J.07_20030605_Lead_ _Arsenic_in_El_Paso_Soils_-_EPA_Drexler_Rpt.pdf

A STUDY ON

THE SOURCE OF ANOMALOUS LEAD and ARSENIC CONCENTRATIONS IN SOILS FROM THE El PASO COMMUNITY--- El PASO, TEXAS.

June 5, 2003

FOR

ENVIRONMENTAL PROTECTION AGENCY

BY

DR. JOHN W. DREXLER

LABORATORY FOR ENVIRONMENTAL AND GEOLOGICAL STUDIES

UNIVERSITY OF COLORADO

BOULDER, CO. 80309

TABLE OF CONTENTS

1.0 Introduction

2.0 Historical and Geological Background

3.0 Lead and Arsenic Geochemistry

4.0 Speciation

Methodology

Sample Preparation

Point Counting

Precision and Accuracy

Plant Soils

Community Soils

Statistical Study–Correlation Analysis

5.0 Lead Isotopic Characterization………………………………………………..47

6.0 Apportionment

7.0 Further Studies

8.0 Conclusions

9.0 References

Tables

Table 1 Common Lead and Arsenic Sources

Table 2 Study Samples..........................................................................................14-15

Table 3 Summary Speciation of Plant .................................................................24-26

Table 4 Summary Speciation of Residential Soils...............................................30-40

Table 5 Plant Lead Correlation Matrix

Table 6 Soil Lead Correlation Matrix .................................................................46-47

Table 7 Lead Apportionment for El Paso Community Soils...............................54-55

Table 8 Arsenic Apportionment for El Paso Community Soils..........................56-57

Figures

Figure 1 El Paso Study Location Map

Figure 2 Summary of Plant-site Speciation

Figure 3 Plant-site Grain-Size Distribution

Figure 4 Summary of Community Soil Speciation

Figure 5. Summary of Community Soils Grain-Size Distribution

Figure 6. Spatial Distribution of Relative Lead Mass......................................Disk

Figure 7. Spatial Distribution of Relative Arsenic Mass......................................Disk

Figure 8. Lead isotopic variations……………………………………………

ABBREVIATIONS

EMPA Electron Microprobe Analysis

EDS Energy Dispersive Spectrometer

SOP Standard Operating Procedure

BSPM Backscatter photomicrograph

Galena (PbS)

Cerussite (PbCO3)

Anglesite (PbSO4)

Sulfosalts ( enargite- Cu3AsS4; tetrahedrite- Cu12Sb4S13; tennantite- Cu12As4S13; bournonite-

PbCuSbS3; and jamesonite-Pb4FeSb6S14)

1.0 INTRODUCTION

The purpose of this study was to characterize the lead and arsenic mineralogy within the El Paso community soils and more specifically the source(s) of the anomalously high (121-1143 mg/kg) lead and (14-192 mg/kg) arsenic concentrations found in the community. Samples were acquired from the ASARCO (1889-present) facility in El Paso, in addition to those collected by

WESTON from the surrounding community. Although the ASARCO facility was not the only smelter to operate in the El Paso community, it was the largest and had the greatest longevity.

The International Smelter operated from 1888-1894 and the Federal smelter operated from 1901-

1904. A site map, with sample locations and selected demographics is provided in Figure 1.

Environmental concerns pertaining to plant discharges began in the early 1920's with various private and city disputes concerning damages to crops and health from excessive smoke releases.

In the early 1970's more aggressive action by the city of El Paso and the state of Texas was undertaken to control air pollution from the facility. During these investigations it was concluded that the ASARCO smelter emitted approximately 1,000 tons of lead, 500 tons of zinc, 10 tons of cadmium and 1 ton of arsenic to the surrounding area over a three year period (People vs

ASARCO, 1971 and Carnow et al., 1973). As a direct result of this litigation ASARCO completed a $90 million dollar renovation to the facility in 1979 to improve emission quality.

However, as recently as 1990, data from the State of Texas indicate that 96 tons of lead per year

(from the ore and fluid beds) and 29 tons of arsenic per year (from the copper stack) are still being emitted from the facility. These modern, measured releases could only pale in comparison to historic releases during the facilities 100+ years of operation.

Fig1

2.0 HISTORICAL and GEOLOGICAL BACKGROUND

History

The El Paso Smelter, was constructed in 1887 as the Consolidated Kansas City Smelting and

Refining Company. In 1899 it became part of the newly formed American Smelting and

Refining Company (ASARCO). It was originally built to process the rich, lead ores from the

West, but was later (1910) expanded by adding a copper circuit, primarily for Arizona ores.

Later in 1930's ~1950, and 1970's facilities were added for cadmium, zinc, and antimony, respectively.

The lead facility originally consisted of a 100 foot wooden stack and six blast furnaces with associated sintering ( 4 roasters ) capacity to handle some 225,000 tons of charge per year. After the 1902 fire, seven lead furnaces were constructed along with a new 400 foot stack. The lead plant was closed in 1985. (Hydrometrics, 2001)

The copper facility consisted of four Herreshoff roasters, one reverberatory furnace, and three

Peirce-Smith converters. Roaster and reverberatory gases are eliminated from a 828 foot stack and the converter gases discharge from a 100 foot stack. Baghouses and electrostatic precipitators (devices used to minimize stack emissions) were introduced to the facility in the early 1900's to limit the loss of metal from fumes. Annual production produced 110,000 tons of anode copper.

In the early 1930's a Godfrey roaster was added for cadmium production and in the 1970's an antimony plant was added.

In 1947 a zinc fuming facility, to treat slags, was added to handle the elevated concentrations of zinc ( up to 10 percent Zn) which were being produced when smelting the New Mexico ores.

The furnace treated 20,000 tons of slag per month. In early 1950's a new 600 foot stack was built to handle the lead and zinc facilities.

In the mid 1980's the antimony plants closed followed by a closing of the zinc and cadmium plants in 1992. The smelter still operates its copper (CONTOP) facility which was added in

1993. The plant has been on a mandatory three-year care and maintenance since 1999.

Geology:

El Paso lies the extreme western tip of Texas, within the southern part of the Basin and Range province. The south-east flowing Rio Grande River marks the southern limits of the city and the international boundary between the United States and Mexico. The climate is arid, with annual precipitation averaging only 9 inches. The prevailing winds are westerly, with dust storms a common occurrence in the early months of the year.

The metropolitan area of El Paso lies primarily within the floodplain of the Rio Grande River, once dominated by a large lake bed (Lake Cabeza de Vaca). Millions of years of river deposition resulted in a complex sedimentary sequence of gravel, silt, clay, and sand called the Fort

Hancock Formation, accumulating to a thickness of more than 9,000 feet. Recent geological activity has been dominated by Basin and Range tectonics and the emplacement of young, 40,000 year old, basalt flows and cinder cones from the Potrillo Volcanic field. There is nothing in the geological record that could account for the elevated metal (Pb, As, Cu, Cd, Zn) concentration found in the residential soils.

For decades, preceding the construction of dams on the Elephant Butte and Caballo lakes in

1916, spring flood waters would move onto the downtown area of El Paso.

3.0 LEAD and ARSENIC GEOCHEMISTRY

Arsenic is found in many minerals and is typically enriched in soils originating from shales/schists and argillaceous sediments. Lead on the other had is more commonly concentrated in silicic magmatic rocks and argillaceous sediments. Uncontaminated soils have mean concentrations of 1-6 mg/kg for arsenic and 3-19 for lead (Fergusson, 1990), worldwide.

The lowest levels are typically found in soils derived from volcanic or carbonate terrain, as are those in the El Paso area ( volcanics and limestones), and average 1-7 mg/kg As and 3-14 mg/kg

Pb. The arid climate in the El Paso area along with the near neutral (6-8.5 pH) acidity of the local soils stimulate very low metal mobility, generally concentrating metals in the surface horizons by preventing there downward distribution over time. Mobility may be enhanced by irrigation, aeration, or by utilization of soil amendments ( Logan and Chaney, 1983).

Numerous sources of lead and/or arsenic can produce elevated concentrations in surface soils.

Table 1 is a compilation of the most common sources, their speciation, along with associated soil concentrations (data from Barzi et al., 1996, Kabata and Pendias, 1993; Fergusson, 1990;

and Drexler, per. communication, 1998).

Table 1. Compilation of common lead and arsenic sources and associated soil-metal concentrations.

Source Arsenic Speciation Associated Soils

As mg/kg

Lead Speciation Associated Soils

Pb mg/kg

Paint Pigments PbCO3, PbSO4 , PbO, PbCrO4 100-900

Mining Sulfosalts, As2S3, FeAsS 23-1023 Sulfosalts, PbS, PbCO3, PbSO4 100-96,000

Chemical Works PbAsO, As2O3 ,R**AsO 10-2000 PbAsO, Pb, PbSO4 100-600

Metal Processing As2O3, AsM*O, PbAsO 33-2500 PbM*O, PbAsO , PbO, FePbO, PbCO3, Slag, PbCl4

100-12,000

Application of Pesticides As2O3, PbAsO, R**AsO, Na-Ca arsenates

38-625 PbAsO, 200-2500

Gardens and orchards PbAsO 38-892 PbAsO 200-2500

Fly Ash Unknown 1-9

Municipal Sludge Unknown 1-6 80-7400

Sheep/Cattle Dip/Tannery As2O3, Na-Ca arsenates 300-1000

Wood Preservatives Cr-Cu arsenates 10-2000

**R = Organic compounds, *M = typically Pb, Ca, Cd, Zn, or Sb.

4.0 SPECIATION

Seven samples from the ASARCO facility and twenty-eight samples from the surrounding community (Table 2.) were speciated for lead and arsenic using electron microprobe (EMPA) techniques. Methodologies used for sample preparation, data collection, and data synthesis are described below.

