&EFA
United States
Environmental Protection
Agency
EPA/600/R-08/060
January 2008
Mine Waste Technology
Program
Linking Waterfowl with
Contaminant Speciation in
Riparian Soils
Bull Run Lake Test Site
Black Rock Slough Test Site
-------
EPA/600/R-08/060
January 2008
MINE WASTE TECHNOLOGY PROGRAM
LINKING WATERFOWL WITH CONTAMINANT
SPECIATION IN RIPARIAN SOILS
By:
Suzzann Nordwick
MSB Technology Applications, Inc.
Mike Mansfield Advanced Technology Center
Butte, Montana 59702
Under Contract No. DE-AC09-96EW96405
Through EPA lAGNo. DW89939550-010-0
Norma Lewis, EPA Project Officer
Systems Analysis Branch
National Risk Management Research Laboratory
Cincinnati, Ohio 45268
This study was conducted in cooperation with
U.S. Department of Energy
Environmental Management Consolidated Business Center
Cincinnati, Ohio 45268
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
-------
Notice
The U.S. Environmental Protection Agency (EPA) through its Office of Research and Development
funded the research described here under IAG DW89939550-010-0 through the U.S. Department of
Energy (DOE) Contract DE-AC09-96EW96405. It has been subjected to the Agency's peer and
administrative review and has been cleared for publication as an EPA document. Reference herein to any
specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise,
does not necessarily constitute or imply its endorsement or recommendation. The views and opinions of
authors expressed herein do not necessarily state or reflect those of EPA or DOE, or any agency thereof.
-------
Foreword
The U.S. Environmental Protection Agency is charged by Congress with protecting the Nation's land, air,
and water resources. Under a mandate of national environmental laws, the Agency strives to formulate
and implement actions leading to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research program is providing data and
technical support for solving environmental problems today and building a science knowledge base
necessary to manage our ecological resources wisely, understand how pollutants affect our health, and
prevent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for investigation of
technological and management approaches for preventing and reducing risks from pollution that threaten
human health and the environment. The focus of the Laboratory's research program is on methods and
their cost effectiveness for prevention and control of pollution to air, land, water, and subsurface
resources; protection of water quality in public water systems; remediation of contaminated sites,
sediments, and groundwater; prevention and control of indoor air pollution; and restoration of
ecosystems. The NRMRL collaborates with both public and private sector partners to foster technologies
that reduce the cost of compliance and to anticipate emerging problems. NRMRL's research provides
solutions to environmental problems by developing and promoting technologies that protect and improve
the environment; advancing scientific and engineering information to support regulatory and policy
decisions; and providing the technical support and information transfer to ensure implementation of
environmental regulations and strategies at the national, state, and community levels.
This publication has been produced as part of the Laboratory's strategic long-term research plan. It is
published and made available by EPA's Office of Research and Development to assist the user
community and to link researchers with their clients.
Sally Gutierrez, Director
National Risk Management Research Laboratory
in
-------
Abstract
This report summarizes the results of Mine Waste Technology Program (MWTP) Activity III, Project 38,
Linking Waterfowl with Contaminant Speciation in Riparian Soils, implemented and funded by the U.S.
Environmental Protection Agency (EPA) and jointly administered by EPA and the U.S. Department of
Energy (DOE). This project addressed EPA's technical issue of Mobile Toxic Constituents - Water and
Acid Generation.
Soil samples were collected from the Coeur d'Alene River Basin and were analyzed for mineralogy and
metal contaminant speciation. Both phosphorus (P)-treated soils and untreated soils were examined to
determine the effect of P-amendment on metal speciation. Previous studies suggested P-amendments
result in precipitation of poorly soluble lead phosphate minerals. In this study, P appears to associate with
iron bearing minerals in the soil, whereas lead associates predominantly with manganese bearing phases.
The research conducted on site mineralogy and speciation generated no irrefutable evidence that P-
amendments promoted formation of poorly soluble lead (Pb)-P mineral phases. In theory, such phases
would lower Pb bioavailability in waterfowl exposed to Pb-contaminated soils and sediments. Thus,
development of a screening-level method for assessing P-treatment effectiveness (and subsequent
reduction in Pb bioavailability) becomes a critical issue.
This need is addressed by the two-step sequential extraction procedure that simulates the gizzard and
intestinal phases of a typical waterfowl's gastrointestinal tract. Dr. Strawn's approach is a modified
version of the physiologically based extraction test (PBET) for estimating Pb bioaccessibility in humans,
and is subsequently called W-PBET. The gizzard phase of this test demonstrated high Pb extraction
reproducibility and accuracy. The Pb bioaccessibility results were positively correlated with those from
waterfowl fed contaminated and in situ-treated soils from the lower Coeur d'Alene River Basin.
Therefore, W-PBET is a promising, cost-effective method for initial assessment of site-specific Pb
bioavailability in waterfowl.
