimension will be measured Indistribution of the principal Pb carrier for each sample analyzed will be Thedepicted Ina histogram. The abundance of each Pb carrier tor every sample will t e depic tedin the form of a bargreph.If the laboratory performing the electron mteroprobe analysis Is papable ofcalculating the area proportion and If the client wishes to have the information fordata Interpretation, the area proportion,, which is obtained from the areameasurement, win be calculated for each Pb carrier phase. The voluma proportionwin be established assuming unit depth. From ft the mass proportbns will bedetermined using sp e c i f i c gravity for each mineral. The area prpporton Isequivalent to the volumetric proportion of the mineral in the bulk samppe providedthat: (a) the total of measured areas Is much larger than Indiv idua l grains of theminerals and, (b) a s tat i s t ical ly adequate number of grains were measured (Jones,1987). The latter can be checked by determining me variation in the massproportions calculated based on 250 and 500 Pb-carrler mineral occurrences in afew control samples.From the mass proportion and the Pb concentration of each Pb-carrier (Mineral, thePb mlneralocilcal distribution will be established.During the scanning of each polished grain mount the presence or absence of Hgend AS species win be noted. These observations are of qualitative nature only.

4.3 Quality ControlThe accuracy of area measurements will be controlled Dy crocking themagnification bar. The magnification bar Is checked against a calibration standard.The JEOL 733 possesses an internal calibration standard. The calibration of theEDS will be checked at the beginning or each analytical session by analyzing a setof minerals comprised of galena, anglesite, cerussite, and pos s ibly barfce obtainedfrom The Geological Survey of Canada. Three polished mounts containing thesephases win be prepared and analyzed in the three fac i l i t i e s . The rendOfn variationIn the data acquired will establish the precision of the electron probe analysis. ForEDS analysis the M f ine s will be used for Pb, the K lines for S, C, O fljjnd P. Thestrong overlap of the Ka S Bne with the M lines of Pb will be resolved by spectrumdeconvolution. The quality of the deconvolution can easily be checked byanalyzing galena. For the bulk of the EDS analyses the S$ndard!essQuantification (SO) program of Tracer Northern will be used.

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in the case of the electron mlcroprobe, the wavelength spectrometers will bepeaked-up d a l l y for Pb, O, C and S using angles t t e and cerussfte. For WDSanalysis crystals and x-ray lines will be selected based on their sensitivity andminimal interference from overlapping lines. As h the case of the EOS analyses,the precision will be checked by analyzing the standards daily. Every effort will bemade to select homogenous mineral grains to be used as secondary standards.Cert i f i ed pure element standards will be used.In order to maintain an internal check between the three fac i l i t i e s , Jthree blindstandards representative of the samples analyzed wilt be analyzed 6t regularIntervals by each laboratory. The Intervals at the beginning will b? every twoweeks, then once a month. This round Robin analyses will ensure lh$t the samequality results are produced by the three fac i l i t i e s .

4.3.1 Error Analysis iIn the characterization of the soils and other samples three sources of &ror shouldbe considered:(a) Errors In the quantitative mlcroprobe analysis by EDS or WD^ of the Pb-carrier minerals.(b) Errors in the measurement of the relative proportions of th* Pb-carrierminerals.(c) Loss of mineral during sample preparation.Errors in the quantitative microprobe analysis may result from analyzing: (a) smallgrains where the volume of X-ray excitation is larger than the volume of the grainitself, (b) phases that are unstable under the electron beam, and (c) carbonate-bearing phases because of the use of carbon coating. These errors, however, areconsidered of minor importance in the case of Pb minerals, because Of the minorvariation in their Pb content and because the primary objective Is to i d e n t i f y the Pbminerals. In the case of Pb-containlng minerals (variable Pb content) cautionshould be exercised because here the objective Is to obtain an accurate measureof their Pb content. In the case of e lag phases, because of the extended periodof operation of the Pb smelters (1670 -1960) with possible variation jn smelt ingpractices, considerable variation In the Pb content of these phases may occur, inaddition, the complication from remnant PbS and PbxOy Inclusions should betaken into consideration e spec ia l ly when analyzing old slag grains.

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The error In establishing the relative proportions of the Pb-carrier minerals In eachsample Is anticipated to be the most s ignif icant, e specially In the case of sampleswith a large range of par t ld e sizes and limited number of Pb-carrier mineral grains.However, when considering groups of samples, because of the larger number ofoccurrences, the errors will be s igni f i cant ly reduced, permit t ing meaningful ends tat i s t i cal ly sound comparisons to be performed.Preparation of polished grain mounts may result in the loss of some very f i n e ,loosely-bound, Pb-carrier minerals.6. R E F E R E N C E S

Jones, M.P. (1987). Applied Mineralogy: A Quantitative Approach. Graham& Trotman, Oxford 259 p.

APPENDIX ESTANDARD OPERATING PLAN FOR OPTICAL M I C R O S C O P Y ANALYSIS BYAMAX RESEARCH & DEVELOPMENT CENTER.