Table 2.0 Speciation sample set.

Cu L ab No. Source Cu mg/kg

Zn mg/kg

As mg/kg

Se mg/kg

Cd mg/kg

Sb mg/kg

Pb mg/kg

EL P-1 Front Y ard 518 656 74 1.0 22 1.0 1084

EL P-2 Front Y ard 379 464 52 ND 14 1.0 448

EL P-3 Front Y ard 189 313 66 1.0 6 1.0 236

EL P-4 Front Y ard 732 712 60 8.9 22 3.7 979

EL P-5 Back Yard 396 496

0.5 11 1.2 400

EL P-6 Front Y ard 812 782 59 2.2 27 2.4 789

EL P-7 Front Y ard 108 226 17 1.2 3 ND 164

EL P-8 Front Y ard 58 229 47 ND 2 1.0 109

EL P-9 Front Y ard 931 1038 71 ND 24 2.0 892

ELP -10 Front Y ard 802 855 57 0.7 24 2.1 1151

ELP -11 Drip Line 666 559 63 1.6 20 2.0 1046

ELP -12 Back Yard 158 317 12 ND 6 1.0 328

ELP -13 Front Y ard 3797 1137 73 ND 21 7.0 939

ELP -14 Front Y ard 832 685 60 1.0 18 1.8 1031

ELP -15 Back Yard 568 611 29 ND 20 1.1 754

ELP -16 Front Y ard 556 610 97 ND 21 1.5 756

ELP -17 Front Y ard 468 468 38 ND 17 0.6 768

ELP -18 Front Y ard 536 1061 98 11.0 9 3.1 515

ELP -19 Front Y ard 286 860 186 1.6 11 1.8 488

ELP -20 Back Yard 838 770 44 ND 30 2.3 1046

ELP -21 Back Yard 551 718 40 ND 17 1.3 831

ELP -22 Front Y ard 321 398 33 ND 11 1.0 408

ELP -30 Front Yard 192 591 14 ND 6 ND 407

ELP -31 Front Yard 213 305 12 ND 6 ND 316

ELP -32 Front Yard 52 98 8 ND 1 ND 108

ELP -33 Front Yard 141 262 13 ND 5 ND 1785

TM Distal Yard 27 29 4 ND 1 1.0 46

Z-1 Distal Yard 52 169 39 ND 1 1.0 53

Sample ID. Cu L ab

No.

Source Cu mg/kg

Zn mg/kg

As mg/kg

Se mg/kg

Cd mg/kg

Sb mg/kg

Pb mg/kg

9600-55-00 ELP -23 Plant 334951 8612 4795 9031 393 773 8244

9605-55-00 ELP -24 Plant 5709 2936 602 16.0 167 15.0 6122

9606-55-00 ELP -25 Plant 183576 67918 24854 11590 6523 1210 9973

9603-55-00 ELP -26 Plant 12198 18643 400 12.0 25 16.0 3397

9602-55-00 ELP -27 Plant 15394 21418 365 11.0 22 19.0 1996

9604-55-00 ELP -28 Plant 1514 729 180 2.0 35 4.0 1312

9601-55-00 ELP -29 Plant 11053 2144 307 8.0 68 13.0 858

4.01 Methodology

Metal speciation was conducted on a JEOL 8600 electron microprobe (EMPA), operating at

15Kv (accelerating voltage) and 15-20 nanoAmps current, at the Laboratory for Geological

Studies at the University of Colorado following the laboratory’s SOP. For a complete description of the methodology a copy of the SOP is available at our website:

htpp://www.colorado.edu/GeolSci/legs

One exception was made in the SOP, in that the samples were not sieved to <250 Fm, as is most common for bioavailability determinations, but the 2mm fraction was used in order to be consistent with previous site studies. The samples were all air dried and prepared for speciation analysis as outlined in the SOP. A combination of both an Energy Dispersive Spectrometer

(EDS) and a Wavelength Dispersive Spectrometer (WDS) were used to collect x-ray spectra and determine elemental concentrations on observed mineral phases. All quantitative analyses are based on certified mineral and metal standards using a Phi Rho Z correction procedure.

Representative backscatter photomicrographs (BSPM) illustrating sample characteristics were acquired.

Data from EMPA will be summarized using three methods. The first method is the determination of FREQUENCY OF OCCURRENCE (F). This is calculated by summing the longest dimension of all the lead or arsenic-bearing phases observed during the point counting and then dividing each phase by the total length for all phases.

Equation 1.0 will serve as an example of how to calculate the frequency of occurrence for an arsenic- bearing compound, lead-bearing particles are handled in a similar manner.

FAs - Frequency of occurrence of arsenic in a single phase.

PLD - An individual particle’s longest dimension

3 (PLD) phase-1

FAs in phase-1 = ______________________________ Eq. 1.0

3 (PLD)phase-1 + 3 (PLD)phase-2 + 3 (PLD)phase-n

%FAs in phase-1 = FAs in phase-1 * 100

Thus, the frequency of occurrence of arsenic in each phase (FAs) is calculated by summing the longest dimension of all particles observed for that phase and then dividing each phase by the total of the longest dimensions for all phases. The data generated thus illustrate which arsenic-bearing phase(s) are the most commonly observed in the sample or relative volume percent.

The second calculation used in this report determines the RELATIVE MASS ARSENIC (RMAs) in a phase.

3 (MAs.) phase-1

RMAs in phase-1 = ______________________________ Eq. 2.0

3 (MAs. )phase-1 + 3 (MAs. )phase-2 + 3 (MAs. )phase-n

%RMAs in phase-1 = RMAs in phase-1 * 100

MAs - Mass of arsenic in a phase SG - Specific Gravity of a phase ppm As - Concentration in ppm of arsenic in phase (see Table A1.0, Appendix I)

MAs = FAs * SG * ppm As Eq. 2.0

The advantage in reviewing the RELATIVE MASS ARSENIC determinations is that it gives one information as to which metal-bearing phase(s) in a sample is likely to control the total bulk concentration for arsenic. As an example, PHASE-1 may, by relative volume, contribute 98% of the sample, however it has a low specific gravity and contains only 1000 ppm arsenic, whereas

PHASE-2 contribute 2% of the sample, has a high specific gravity and contains 850000 ppm of arsenic. In this example it is PHASE-2 that is the dominant source of arsenic to the sample.

The third calculation is to determine the MINERAL MASS ARSENIC (MinAs). In this calculation the RMAs is simply multiplied by the bulk concentration of arsenic found in the sample:

MinAs = RMAS * As Bulk Eq. 3.0

Where As Bulk is the bulk arsenic for the sample speciated. These values are most useful for geostatistical calculations, such as kriging, or apportionment since values are not forced to

100%.

4.02 Point Counting

Point counts (weighted on longest dimension) are made by traversing each sample from left-to-right and top-to-bottom. The amount of vertical movement for each traverse would depend on magnification and CRT (cathode-ray tube) size. This movement should be minimized so that NO portion of the sample is missed when the end of a traverse is reached. Two magnification settings should be used. One ranging from 40 to 100X and a second from 300 to 600X. The last setting will allow one to find the smallest identifiable (1-2 micron) phases. The portion of the sample examined in the second pass, under the higher magnification, will depend on the time available, the number of metal-bearing particles, and the complexity of metal mineralogy. A maximum of 8 hours will be spent per sample.

The point counting procedure in petrography is a well established technique as outlined by

Chayes, 1949. For our procedure we have simply substituted the electron microprobe for a simple petrographic microscope as a means of visually observing a particle and identifying its composition using the attached x-ray analyzers. The operator error (identification of phase and sizing) is generally negligible. However the particle counting error can be significant depending on the total number of particles counted and the fraction of an individual component (species) percent. Based on studies in El-Hinnawi, 1966, it was shown that the relative error of a point count based on 100 total particles versus one of 300 total particles is only 10% and 6% , respectively (for a species representing 30% of the count). It is our belief that this small decrease in error is not justified when cost and time of analysis are considered, and that it is much more beneficial to increase your total sample population and address representativeness.

4.03 Precision and Accuracy

The precision of the EMPA speciation will be evaluated based on sample duplicates analyzed at a frequency of 10% as selected by the laboratory, however the client may also submit “blind” duplicates for analyses. The precision of the data generated by the “EMPA point count” will be evaluated by calculating RPD values for all major (>20% frequency) phases, comparing the original result with the duplicate result. If the duplicate analyses are from samples that have produced at least 100 total particles it is expected that all (100%) of the dominant species

(representing 60% of frequency) be found in both, and that their individual frequency of occurrence not vary by more than 30%, relative. In the evaluation of the method precision it is most important to consider the variation in results among all samples studied for a particular media, since the overall particle count is very large Data generated by the “EMPA point count” will be further evaluated statistically based on the methods of Mosimann (1965) at the 95% confidence level on the frequency data following Equation 4.

E0.95 = 2P(100-P)/N (Eq. 4)

Where: E0.95 = Probable error at the 95% confidence level

P = Percentage of N of an individual metal-bearing phase based on percent length frequency

N = Total number of metal-bearing grains counted

Accuracy of quantitative metal analyses on non-stoichimetric metal phases is based on established EMPA procedures, and data reduction, Heinrich, 1981 and is generally 1-2% relative. All quantitative analyses will be performed using a series of certified mineral standards. In general, site-specific concentrations for these variable, metal-bearing forms will be determined by performing “peak counts” on the appropriate wavelength spectrometer. Average concentrations will then be used for further calculations. Data on specific gravity will be collected from referenced databases or estimated based on similar compounds.