IV
-------
Contents
Page
Notice ii
Foreword iii
Abstract iv
Contents v
Figures vii
Tables ix
Acronyms and Abbreviations x
Acknowledgments xii
Executive Summary ES-1
1. Introduction 1
1.1 Project Description 1
1.2 Background 1
1.3 Scope of Work 2
1.4 Goals and Objectives 2
2. Technologies 4
2.1 Physicochemical Characterization Tools 4
2.1.1 Mineralogical Analysis 4
2.1.2 Chemical Cycling Analysis 4
2.1.3 Thermodynamic Database 4
2.2 Lead Bioavailability versus Bioaccessibility Assessment Tools 4
2.2.1 Waterfowl Feeding Study 4
2.2.2 Lead Bioaccessibility Estimation 5
2.2.3 Data Correlation 5
3. Mineral and Contaminant Characterization in Soils from the Coeur d'Alene River Basin 6
3.1 Sampling 6
3.2 Analysis 6
3.2.1 Electron Microprobe Analysis 6
3.2.2 X-Ray Diffraction 7
3.3 Results Summary 7
3.3.1 Electron Microprobe Analysis 8
3.3.2 AOD and CBD Extractable Iron and Manganese Results 8
3.3.3 FTIR Analysis 9
3.3.4 XRD Analysis 9
3.4 Conclusions 9
4. Lead Bioaccessibility to Waterfowl in the Lower Coeur d'Alene Basin Part 1: Development of a
Physiologically Based Extraction Test for Waterfowl 19
4.1 Introduction 19
4.1 Waterfowl Physiologically Based Extraction Test Design 20
4.2 Gastric and Small Intestine pH 20
4.3 Soil Mass and Fluid Volume 21
4.4. Stomach Mixing 21
-------
Contents (Cont'd)
Page
4.5 Soil Particle Size 21
4.6 Stomach Emptying Rate and Small Intestinal Transit Time 21
4.7 Temperature 21
4.8 Gastrointestinal Fluids 21
4.9 Soils 22
4.10 W-PBET Procedure 23
4.10.1 Gizzard Phase 23
4.10.2 Intestinal Phase 23
4.11 Effect of W-PBET Parameters on Metal Extractability 23
4.12 Data Analysis 23
4.13 Results and Discussion 24
4.13.1 Sensitivity Analyses 24
4.13.2 W-PBET Lead and In Vivo Lead Comparison 25
4.13.3 W-PBET Results for Lead, Zinc, Cadmium, and Manganese 25
4.14 Discussion and Conclusions 27
5. Lead Bioaccessibility to Waterfowl in the Lower Coeur d'Alene River Basin Part 2: Seasonal
Effect on Metal Bioaccessibility 33
5.1 Introduction 33
5.1 Soil Sampling 33
5.2 W-PBET Experiment 34
5.3 Data Analysis 34
5.4 Results and Discussion 35
5.5 Conclusions 37
6. Geochemical Modeling 41
6.1 Introduction 41
6.2 Methods 41
6.3 Results of Geochemical Modeling for Pb and Fe in Soils 42
6.4 Evaluation Cd and Zn Solubility 44
6.5 Summary 44
7. Summary of Quality Assurance Activities 61
7.1 Introduction 61
7.2 Quality Assurance Assessment 61
8. Conclusions and Recommendations 63
8.1 Conclusions 63
8.1.1 Mineralogical Analyses 63
8.1.2 Metals Bioaccessibility to Waterfowl 63
8.1.3 Geochemical Modeling 63
8.2 Recommendations 63
9. References 65
Appendix A: D. G. Strawn's Final Report to MSE, dated January 26, 2006 A-l
vi
-------
Figures
Page
1-1. Coeur d'Alene Basin location map 3
3-la. 2003 photograph of Bull Run Lake test site near Rose Lake, Idaho 10
3-lb. 2003 photograph of Black Rock Slough test site near Rose Lake, Idaho 11
3-2. Plot schematic 11
3-3. FTIR spectra of clay-size fraction of soils from Plot 2, 4, 6, and 8 12
3-4. FTIR spectra of AOD-treated soil samples (clay-size fraction) 12
3-5. FTIR spectra of CBD-treated soil samples (clay-size fraction) 13
3-6. XRD analysis of clay sample from site 2, showing stick patterns of the mineral set (kaolinite,
muscovite, quartz, siderite, clinochlore, and lepidocrocite) 13
3-7. XRD analysis of clay sample from site 4, showing stick patterns of the mineral set (kaolinite,
muscovite, quartz, siderite, clinochlore, and lepidocrocite) 14
3-8. XRD analysis of clay sample from site 6, showing stick patterns of the mineral set (kaolinite,
muscovite, quartz, and siderite) 14
3-9. XRD analysis of clay sample from site 8, showing stick patterns of the mineral set (kaolinite,
muscovite, quartz, and siderite) 15
3-10. XRD data with peaks forgoethite (G) and ferrihydrite (F) indicated 15
3-11. Differential XRD for composite sample 4. Peaks for goethite (G) and ferrihydrite (F) indicated. 16
3-12. Diagram illustrating biogeochemical cycling of Pb in the environment 16
4-1. pH effect on Pb extractability in the gizzard. Error bars represent one standard deviation of