363WA OULOnMCTAL IPEC\APFEND.TXTWOW! aJh

AMAX Research & Development Center5950 Mclntyre StreetGolden, CO 80403-7499

S T A N D A R D O P E R A T I N G PROCEDUREMICROSCOPIC INVESTIGATION OF LEAD-BEARING SAMPLESC A L I F O R N I A G U L C H S I T E , L E A D V I L L E , COLORADO

As part of a characterization study to determine the mode of occurrence of toxic elements, mere is arequirement for a study of the mineralogical composition of these samples by means of opticalmicroscopy. The results of this mineralogical analysis would be incorporated in the overall study toallow interpretation of other analyses including XRF, electron microprobe and other analyses relativeto the mode of occurrence of the toxic metals.For this investigation, we would propose to prepare separate thin and polished sections from thesesamples for transmitted- and incident-light microscopic analysis.In the transmitted-light microscopic analysis, the transparent and translucent (i.e., rock-forming)minerals would be id en t i f i ed by standard petrographic procedures. Included would be a modalanalysis in volume percent and a description of the individual components with their texturalcharacteristics and pertinent alteration features.In the incident-light polished-section analysis, the opaque or metal l i c minerals, such as oxides,s u l f i d e s , s u l f o s a l t s , and native elements, would be id en t i f i ed and characterized with respect to gramsize, mineral associations, textures, alteration features, etc.The procedures for section preparation are standard and involve vacuum impregnation with epoxyf o l l owed by grinding to a thickness of 30 microns for the thin sections and preparation of one-inch-diameter polished sections.Examination would be performed with high-quality research optical microscopes.Data would be transmitted intermittently as it becomes available.

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APPENDIX GC U R R I C U L U M V T T A E F O R P R I N C I P A L PROJECT S C I E N T I S T S

9SnCA OULCMMErAL IPECVAPPEND.TXTwroim nib

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N E W M O N T M I N I N G C O R P O R A T I O N

Ronald K. Cor f c e t tMineralogi s tE D U C A T I O N 1973-1974 C r y s t a l l o g r a p h y and Minera l ogy ,Virginia polytechnic inst i tute 4 stateUnivereity, aiacksburg, VA.

1972 K.S.i Oeoiogy, Universi ty o f A r i t o n a ,A Z .1976 B . f i . r H i g h Die t ine t i en , G e o l o g y , ColoradoS t a t e Univer s i ty , Fort C o l l i n t , CO.1987 - praaant Research S c i e n t i s t , AKAX RtDCenter, G o l d e n , CO. A p p l i e d raaaaroh inmineralogy and aaterial s ar.alyiia by &aana of xray d i f f r a c t i o n , l i gh t microscopy, alaetronn l c r o « c o p y / t t i c T o p r o b a and othar nathoda.

P R O F E S S I O N A LE X P E R I E N C E

1964-66 f ianior Standard! Enginaar,I n t a m a t i o n a l , o o ldan, CO. Praparation andc a r t l f i c a t i o n ef i s o t ep l c atandarda. Gaama rayepaetroaeopy. Davelopntnt and vodi£ieation efcomputer a o f t w t r a for oaaaa *ptc tro6copy,a ta t ia t i ea l analyait of d a t a r and p l o t t a routput * u t i l i s ing FORTRAN and &ASZC languagai .1975-83 Sanior Pro j act K l n t r a l o g i a t , C o l o r a d oSchool of K i n a a Resaarch Z n a t i t u t a r O o l d t n , CO.A p p l i a d raaaarch in catariala analyaia. Charac-taricat i en ef a wida variaty of aatariala bymeans ef x-ray d i f f r a c t i o n and f l u o r a t c a n o a ,tharaegraviaatrio analyaia, l ight Bioroaeopy,aeanning alaetron e i cro ioopy, and alaetront t icroprebe analyaii. spiolnl anphaaia en oraaof precieua and baaa m t t t l t and on haavy ainaralacEeioblagaa. T o t a l p r o j a c t ra»pvn«ibil i tLaa,inc luding writing ef p r o p o s a l a, conductingravaarcht integrating rasulta, and preparingreporta and oral pra i en ta t l ona .

A C C O H P U 6 H H E K T SAND HONORS Konora graduata of Colorado S t a t e University.Honor S o c i e t y o f P h i K a p p a P h i ( C S I L / I f i 7 0 ) ."outstanding f ianior in ecology" (CSV, 1970) «Research socie ty o f Bigaa XI (U, o f A r i t . ,1 6 7 2 ) . N S F Graduat e T r a i n a t f h i p a ( v . o f Aria . ,1970-72 and Va. Polyteen Znat . 1973-74).Nuneroui aeholarahipa.

P. 02

0 & C A N X Z J & I O N 5 Antrioan A t a o c i a t i o n o f Patrolaua Oto l og i s t s .Anarican X n t t i t u t a of Mining Snginaar t , Anarioaif i o e ia ty f o r K a t a l t .U . K . , i » l t , L i i u i t l i i v F 4 * t 6 1 ' * f * l 'd i f f r a c t i o n in tha G a n d o l f i x-ray cantra- AD i t e u t f i o n i Povdar D i f f r a c t i o n . I n p r a f i f i .

C o r b a t t j U . K . , 1979, A p p l i c a t i o n * o f thaO a n d o l f i x»ray eaaara In »ln»ral» industryraiaaroht in McCarthy, G . J . , at. al., «dX d v a n e e i i in ^̂ pv X n f t l v « t « . v. 82, PlanUp. 301-206.H & u n i i o w , A.W., xrauae, J . B . , and cerbatt, R.K. ,19 T 6 , Kul t i o oaponan t uixturas — If x-rayd i f f r a c t i o n adaquata? ( a b t t . i t £&f i&f i r 3rd Ann.Hovaobar 1 S 7 6 , t h i l a d a l p h i a .Corbet t , R . K . , 197 J, X-ray "pevdar" data forOhal eophy l l i t a t f^ay. Hinara l . . v. 58, p. 792-93.B i n f l h , K . W i i Corbt t t i R.K«. K c L t a n , H t J n t n dZiaughon, R , B , , 1978, Tha crystal struetura oft i l a t i t a t A«oj> Minaral . . v, 57, p. 1680-84.Corbat t , U . K . , 1978, X Rtthod for obtaining x--le crystal*e f f & i a n c c . .ray "powder photograph!" from t i n g l e crystal*( a b t t « ) t J o u r , e f the X r i t . Aead. e16th Ann. M t g M v. 7, p. 48.