Plant-site Samples

During the 116 year operational history of the ASARCO facility, numerous sources for heavy-metal emissions existed, including:

Roasters, blast furnaces

Storage piles

Plant road dust

Loading/unloading facilities

Baghouses/dust collectors

Few of these sources are available today for direct sampling, therefore, plant-site samples were limited. In terms of the historical speciation of lead and arsenic at the plant, these samples are most certainly incomplete. Thus these samples provide only a partial “source fingerprint”.

Approximately 2100 particles containing either lead or arsenic were counted in the six soil samples from the ASARCO plant, Table 3. These samples can be generally characterized as representing three distinct media at the site; 1) a slag-rich (ELP 26,27) 2) a copper circuit (ELP

25) and 3) general plant soil (ELP 28,29). As a whole, plant samples studied to date have lead masses dominated (78% of the relative lead mass) by the following lead-bearing phases: PbS, PbMSO4, CuMSO4, CrMSO4, PbAsO, and PbO Figure 2, Photos 1-3. The most common metals

“M” are As, Sb or Cd. Arsenic masses dominated (85% of the relative arsenic mass) by the following arsenic-bearing phases: CuMSO4, CuM, PbAsO, and PbMSO4 Figure 2, Photos 1-3.

The most common metals “M” are Pb or Sb. These primary phases are consistent with the facilities operations.

Particle size of lead and arsenic phases are trimodal in their distribution with populations at 2,10 and 100 microns, Figure 3. The 2 micron population is dominated by PbS, the 10 micron by

CuMSO4, and the coarser, 100+ micron population by slag.

Each of the plant samples show unique lead and arsenic speciation and the site summary, Figure

2, is dominated by a large number of CuM and CuMSO4 particles that are only found in two of the samples. If one would exclude those two samples, the dominant species of lead would be

PbS, PbO, PbMSO4, and PbAsO while arsenic would be primarily found in PbAsO, PbMSO4, and sulfosalts species.

Table 3

TABLE 3. Summary Plant Speciation

Analyses.

F% RM-Pb RM -As E-95* Min-Pb Min-As

ELP-23 BiMO 5.18% 1.83% 0.05% 2.56% 214 2

Cerussite 0.46% 1.85% 0.00% 0.78% 216 0

Cu 55.97% 0.39% 91.22% 5.74% 46 4659

CuMO 7.95% 1.35% 1.31% 3.13% 157 67

Galena 10.60% 53.96% 0.00% 3.56% 6309 0

PbAsO 0.46% 1.28% 1.20% 0.78% 150 61

PbMO 4.03% 7.05% 1.25% 2.28% 824 64

PbMSO4 6.14% 10.10% 2.95% 2.78% 1181 151

PbO 1.73% 11.97% 0.00% 1.51% 1399 0

PbSiO4 3.84% 9.03% 0.06% 2.22% 1056 3

Phosphate 0.31% 0.33% 0.03% 0.64% 39 1

(Sb,Sn)MO 0.12% 0.03% 0.00% 0.39% 3 0

Sulfosalts 3.53% 0.83% 1.94% 2.14% 97 99

ELP-24 Clay 0.12% 0.04% 0.03% 0.43% 3 0

Anglesite 0.47% 5.11% 0.00% 0.84% 422 0

AsFeO 0.18% 0.10% 1.21% 0.52% 8 10

AsMO 0.60% 0.65% 11.94% 0.94% 54 100

Calcite 75.64% 11.75% 0.63% 5.23% 971 5

CuMO 0.12% 0.07% 0.17% 0.43% 5 1

FeOOH 3.70% 1.06% 0.71% 2.30% 87 6

MnOOH 0.52% 0.98% 0.11% 0.88% 81 1

PbAsO 2.72% 24.18% 59.86% 1.98% 1998 502

PbFeOOH 1.50% 3.68% 4.68% 1.48% 304 39

PbMO 2.51% 13.99% 6.56% 1.90% 1156 55

PbMSO4 2.03% 10.68% 8.26% 1.72% 882 69

PbO 0.47% 10.48% 0.00% 0.84% 866 0

PbSiO4 2.06% 15.50% 0.29% 1.73% 1280 2

Phosphate 0.05% 0.16% 0.04% 0.26% 13 0

Pyrite 0.37% 0.01% 0.34% 0.74% 1 3

(Sb,Sn)MO 4.22% 0.03% 0.01% 0.26% 3 0

Slag 0.05% 0.05% 0.02% 2.45% 4 0

Sulfosalts 0.87% 0.67% 4.12% 1.14% 55 35

FeSO4 1.77% 0.84% 1.02% 1.61% 69 9

ELP-25 Anglesite 0.09% 1.25% 0.00% 0.29% 655 0

AsMSO4 0.02% 0.09% 0.21% 0.13% 47 50

BiMO 0.01% 0.02% 0.00% 0.12% 11 0

CrMSO4 1.61% 0.82% 0.00% 1.25% 432 0

Cu 0.30% 0.01% 3.38% 0.54% 5 809

CuMSO4 91.92% 61.31% 79.19% 2.71% 32193 18953

PbAsO 0.02% 0.27% 0.40% 0.15% 142 96

PbAsVO 0.04% 0.43% 0.01% 0.19% 225 3

PbMSO4 5.01% 35.74% 16.63% 2.17% 18769 3981

Slag 0.94% 0.01% 0.00% 0.96% 7 1

Sulfosalts 0.04% 0.05% 0.17% 0.21% 24 41

ELP-26 Anglesite 1.01% 22.22% 0.00% 1.14% 506 0

CuMO 0.13% 0.14% 2.27% 0.41% 3 8

Galena 1.61% 53.06% 0.00% 1.43% 1209 0

PbAsO 0.07% 1.29% 19.88% 0.30% 29 73

PbMO 0.01% 0.16% 0.47% 0.14% 4 2

PbMSO4 0.97% 10.36% 49.92% 1.11% 236 182

PbO 0.22% 9.94% 0.00% 0.53% 227 0

Slag 95.41% 2.10% 6.07% 2.38% 48 22

Sulfosalts 0.34% 0.51% 19.74% 0.66% 12 72

FeSO4 0.23% 0.22% 1.66% 0.54% 5 6

ELP-27 CuMO 0.03% 0.11% 1.71% 0.15% 2 6

Galena 0.59% 72.30% 0.00% 0.69% 1445 0

PbMO 0.07% 2.94% 8.02% 0.24% 59 28

PbMSO4 0.02% 0.77% 3.49% 0.13% 15 12

PbO 0.08% 13.98% 0.00% 0.26% 280 0

Slag 98.89% 8.08% 21.82% 0.94% 162 75

Sulfosalts 0.32% 1.80% 64.96% 0.51% 36 223

*E-95= Estimated counting error at 95% confidence level, Mosiann, 1965.

ELP-28 Clay 10.10% 1.19% 0.74% 1.59% 27 2

Anglesite 1.18% 4.63% 0.00% 3.09% 106 0

AsMO 3.00% 1.18% 17.56% 1.59% 27 57

Arsenopyrite 0.77% 0.00% 9.66% 0.00% 0 31

CuMO 0.41% 0.08% 0.17% 0.42% 2 1

FeOOH 10.32% 1.07% 0.58% 1.51% 25 2

Galena 3.41% 20.14% 0.00% 5.89% 462 0

PbAsO 9.14% 29.50% 58.77% 6.70% 677 190

PbFeOOH 2.18% 1.94% 1.99% 2.03% 45 6

PbMO 4.05% 8.20% 3.10% 4.03% 188 10

PbMSO4 2.73% 5.20% 3.24% 3.26% 119 10

PbO 2.59% 20.82% 0.00% 5.96% 478 0

PbSiO4 1.46% 3.97% 0.06% 2.87% 91 0

Pyrite 5.18% 0.03% 1.41% 0.26% 1 5

(Sb,Sn)MO 0.14% 0.04% 0.01% 0.28% 1 0

Slag 32.88% 0.13% 0.05% 0.53% 3 0

Sulfosalts 0.77% 0.21% 1.05% 0.67% 5 3

FeSO4 9.69% 1.66% 1.62% 1.88% 38 5

ELP-29 Anglesite 1.16% 3.58% 0.00% 2.54% 48 0

AsFeO 1.78% 0.27% 1.90% 0.71% 4 6

AsMO 3.61% 1.12% 11.66% 1.44% 15 38

Arsenopyrite 1.56% 0.00% 10.76% 0.00% 0 35

BiMO 2.23% 0.72% 0.03% 1.16% 10 0

Cerussite 0.09% 0.33% 0.00% 0.78% 4 0

CuMO 2.77% 0.43% 0.62% 0.89% 6 2

FeOOH 8.97% 0.73% 0.28% 1.17% 10 1

Galena 1.61% 7.47% 0.00% 3.60% 101 0

Native Pb 0.13% 1.08% 0.00% 1.42% 15 0

PbAsO 16.47% 41.86% 58.36% 6.75% 566 188

PbMO 1.38% 2.21% 0.58% 2.01% 30 2

PbMSO4 10.66% 16.02% 6.98% 5.02% 217 22

PbO 1.12% 7.06% 0.00% 3.51% 95 0

PbSiO4 3.57% 7.67% 0.08% 3.64% 104 0

Phosphate 6.07% 6.00% 0.76% 3.25% 81 2

Pyrite 1.74% 0.01% 0.26% 0.13% 0 1

(Sb,Sn)MO 0.13% 0.03% 0.01% 0.23% 0 0

Slag 15.39% 0.05% 0.01% 0.30% 1 0

Sulfosalts 9.01% 1.94% 6.75% 1.89% 26 22

FeSO4 10.53% 1.42% 0.97% 1.62% 19 3

Fig2

Fig3

Community Soils

Community soil sample set (Figure 1) includes soils with varied bulk lead and arsenic concentrations 46-1785 mg/kg, and 4-186 mg/kg, respectively. From these samples over 2400 lead and or arsenic bearing particles were counted, Table 4. These data indicate that slag, iron oxide and phosphate are the most commonly found lead/arsenic-bearing phases in the residential soils. However, lead masses almost exclusively (84% of the relative lead mass) are dominated by phosphate, PbS, PbAsO, PbMO, PbCO3, PbMSO4, and PbSO4, with minor contributions from other lead forms, Figure 4. Five of these six dominant forms of lead are consistent with those found at the ASARCO facility and three of the five forms could only be associated with a pyrometalurgical facility. Arsenic masses almost exclusively (85% of the relative arsenic mass) dominated by arsenopyrite, PbAsO, AsMO, PbMSO4 and phosphate, Figure 4, Photos 4-11.

Again, three of the four dominant forms of arsenic in community soils are consistent with

ASARCO facility speciation results and two of the three could only be associated with a pyrometalurgical facility. Approximately 62% of the residential yards had apportionable lead paint, however, only 12% of those yards had paint as a dominant lead phase. No evidence morphological, demographical, or mineralogical could be established to support lead or arsenic contributions from either pesticides or herbicides.

The particle- size distribution for all lead and arsenic species is bimodal, at approximately 2 and

40 microns, Figure 5. The 2 micron size population is not dominated by a particular phase, however, the coarser (40 micron) population is composed in general of liberated, slag grains.

Table 4

TABLE 4. Summary of Residential Speciation

Analyses.

F% RM-Pb RM -As E-95* Min-Pb Min-As

ELP-9 Clay 2.61% 0.73% 0.97% 3.19% 6 1

AsFeOOH 0.97% 0.44% 9.49% 1.96% 4 6

FeOOH 27.22% 6.68% 7.76% 8.90% 57 5

Galena 0.22% 3.13% 0.00% 0.95% 27 0

Paint 3.36% 1.95% 0.00% 3.60% 17 0

PbAsO 0.60% 4.56% 19.48% 1.54% 39 13

PbM(Cl,SO,O) 5.37% 25.77% 20.87% 4.51% 219 14

PbMSO4 2.98% 13.47% 17.99% 3.40% 114 12

Phosphate 13.42% 39.87% 15.44% 6.82% 339 10

SbMO 0.82% 0.53% 0.34% 1.80% 4 Tr

Slag 36.39% 0.34% 0.27% 9.62% 3 Tr

Sulfosalts 0.37% 0.24% 2.57% 1.22% 2 2

FeMSO4 5.67% 2.30% 4.82% 4.63% 20 3

ELP-8 Anglesite 2.33% 8.03% 0.00% 4.67% 10 0

AsFeOOH 3.10% 0.52% 1.70% 5.37% 1 1

Arsenopyrite 26.74% 0.00% 95.17% 13.72% 0 54

FeOOH 13.57% 1.24% 0.22% 10.61% 1 Tr

Galena 16.67% 86.77% 0.00% 11.55% 105 0

PbM(Cl,SO,O) 0.39% 0.69% 0.08% 1.93% 1 Tr

PbMSO4 0.78% 1.30% 0.26% 2.72% 2 Tr

Pyrite 27.91% 0.15% 2.16% 13.90% Tr 1

FeMSO4 8.53% 1.29% 0.41% 8.66% 2 Tr

ELP-7 Anglesite 0.90% 4.69% 0.00% 3.62% 8 0

AsMO 2.24% 1.18% 10.90% 5.69% 2 2

Arsenopyrite 6.28% 0.00% 65.18% 9.32% 0 10

Galena 0.45% 3.53% 0.00% 2.57% 6 0

PbMSO4 13.45% 34.25% 13.27% 13.12% 57 2

Phosphate 29.60% 49.57% 5.57% 17.55% 82 1

Pyrite 4.48% 0.04% 1.01% 7.96% Tr Tr

Slag 13.45% 0.07% 0.02% 13.12% Tr Tr

FeMSO4 29.15% 6.67% 4.06% 17.47% 11 1

ELP-6 Anglesite 8.82% 33.35% 0.00% 4.86% 279 0

AsMO 0.86% 0.33% 16.36% 1.58% 3 9

CuM(SO,O) 2.77% 0.58% 0.00% 2.81% 5 0

FeOOH 9.17% 0.92% 1.68% 4.94% 8 1

Galena 4.08% 23.26% 0.00% 3.39% 195 0

Paint 16.89% 4.00% 0.00% 6.42% 34 0

PbAsO 1.66% 5.18% 34.91% 2.19% 43 20

PbFeOOH 1.11% 0.95% 3.30% 1.79% 8 2

PbM(Cl,SO,O) 2.27% 4.44% 5.67% 2.55% 37 3

PbMSO4 6.75% 12.43% 26.17% 4.30% 104 15

Phosphate 11.04% 13.36% 8.16% 5.37% 112 5

Slag 27.97% 0.11% 0.13% 7.69% 1 Tr

FeMSO4 6.60% 1.09% 3.61% 4.25% 9 2

ELP-5 Anglesite 1.99% 9.98% 0.00% 3.53% 39 0

AsFeOOH 2.99% 0.73% 6.45% 4.31% 3 3

AsMO 2.24% 1.13% 14.69% 3.74% 4 6

Arsenopyrite 3.48% 0.00% 48.80% 4.64% 0 20

Cerussite 0.25% 1.48% 0.00% 1.26% 6 0

CuM(SO,O) 1.74% 0.49% 0.00% 3.31% 2 0

FeOOH 41.79% 5.54% 2.63% 12.48% 22 1

Galena 3.48% 26.32% 0.00% 4.64% 102 0

PbAsO 2.74% 11.30% 19.73% 4.13% 44 8

PbM(Cl,SO,O) 1.49% 3.87% 1.28% 3.07% 15 1

Phosphate 24.13% 38.75% 6.13% 10.83% 150 2

Slag 12.19% 0.06% 0.02% 8.28% Tr Tr

FeMSO4 1.49% 0.33% 0.28% 3.07% 1 Tr

ELP-4 Clay 2.88% 0.63% 0.66% 2.95% 6 Tr

FeOOH 9.63% 1.85% 1.71% 5.21% 17 1

MnOOH 1.66% 2.10% 0.33% 2.26% 20 Tr

Organic 7.75% 0.34% 0.01% 4.72% 3 Tr

PbAsO 3.65% 21.88% 74.24% 3.32% 204 38

PbFeOOH 0.72% 1.19% 2.08% 1.49% 11 1

PbM(Cl,SO,O) 0.17% 0.62% 0.40% 0.72% 6 Tr

PbSiO4 1.33% 6.72% 0.17% 2.02% 63 Tr

Phosphate 27.50% 64.04% 19.69% 7.89% 597 10

Slag 43.77% 0.32% 0.20% 8.77% 3 Tr

FeMSO4 0.94% 0.30% 0.50% 1.71% 3 Tr

ELP-3 AsFeOOH 0.40% 0.43% 0.44% 2.09% 1 Tr

Arsenopyrite 13.50% 0.00% 95.30% 11.32% 0 45

FeOOH 23.93% 13.80% 0.76% 14.14% 30 Tr

Galena 0.67% 21.97% 0.00% 2.70% 48 0

MnOOH 2.81% 10.65% 0.10% 5.47% 23 Tr

PbMSO4 0.27% 2.84% 0.18% 1.71% 6 Tr

Phosphate 6.42% 44.81% 0.82% 8.12% 97 Tr

Pyrite 11.10% 0.38% 1.70% 10.41% 1 1

Slag 36.63% 0.80% 0.03% 15.96% 2 Tr

Sulfosalts 0.40% 0.61% 0.31% 2.09% 1 Tr

FeMSO4 3.88% 3.70% 0.37% 6.40% 8 Tr

ELP-22 AsFeOOH 0.58% 0.35% 4.59% 1.97% 1 1

Arsenopyrite 1.16% 0.00% 59.50% 2.78% 0 19

FeOOH 27.06% 8.88% 6.23% 11.53% 34 2

MnOOH 1.63% 3.51% 0.42% 3.28% 13 Tr

PbAsO 0.23% 2.37% 6.12% 1.25% 9 2

Phosphate 20.67% 82.16% 19.19% 10.51% 313 6

Pyrite 1.28% 0.03% 1.42% 2.92% Tr Tr

SbMO 0.58% 0.50% 0.19% 1.97% 2 Tr

Slag 43.79% 0.54% 0.26% 12.88% 2 Tr

FeMSO4 3.02% 1.64% 2.07% 4.44% 6 1

ELP-21 Anglesite 0.44% 1.76% 0.00% 1.34% 14 0

AsFeOOH 2.81% 0.55% 5.17% 3.34% 4 2

AsMO 0.89% 0.35% 4.96% 1.90% 3 2

Arsenopyrite 2.81% 0.00% 33.53% 3.34% 0 14

FeOOH 20.12% 2.11% 1.08% 8.10% 17 Tr

Galena 3.55% 21.22% 0.00% 3.74% 174 0

Paint 6.36% 1.58% 0.00% 4.93% 13 0

PbAsO 5.92% 19.33% 36.31% 4.77% 158 15

PbFeOOH 1.18% 1.07% 1.03% 2.19% 9 Tr

PbM(Cl,SO,O) 2.81% 5.77% 2.05% 3.34% 47 1

PbMSO4 7.69% 14.85% 8.72% 5.39% 121 4

PbSiO4 1.18% 3.27% 0.05% 2.19% 27 Tr

Phosphate 19.38% 24.61% 4.19% 7.99% 201 2

Pyrite 0.44% 0.00% 0.12% 1.34% 0 Tr

SbMO 2.51% 0.69% 0.20% 3.17% 6 Tr

Slag 5.62% 0.02% 0.01% 4.66% Tr Tr

FeMSO4 16.27% 2.83% 2.60% 7.46% 23 1

ELP-20 Anglesite 0.82% 4.94% 0.00% 1.51% 57 0

AsMO 5.60% 3.41% 59.09% 3.85% 40 26

CuM(SO,O) 9.63% 3.24% 0.00% 4.94% 38 0

FeOOH 32.05% 5.13% 3.24% 7.81% 60 1

Galena 1.40% 12.77% 0.00% 1.97% 148 0

Paint 11.97% 4.53% 0.00% 5.44% 53 0

PbAsO 1.75% 8.72% 20.29% 2.20% 101 9

PbM(Cl,SO,O) 4.32% 13.51% 5.96% 3.40% 157 3

PbMSO4 0.58% 1.72% 1.25% 1.28% 20 1

Phosphate 20.61% 39.90% 8.41% 6.77% 464 4

SbMO 1.93% 0.81% 0.28% 2.30% 9 Tr

Slag 4.50% 0.03% 0.01% 3.47% Tr Tr

FeMSO4 4.85% 1.28% 1.46% 3.60% 15 1

ELP-19 Arsenopyrite 12.30% 0.00% 85.12% 9.60% 0 163

FeOOH 12.94% 2.30% 0.40% 9.81% 12 1

Galena 3.24% 32.78% 0.00% 5.17% 173 0

PbFeOOH 6.47% 9.90% 3.27% 7.19% 52 6

PbM(Cl,SO,O) 2.27% 7.88% 0.96% 4.35% 42 2

PbMSO4 3.88% 12.71% 2.55% 5.64% 67 5

Phosphate 12.30% 26.47% 1.54% 9.60% 140 3

Pyrite 21.68% 0.23% 3.26% 12.04% 1 6

SbMO 1.29% 0.61% 0.06% 3.30% 3 Tr

Sulfosalts 0.97% 0.45% 0.73% 2.86% 2 1

FeMSO4 22.65% 6.67% 2.10% 12.23% 35 4

ELP-18 Arsenopyrite 3.75% 0.00% 70.06% 4.45% 0 46

CuM(SO,O) 0.26% 0.25% 0.00% 1.20% 2 0

FeOOH 12.48% 5.75% 1.05% 7.74% 35 1

Galena 0.07% 1.73% 0.00% 0.60% 10 0

Paint 1.84% 2.01% 0.00% 3.15% 12 0

PbAsO 1.45% 20.75% 13.91% 2.80% 125 9

PbFeOOH 1.31% 5.21% 1.80% 2.67% 31 1

PbM(Cl,SO,O) 0.85% 7.70% 0.98% 2.16% 46 1

PbMSO4 5.58% 47.36% 9.93% 5.38% 286 7

PbO 0.20% 7.04% 0.00% 1.04% 43 0

Phosphate 0.07% 0.37% 0.02% 0.60% 2 Tr

Pyrite 4.73% 0.13% 1.92% 4.97% 1 1

Slag 66.16% 1.16% 0.15% 11.08% 7 Tr

FeMSO4 0.72% 0.55% 0.18% 1.98% 3 Tr

ELP-17 AsFeOOH 0.09% 0.03% 0.71% 0.56% Tr Tr

AsMO 0.27% 0.17% 6.44% 0.97% 2 3

Barite 0.27% 0.08% 0.00% 0.97% 1 0

Cerussite 0.18% 1.37% 0.00% 0.79% 13 0

Cr 28.60% 6.24% 0.00% 8.33% 59 0

CuM(SO,O) 0.09% 0.03% 0.00% 0.56% 0 0

FeOOH 33.73% 5.59% 7.58% 8.72% 53 3

Galena 0.09% 0.87% 0.00% 0.56% 8 0

PbAsO 1.56% 8.04% 40.10% 2.28% 76 18

PbAsVO 2.66% 13.61% 1.54% 2.97% 129 1

PbFeOOH 1.19% 1.70% 4.35% 2.00% 16 2

PbM(Cl,SO,O) 4.31% 13.97% 13.19% 3.74% 132 6

PbMSO4 0.73% 2.24% 3.48% 1.57% 21 2

Solder 0.18% 0.12% 0.00% 0.79% 1 Tr

Phosphate 22.36% 44.88% 20.27% 7.68% 425 9

SbMO 0.37% 0.16% 0.12% 1.11% 2 Tr

FeMSO4 3.30% 0.91% 2.21% 3.29% 9 1

ELP-16 Anglesite 0.86% 4.05% 0.00% 1.61% 37 0

AsFeOOH 7.26% 1.67% 12.99% 4.51% 15 14

AsMO 2.34% 1.11% 12.70% 2.63% 10 14

Arsenopyrite 1.48% 0.00% 17.13% 2.10% 0 19

CuM(SO,O) 0.62% 0.16% 0.00% 1.36% 1 0

FeOOH 23.74% 2.95% 1.24% 7.40% 27 1

Galena 1.72% 12.20% 0.00% 2.26% 111 0

MnOOH 0.62% 0.50% 0.04% 1.36% 5 Tr

PbAsO 6.03% 23.34% 35.98% 4.14% 213 40

PbAsVO 0.86% 3.31% 0.12% 1.61% 30 Tr

PbFeOOH 4.31% 4.61% 3.65% 3.53% 42 4

PbM(Cl,SO,O) 9.84% 23.94% 6.99% 5.18% 218 8

PbMSO4 5.29% 12.10% 5.83% 3.89% 110 6

Phosphate 4.80% 7.22% 1.01% 3.72% 66 1

Pyrite 1.72% 0.01% 0.43% 2.26% Tr Tr

SbMO 1.11% 0.36% 0.08% 1.82% 3 Tr

Slag 15.87% 0.07% 0.02% 6.35% 1 Tr

FeMSO4 11.56% 2.38% 1.80% 5.56% 22 2

ELP-15 AsFeOOH 1.75% 0.28% 6.50% 2.60% 2 2

FeOOH 20.26% 1.73% 2.18% 7.96% 14 1

Galena 8.61% 41.97% 0.00% 5.55% 337 0

PbAsO 4.63% 12.32% 57.12% 4.16% 99 18

PbFeOOH 4.15% 3.05% 7.27% 3.95% 25 2

PbM(Cl,SO,O) 3.67% 6.14% 5.39% 3.72% 49 2

PbMSO4 2.23% 3.51% 5.09% 2.93% 28 2

PbO 0.32% 2.11% 0.00% 1.12% 17 0

Phosphate 25.52% 26.42% 11.10% 8.63% 212 3

SbMO 12.12% 0.11% 0.07% 1.37% 1 Tr

Slag 0.48% 0.04% 0.03% 6.46% Tr Tr

FeMSO4 16.27% 2.30% 5.24% 7.31% 18 2

ELP-14 Clay 2.43% 0.39% 0.30% 2.54% 4 Tr

AsFeOOH 0.47% 0.12% 1.52% 1.13% 1 1

AsMO 1.31% 0.69% 12.90% 1.88% 8 9

CuM(SO,O) 0.28% 0.08% 0.00% 0.87% 1 0

FeOOH 26.07% 3.63% 2.47% 7.25% 40 2

MnOOH 16.45% 15.05% 1.76% 6.12% 168 1

PbAsO 4.58% 19.84% 49.63% 3.45% 221 34

PbFeOOH 0.93% 1.11% 1.43% 1.58% 12 1

PbM(Cl,SO,O) 9.44% 25.68% 12.18% 4.83% 287 8

PbMSO4 2.06% 5.26% 4.11% 2.34% 59 3

Phosphate 14.39% 24.24% 5.49% 5.79% 270 4

Slag 5.89% 0.03% 0.01% 3.89% Tr Tr

Sulfosalts 1.87% 0.68% 4.28% 2.24% 8 3

FeMSO4 13.83% 3.19% 3.91% 5.70% 36 3

ELP-13 Clay 0.09% 0.11% 0.14% 0.47% 1 Tr

Anglesite 0.11% 4.58% 0.00% 0.52% 42 0

AsMO 0.02% 0.07% 2.02% 0.20% 1 1

CuM(SO,O) 0.30% 0.67% 0.00% 0.85% 6 0

FeOOH 0.72% 0.78% 0.87% 1.33% 7 1

Galena 0.21% 12.83% 0.00% 0.72% 117 0

MnOOH 0.07% 0.51% 0.10% 0.42% 5 Tr

PbAsO 0.02% 0.54% 2.22% 0.20% 5 1

PbFeOOH 0.50% 4.62% 9.77% 1.10% 42 6

PbM(Cl,SO,O) 0.17% 3.56% 2.77% 0.64% 32 2

PbMSO4 2.74% 54.66% 70.31% 2.56% 498 46

Phosphate 0.89% 11.64% 4.34% 1.47% 106 3

Pyrite 0.06% 0.00% 0.33% 0.37% Tr Tr

Slag 93.25% 3.82% 2.95% 3.94% 35 2

Sulfosalts 0.04% 0.11% 1.17% 0.31% 1 1

FeMSO4 0.83% 1.49% 3.01% 1.43% 14 2

ELP-12 Anglesite 0.93% 3.43% 0.00% 2.68% 13 0

AsFeOOH 0.79% 0.14% 15.46% 2.49% 1 2

AsMO 0.40% 0.15% 23.46% 1.76% 1 3

FeOOH 8.21% 0.80% 4.65% 3.78% 3 1

Galena 1.46% 8.13% 0.00% 7.69% 31 0

MnOOH 2.78% 1.79% 1.78% 3.36% 7 Tr

Paint 67.55% 37.24% 0.00% 4.60% 140 0

PbAsO 0.26% 0.81% 17.19% 13.11% 3 2

PbM(Cl,SO,O) 0.26% 0.51% 2.05% 1.44% 2 Tr

PbMSO4 0.93% 1.67% 11.11% 1.44% 6 2

Phosphate 7.42% 8.79% 16.95% 2.68% 33 2

Slag 6.62% 0.02% 0.10% 7.34% Tr Tr

Sulfosalts 0.53% 0.14% 7.26% 6.96% 1 1

Brass 1.85% 0.00% 0.02% 2.03% Tr Tr

ELP-11 Clay 1.81% 0.31% 0.31% 2.25% 4 Tr

Anglesite 0.50% 2.82% 0.00% 1.19% 32 0

AsMO 1.71% 0.97% 23.41% 2.18% 11 15

CuM(SO,O) 0.20% 0.06% 0.00% 0.76% 1 0

FeOOH 40.96% 6.09% 5.39% 8.30% 70 3

MnOOH 4.12% 4.03% 0.61% 3.35% 46 Tr

Paint 6.22% 2.19% 0.00% 4.08% 25 0

PbAsO 2.91% 13.49% 43.88% 2.84% 154 27

PbFeOOH 1.31% 1.67% 2.79% 1.91% 19 2

PbM(Cl,SO,O) 3.11% 9.06% 5.58% 2.93% 104 3

Solder 1.41% 0.84% 0.02% 1.99% 10 Tr

Phosphate 32.13% 57.86% 17.05% 7.88% 661 11

Slag 1.20% 0.01% 0.00% 1.84% Tr Tr

FeMSO4 2.41% 0.59% 0.95% 2.59% 7 1

ELP-10 AsFeOOH 0.41% 0.15% 1.92% 1.52% 1 1

AsMO 1.22% 0.90% 17.50% 2.63% 8 10

Arsenopyrite 0.20% 0.00% 6.23% 1.08% 0 3

CuM(SO,O) 0.51% 0.21% 0.00% 1.70% 2 0

FeOOH 27.26% 5.30% 3.75% 10.66% 45 2

Galena 0.31% 3.38% 0.00% 1.32% 29 0

Paint 23.60% 10.86% 0.00% 10.17% 93 0

PbAsO 2.03% 12.31% 32.04% 3.38% 105 18

PbFeOOH 5.19% 8.68% 11.60% 5.31% 74 6

PbM(Cl,SO,O) 7.02% 26.67% 13.16% 6.12% 228 7

PbMSO4 0.81% 2.91% 2.37% 2.15% 25 1

InMS 0.20% 0.01% 0.00% 1.08% Tr Tr

Phosphate 10.68% 25.12% 5.92% 7.40% 215 3

Pyrite 0.81% 0.01% 0.54% 2.15% Tr Tr

Slag 9.16% 0.07% 0.03% 6.91% 1 Tr

Sulfosalts 0.20% 0.10% 0.68% 1.08% 1 Tr

FeMSO4 10.38% 3.34% 4.26% 7.30% 28 2

ELP-1 AsCaO 7.09% 0.52% 41.35% 4.39% 5 27

AsMO 3.72% 1.96% 23.37% 3.24% 20 15

FeOOH 27.37% 3.79% 1.65% 2.26% 38 1

Galena 1.77% 13.98% 0.00% 7.64% 141 0

MnOOH 1.42% 1.29% 0.10% 2.26% 13 Tr

Paint 4.43% 1.45% 0.00% 2.02% 15 0

PbAsO 3.10% 13.37% 21.41% 3.52% 135 14

PbM(Cl,SO,O) 1.77% 4.80% 1.46% 2.97% 48 1

PbMSO4 1.77% 4.52% 2.26% 2.26% 45 1

PbSiO4 0.18% 0.65% 0.01% 2.26% 7 Tr

Phosphate 31.09% 52.14% 7.56% 0.72% 525 5

SbMO 1.68% 0.61% 0.15% 7.93% 6 Tr

Slag 9.03% 0.05% 0.01% 2.20% Tr Tr

FeMSO4 3.81% 0.87% 0.69% 4.91% 9 Tr

Cerussite 1.77% 9.93% 0.00% 3.28% 100 0

ELP-2 Anglesite 1.57% 10.12% 0.00% 2.30% 39 0

AsFeOOH 1.12% 0.35% 2.43% 1.95% 1 1

AsMO 1.57% 1.02% 10.33% 2.30% 4 5

Arsenopyrite 4.26% 0.00% 59.91% 3.74% 0 29

Cerussite 0.22% 1.72% 0.00% 0.88% 7 0

FeOOH 12.91% 2.20% 0.81% 6.21% 9 Tr

Galena 3.14% 30.50% 0.00% 3.23% 118 0

PbAsO 2.24% 11.91% 16.22% 2.74% 46 8

PbFeOOH 0.11% 0.16% 0.12% 0.62% 1 Tr

PbM(Cl,SO,O) 2.58% 8.60% 2.22% 2.94% 33 1

PbMSO4 2.81% 8.79% 3.74% 3.06% 34 2

Phosphate 11.00% 22.68% 2.80% 5.79% 88 1

Pyrite 0.79% 0.01% 0.24% 1.64% Tr Tr

Slag 49.94% 0.32% 0.08% 9.26% 1 Tr

FeMSO4 5.72% 1.61% 1.08% 4.30% 6 1

ELP-30 Arsenopyrite 1.10% 0.00% 61.62% 1.93% 0 9

Cerussite 4.69% 39.67% 0.00% 3.92% 44 0

CuM(SO,O) 0.10% 0.04% 0.00% 0.57% Tr 0

FeOOH 25.48% 4.79% 6.40% 8.07% 5 1

Galena 0.57% 6.16% 0.00% 1.40% 7 0

Paint 30.41% 13.55% 0.00% 8.52% 15 0

PbAsO 0.24% 1.40% 6.89% 0.91% 2 1

Pyrite/Chalcopyrite 0.67% 0.00% 0.82% 1.51% Tr Tr

PbFeOOH 0.48% 0.78% 1.96% 1.28% 1 Tr

PbM(Cl,SO,O) 3.21% 11.81% 10.99% 3.26% 13 2

PbMSO4 0.14% 0.50% 0.76% 0.70% 1 Tr

Pb 0.14% 2.70% 0.00% 0.70% 3 0

PbSiO4 0.05% 0.24% 0.01% 0.41% 0 Tr

Solder 0.91% 0.69% 0.02% 1.76% 1 Tr

Phosphate 7.09% 16.14% 7.18% 4.75% 18 1

SbMO 0.14% 0.07% 0.05% 0.70% Tr Tr

Slag 20.35% 0.15% 0.13% 7.46% Tr Tr

FeMSO4 4.21% 1.31% 3.16% 3.72% 1 Tr

ELP-31 AsMO 6.95% 5.74% 55.74% 6.38% 18 6

Barite 1.74% 0.66% 0.00% 3.28% 2 0

Cerussite 0.77% 7.53% 0.00% 2.20% 24 0

FeOOH 41.12% 8.93% 3.16% 12.35% 29 Tr

Galena 0.58% 7.16% 0.00% 1.90% 23 0

MnOOH 1.93% 2.76% 0.17% 3.45% 9 Tr

Paint 2.70% 1.39% 0.00% 4.07% 4 0

PbAsO 3.47% 23.49% 30.62% 4.60% 75 3

PbM(Cl,SO,O) 6.56% 27.86% 6.88% 6.21% 89 1

Solder 2.32% 2.03% 0.02% 3.78% 6 Tr

Phosphate 3.28% 8.62% 1.02% 4.47% 28 Tr

Slag 18.34% 0.15% 0.04% 9.71% Tr Tr

FeMSO4 10.23% 3.68% 2.35% 7.61% 12 Tr

ELP-32 Anglesite 1.85% 11.69% 0.00% 4.13% 13 0

AsFeOOH 2.96% 0.92% 2.47% 5.19% 1 Tr

AsMO 10.00% 6.36% 25.35% 9.18% 7 2

Arsenopyrite 11.48% 0.00% 62.18% 9.76% 0 5

Cerussite 5.93% 44.48% 0.00% 7.23% 48 0

FeOOH 13.70% 2.29% 0.33% 10.53% 2 Tr

PbAsO 2.96% 15.42% 8.26% 5.19% 16 1

PbM(Cl,SO,O) 1.48% 4.84% 0.49% 3.70% 5 Tr

Brass 2.96% 0.01% 0.00% 5.19% Tr Tr

Phosphate 6.30% 12.73% 0.62% 7.44% 14 Tr

Slag 36.67% 0.23% 0.02% 14.75% Tr Tr

FeMSO4 3.70% 1.02% 0.27% 5.78% 1 Tr

ELP-33 AsMO 0.37% 0.23% 22.74% 1.21% 4 3

Barite 1.10% 0.32% 0.00% 2.09% 6 0

Cerussite 7.08% 53.15% 0.00% 5.13% 949 0

FeOOH 42.59% 7.11% 25.25% 9.89% 127 3

MnOOH 4.23% 4.65% 2.83% 4.03% 83 Tr

PbM(Cl,SO,O) 0.46% 1.50% 3.72% 1.35% 27 Tr

Solder 1.66% 1.12% 0.10% 2.55% 20 Tr

Phosphate 14.72% 29.76% 35.19% 7.09% 531 5

Pyrite/Chalcopyrite 1.10% 0.00% 3.17% 2.09% Tr Tr

SbMO 3.22% 1.42% 2.77% 3.53% 25 Tr

Slag 21.25% 0.13% 0.33% 8.18% 2 Tr

FeMSO4 2.21% 0.61% 3.91% 2.94% 11 1

TM Brass 7.14% 0.02% 0.00% 5.15% Tr Tr

PbAsO 21.43% 55.45% 85.98% 8.21% 26 3

PbM(Cl,SO,O) 21.43% 34.83% 10.23% 8.21% 16 Tr

Solder 14.29% 4.79% 0.05% 7.00% 2 Tr

FeMSO4 35.71% 4.91% 3.73% 9.59% 2 Tr

Z-1 Arsenopyrite 9.72% 0.00% 97.75% 8.05% 0 38

Brass 1.54% 0.07% 0.00% 3.35% Tr Tr

CuM(SO,O) 0.62% 2.32% 0.00% 2.13% 1 0

Galena 0.62% 62.91% 0.00% 2.13% 33 0

MnOOH 1.23% 14.53% 0.06% 3.00% 8 Tr

Pyrite/Chalcopyrite 6.48% 0.02% 1.42% 6.69% Tr 1

Slag 74.69% 5.06% 0.09% 11.82% 3 Tr

FeMSO4 5.09% 15.08% 0.69% 5.98% 8 Tr

ELP-16-Dup Anglesite 0.49% 2.50% 0.00% 1.25% 23 0

AsFeOOH 6.27% 1.56% 12.29% 4.34% 14 14

AsMO 1.35% 0.69% 8.05% 2.07% 6 9

Arsenopyrite 1.47% 0.00% 18.75% 2.16% 0 21

FeOOH 27.27% 3.68% 1.56% 7.97% 34 2

Galena 1.47% 11.32% 0.00% 2.16% 103 0

MnOOH 0.61% 0.54% 0.04% 1.40% 5 0

PbAsO 6.02% 25.27% 39.40% 4.26% 230 43

PbFeOOH 2.33% 2.71% 2.17% 2.70% 25 2

PbM(Cl,SO,O) 9.09% 23.96% 7.08% 5.14% 219 8

PbMSO4 5.90% 14.62% 7.13% 4.21% 133 8

Solder 0.61% 0.33% 0.00% 1.40% 3 0

Phosphate 6.02% 9.82% 1.39% 4.26% 90 2

SbMO 0.49% 0.17% 0.04% 1.25% 2 0

Slag 18.43% 0.09% 0.03% 6.94% 1 0

FeMSO4 12.16% 2.71% 2.07% 5.85% 25 2

ELP-30-Dup Arsenopyrite 0.73% 0.00% 44.22% 1.66% 0 6

Cerussite 4.67% 40.69% 0.00% 4.11% 166 0

FeOOH 29.73% 5.77% 8.06% 8.91% 23 1

Paint 16.67% 7.66% 0.00% 7.27% 31 0

PbAsO 0.33% 2.01% 10.34% 1.12% 8 1

Pyrite/Chalcopyrite 0.87% 0.00% 1.14% 1.81% 0 0

PbFeOOH 1.13% 1.89% 4.99% 2.06% 8 1

PbM(Cl,SO,O) 4.47% 16.95% 16.49% 4.03% 69 2

PbSiO4 0.33% 1.70% 0.07% 1.12% 7 0

Solder 0.33% 0.26% 0.01% 1.12% 1 0

Phosphate 8.93% 20.99% 9.76% 5.56% 85 1

Slag 25.93% 0.19% 0.18% 8.55% 1 0

FeMSO4 5.87% 1.88% 4.74% 4.58% 8 1

*E-95%= Estamated counting error at 95% confidence, Mossiman, 1965.

Fig 4

Fig5

Statistical Study–Correlation Analysis

A matrix was constructed using twenty-six variables and 26 cases (soil samples) and twenty-six variables and 6 cases (plant samples) to conduct a correlation analysis using STATISTICA. The variables included data from the El Paso speciation study (MinPb), and bulk metals concentrations.

Based on these data a correlation matrix was computed for each group.

Correlations within the residential samples can be used for apportionment calculations. These correlations are often valuable in assigning source(s) to “non-specific” phases and phases that can be common to multiple sources. However, one must remember that a correlation does not necessarily indicate an association! Other statistical techniques can be applied to the data and may offer further insight. The most significant correlations between variable pairs have been marked in bold in Tables 5- 6. Many of these correlations support the categories established later in

Chapter 6.

For plant soils, correlation coefficients suggest; 1) bulk lead and arsenic concentrations at the plant are dominated by emission products and 2) all of the pyrometalurgical phases (except slag) proposed in Chapter 6 show a strong correlation and 3) all concentrate phases (except anglesite) proposed in Chapter 6 show a strong correlation.

For community soils a number of observations that one can make from the data, which may be important to this study, are; 1) that bulk lead and arsenic do not correlate highly (r> 0.80, p<0.05) with any particular phase 2) bulk cadmium however does correlate well with all emission products 3) concentrate phases, other than pyrite and sulfosalts are poorly correlated to other factors 4) the total lack of a correlation between paint and any other phase, particularly anglesite, cerussite or lead oxide, or bulk metal concentration 5) “solder” may be miss-identified as an anthropogenic phase, and may be a by product from the facility and 6) most (9 out of 12) of the proposed pyrometalurgical phases show good inter-phase correlation.

Table 5. Correlation matrix of Factor Analysis TABLE 5. Plant speciation correlations.

Marked correlations are significant at p < .05000

Anglesit e

AsFeO

OH

AsMO AsMSO

BiMO Cerussi te

CrMO Cu CuMO CuMSO

FeOOH Galena MnOO H

PbAsO PbVAs O

PbFeO

OH

PbMO PbMSO

PbO PbSiO4 Phos Slag SS FeMSO

Bulk Pb Bulk As

Anglesit e

1.00 0.10 0.04 0.67 -0.39 -0.41 0.67 -0.33 -0.41 0.67 0.16 -0.46 0.26 0.12 0.67 0.23 -0.10 0.67 -0.38 -0.11 -0.47 -0.25 -0.34 0.23 0.65 0.60

AsFeO

OH

0.10 1.00 0.84 -0.24 -0.24 -0.23 -0.24 -0.27 -0.21 -0.24 0.88 -0.37 0.89 0.91 -0.24 0.87 0.61 -0.22 0.15 0.59 0.32 -0.31 0.16 0.90 -0.19 -0.27

AsMO 0.04 0.84 1.00 -0.30 -0.32 -0.30 -0.30 -0.33 -0.28 -0.30 0.96 -0.42 0.85 0.98 -0.30 0.90 0.61 -0.29 0.22 0.53 0.03 -0.38 -0.04 0.89 -0.26 -0.35 AsMSO

0.67 -0.24 -0.30 1.00 -0.13 -0.17 1.00 -0.06 -0.19 1.00 -0.24 -0.27 -0.17 -0.23 1.00 -0.19 -0.31 1.00 -0.42 -0.29 -0.27 -0.18 -0.17 -0.20 0.98 0.98

BiMO -0.39 -0.24 -0.32 -0.13 1.00 1.00 -0.13 1.00 1.00 -0.13 -0.26 0.95 -0.19 -0.24 -0.13 -0.22 0.47 -0.08 0.81 0.55 0.32 -0.26 0.86 -0.22 0.04 0.07 Cerussi te

-0.41 -0.23 -0.30 -0.17 1.00 1.00 -0.17 0.99 1.00 -0.17 -0.24 0.96 -0.17 -0.23 -0.17 -0.20 0.49 -0.12 0.83 0.57 0.30 -0.24 0.86 -0.20 0.00 0.03

CrMO 0.67 -0.24 -0.30 1.00 -0.13 -0.17 1.00 -0.06 -0.19 1.00 -0.24 -0.27 -0.17 -0.23 1.00 -0.19 -0.31 1.00 -0.42 -0.29 -0.27 -0.18 -0.17 -0.20 0.98 0.98 Cu -0.33 -0.27 -0.33 -0.06 1.00 0.99 -0.06 1.00 0.99 -0.06 -0.27 0.95 -0.19 -0.25 -0.06 -0.22 0.46 -0.01 0.80 0.55 0.26 -0.26 0.86 -0.22 0.11 0.14 CuMO -0.41 -0.21 -0.28 -0.19 1.00 1.00 -0.19 0.99 1.00 -0.19 -0.22 0.96 -0.15 -0.21 -0.19 -0.18 0.50 -0.14 0.84 0.59 0.31 -0.24 0.87 -0.18 -0.02 0.01 CuMSO

0.67 -0.24 -0.30 1.00 -0.13 -0.17 1.00 -0.06 -0.19 1.00 -0.24 -0.27 -0.17 -0.23 1.00 -0.19 -0.31 1.00 -0.42 -0.29 -0.27 -0.18 -0.17 -0.20 0.98 0.98

FeOOH 0.16 0.88 0.96 -0.24 -0.26 -0.24 -0.24 -0.27 -0.22 -0.24 1.00 -0.36 0.95 0.99 -0.24 0.99 0.71 -0.22 0.29 0.64 -0.07 -0.31 0.09 0.98 -0.17 -0.27 Galena -0.46 -0.37 -0.42 -0.27 0.95 0.96 -0.27 0.95 0.96 -0.27 -0.36 1.00 -0.27 -0.37 -0.27 -0.30 0.38 -0.23 0.79 0.45 0.17 -0.01 0.81 -0.30 -0.11 -0.08 MnOO H

0.26 0.89 0.85 -0.17 -0.19 -0.17 -0.17 -0.19 -0.15 -0.17 0.95 -0.27 1.00 0.92 -0.17 0.99 0.77 -0.14 0.32 0.71 -0.09 -0.21 0.23 1.00 -0.08 -0.18

PbAsO 0.12 0.91 0.98 -0.23 -0.24 -0.23 -0.23 -0.25 -0.21 -0.23 0.99 -0.37 0.92 1.00 -0.23 0.95 0.70 -0.21 0.27 0.63 0.08 -0.41 0.09 0.95 -0.17 -0.26 PbVAs O

0.67 -0.24 -0.30 1.00 -0.13 -0.17 1.00 -0.06 -0.19 1.00 -0.24 -0.27 -0.17 -0.23 1.00 -0.19 -0.31 1.00 -0.42 -0.29 -0.27 -0.18 -0.17 -0.20 0.98 0.98

PbFeO

OH

0.23 0.87 0.90 -0.19 -0.22 -0.20 -0.19 -0.22 -0.18 -0.19 0.99 -0.30 0.99 0.95 -0.19 1.00 0.76 -0.17 0.33 0.69 -0.13 -0.25 0.17 1.00 -0.11 -0.22

PbMO -0.10 0.61 0.61 -0.31 0.47 0.49 -0.31 0.46 0.50 -0.31 0.71 0.38 0.77 0.70 -0.31 0.76 1.00 -0.25 0.85 0.99 0.08 -0.35 0.73 0.75 -0.12 -0.19 PbMSO

0.67 -0.22 -0.29 1.00 -0.08 -0.12 1.00 -0.01 -0.14 1.00 -0.22 -0.23 -0.14 -0.21 1.00 -0.17 -0.25 1.00 -0.37 -0.23 -0.26 -0.21 -0.12 -0.17 0.99 0.99

PbO -0.38 0.15 0.22 -0.42 0.81 0.83 -0.42 0.80 0.84 -0.42 0.29 0.79 0.32 0.27 -0.42 0.33 0.85 -0.37 1.00 0.86 0.11 -0.26 0.85 0.31 -0.23 -0.25 PbSiO4 -0.11 0.59 0.53 -0.29 0.55 0.57 -0.29 0.55 0.59 -0.29 0.64 0.45 0.71 0.63 -0.29 0.69 0.99 -0.23 0.86 1.00 0.18 -0.38 0.80 0.69 -0.09 -0.16 Phos -0.47 0.32 0.03 -0.27 0.32 0.30 -0.27 0.26 0.31 -0.27 -0.07 0.17 -0.09 0.08 -0.27 -0.13 0.08 -0.26 0.11 0.18 1.00 -0.37 0.31 -0.08 -0.25 -0.22 Slag -0.25 -0.31 -0.38 -0.18 -0.26 -0.24 -0.18 -0.26 -0.24 -0.18 -0.31 -0.01 -0.21 -0.41 -0.18 -0.25 -0.35 -0.21 -0.26 -0.38 -0.37 1.00 -0.12 -0.24 -0.26 -0.24 SS -0.34 0.16 -0.04 -0.17 0.86 0.86 -0.17 0.86 0.87 -0.17 0.09 0.81 0.23 0.09 -0.17 0.17 0.73 -0.12 0.85 0.80 0.31 -0.12 1.00 0.19 0.02 0.01 FeMSO

0.23 0.90 0.89 -0.20 -0.22 -0.20 -0.20 -0.22 -0.18 -0.20 0.98 -0.30 1.00 0.95 -0.20 1.00 0.75 -0.17 0.31 0.69 -0.08 -0.24 0.19 1.00 -0.11 -0.22

Bulk Pb 0.65 -0.19 -0.26 0.98 0.04 0.00 0.98 0.11 -0.02 0.98 -0.17 -0.11 -0.08 -0.17 0.98 -0.11 -0.12 0.99 -0.23 -0.09 -0.25 -0.26 0.02 -0.11 1.00 0.99 Bulk As 0.60 -0.27 -0.35 0.98 0.07 0.03 0.98 0.14 0.01 0.98 -0.27 -0.08 -0.18 -0.26 0.98 -0.22 -0.19 0.99 -0.25 -0.16 -0.22 -0.24 0.01 -0.22 0.99 1.00

Table 6 TABLE 6. Corre lation ma trix for R esid ential So ils

Marked correlations are significant at p < .05000

Anglesi te

AsFeO

OH

AsMO Arseno pyrite

Cerussi te

CuMO FeOOH Galena MnOO H

Paint PbAsO PbFeO

OH

PbMO PbMS O4

PbO PbSiO4 Solder Phosph ate

Pyrite SbMO Slag Sulfosa lt

FeMSO

Bulk Pb Bulk As Bulk Cd

Angle site

1.00 0.26 0.29 -0.01 0.12 0.32 0.04 0.31 0.02 0.23 -0.05 0.07 -0.05 0.01 0.19 0.16 0.27 -0.15 0.26 0.25 0.21 0.25 0.17 -0.03 0.02 0.37

AsFe

OOH

0.26 1.00 0.90 0.42 0.67 0.92 0.60 0.06 0.44 0.42 0.12 0.67 0.12 0.06 0.89 0.81 0.98 -0.17 0.99 0.99 0.92 0.98 0.88 -0.35 0.25 0.91

AsM

O

0.29 0.90 1.00 0.30 0.73 0.97 0.72 0.09 0.45 0.49 0.19 0.57 0.20 -0.02 0.80 0.72 0.94 0.05 0.91 0.91 0.84 0.91 0.82 -0.14 0.20 0.93

Arsen opyrit e

-0.01 0.42 0.30 1.00 0.21 0.35 0.07 0.16 0.07 -0.01 -0.28 0.48 -0.20 0.01 0.44 0.29 0.41 -0.38 0.44 0.44 0.37 0.44 0.49 -0.53 0.77 0.24

Ceru ssite

0.12 0.67 0.73 0.21 1.00 0.62 0.50 0.12 0.30 0.28 0.14 0.35 -0.01 -0.02 0.60 0.58 0.68 0.15 0.69 0.72 0.63 0.68 0.56 -0.08 0.20 0.69

CuM

O

0.32 0.92 0.97 0.35 0.62 1.00 0.66 0.10 0.40 0.49 0.07 0.59 0.13 0.06 0.84 0.75 0.96 -0.06 0.93 0.92 0.89 0.93 0.82 -0.24 0.19 0.92

FeO

OH

0.04 0.60 0.72 0.07 0.50 0.66 1.00 -0.26 0.46 0.32 0.36 0.44 0.53 -0.11 0.56 0.44 0.67 0.45 0.61 0.62 0.52 0.62 0.60 0.22 0.19 0.72

Ga le na

0.31 0.06 0.09 0.16 0.12 0.10 -0.26 1.00 -0.27 -0.09 -0.06 0.09 -0.17 0.08 0.06 -0.03 0.03 -0.20 0.04 0.06 0.04 0.02 0.14 0.05 0.13 0.14

MnO

OH

0.02 0.44 0.45 0.07 0.30 0.40 0.46 -0.27 1.00 0.11 0.44 0.26 0.44 -0.06 0.37 0.38 0.46 0.13 0.46 0.44 0.41 0.52 0.56 0.07 0.11 0.44

Paint 0.23 0.42 0.49 -0.01 0.28 0.49 0.32 -0.09 0.11 1.00 -0.06 0.38 0.13 -0.12 0.38 0.30 0.46 -0.11 0.44 0.43 0.38 0.44 0.36 -0.05 -0.13 0.45

PbAs

O

-0.05 0.12 0.19 -0.28 0.14 0.07 0.36 -0.06 0.44 -0.06 1.00 0.19 0.55 -0.05 0.11 0.30 0.08 0.45 0.05 0.07 -0.01 0.07 0.20 0.60 0.09 0.25

PbFe

OOH

0.07 0.67 0.57 0.48 0.35 0.59 0.44 0.09 0.26 0.38 0.19 1.00 0.31 0.31 0.66 0.50 0.65 -0.19 0.66 0.66 0.69 0.66 0.78 0.01 0.55 0.68

PbM

O

-0.05 0.12 0.20 -0.20 -0.01 0.13 0.53 -0.17 0.44 0.13 0.55 0.31 1.00 0.00 0.01 -0.07 0.08 0.22 0.05 0.07 0.01 0.10 0.37 0.56 0.16 0.28

PbM

SO4

0.01 0.06 -0.02 0.01 -0.02 0.06 -0.11 0.08 -0.06 -0.12 -0.05 0.31 0.00 1.00 0.20 -0.01 0.03 -0.32 0.05 0.06 0.35 0.06 0.10 0.14 0.29 0.10

PbO 0.19 0.89 0.80 0.44 0.60 0.84 0.56 0.06 0.37 0.38 0.11 0.66 0.01 0.20 1.00 0.73 0.90 -0.23 0.91 0.90 0.87 0.90 0.76 -0.36 0.27 0.81

PbSi

O4

0.16 0.81 0.72 0.29 0.58 0.75 0.44 -0.03 0.38 0.30 0.30 0.50 -0.07 -0.01 0.73 1.00 0.81 0.12 0.82 0.83 0.77 0.81 0.68 -0.16 0.17 0.79

Solde r

0.27…