triplicates (R2 = 0.97) 28
4-2. Incubation time effect on Pb solubility in the gizzard phase. Error bars represent one standard
deviation of triplicates 28
4-3. Effect of grinding on extractable Pb in the simulated gizzard. Error bars represent one
standard deviation of triplicates 29
4-4. Relationship between extractable metal in the simulated gizzard and soil to fluid ratio in the
simulated gizzard solution (R2 = 0.96) 29
4-5. Log (a) and linear (b) correlations between Pb concentrations in the simulated gizzard and Pb
concentrations in the blood 30
4-6. Lead, Zn, Mn, and Cd release in the W-PBET gizzard extractions from the Lower Coeur
d'Alene Basin soils. Error bars represent one standard deviation (N = 4) 30
4-7. Correlation between Zn and Cd extractability in the W-PBET gizzard phase from the P-amended
and unamended Lower Coeur d'Alene River soils (R2 = 0.96) 31
5-1. Hypothesized Eh-pH stability diagram for Pb at the test plots. Assumed aqueous concentrations
are listed at top 38
5-2. W-PBET bioaccessibility of Pb (a), Cd (b), Zn (c) and Mn(d) in the soils collected from Bull
Run Lake and Black Rock Slough soils at different times. Plots Bull-P and Black-P are P-
amended; Plots Bull and Black are unamended. Error bars represent one standard deviation
from discrete samples within aplot (N = 3) 39
6-1. Aqueous Pb speciation as a function of pH. Input data are listed in Table 6.1. No solids were
allowed to precipitate 46
6-2. Saturation index for Pb minerals as a function of pH. System parameters are defined in Tables
6-land6-2(pe = 3.5) 46
6-3. Saturation index for Pb minerals as a function of pH. System parameters are defined in Tables
6-1 and 6-2 (pe = 0) 47
vn
-------
Figures (Cont'd)
Page
6-4. Saturation index for Pb minerals as a function of pH. System parameters are defined in Tables
6-1 and 6-2 (pe =-2.6) 47
6-5. Aqueous Pb concentrations as a function of pH controlled by several Pb-phosphate minerals and
observed Pb concentrations in P-amended and non-amended field sites 48
6-6. Total dissolved Pb concentrations as a function of temperature controlled by chloropyromorphite
dissolution 48
6-7. Saturation index for Fe minerals as a function of pH. System parameters are defined in Table
6-1 and Table 6-2 (pe = 3.5) 49
6-8. Saturation index for Fe minerals as a function of pH. System parameters are defined in Table
6- land Table 6-2 (pe = 0) 49
6-9. Saturation index for Fe minerals as a function of pH. System parameters are defined in Table
6-1 and Table 6-2 (pe = -2.6) 50
6-10. Redox stability diagram for Fe, T = 15 °C, P = 1.013 bars, aFe= lO^301, aci = 10~3405, aHCo3-= 10"
2499, aHpo4-= 10~2824, aSo4-= 10~2807; Suppressed: goethite, hematite, magnetite 51
6-11. Stability diagram for Pb minerals as a function of HPO42 concentration and pH (Nriagu, 1984).
Calculated for aso42- = aHco3- = 10"3, aAB+ = 10"6. Solid lines are for aPb2+ = 10"6; dashed lines
are for apb2+ = 10"5 52
6-12. Activity ratio/product diagram showing the relative stability of Pb bearing minerals as a function
of pH, H2PO4- activity, and Pb activity 53
6-13. The solubility of various Pb silicates and phosphates compared to cerussite when phosphate is
controlled by various solid phases, as indicated above x-axis, and CO2(g) is 0.003 atm. From
Lindsay (1979) 54
6-14. Stability diagram for Pb minerals as a function of redox potential and pH, adapted from Nriagu
(1984) 55
6-15. Redox stability diagram specific to soil pore water conditions given in Table 6-1 56
6-16. Saturation index for Cd minerals as a function of pH. System parameters are defined in Table 1
and Table 2 (pe = 3.5, except as noted) 57
6-17. Saturation index for Zn minerals as a function of pH. System parameters are defined in Table
6-1 and Table 6-2 (pe = 3.5, except as noted) 57
Vlll
-------
Tables
Page
2-1. General Study Design for the Waterfowl Feeding Study 5
3-1. Elemental Analysis Results of Composite Soils from Study Plots 2, 4, 6, and 8 (values in
parenthesis are standard deviation of 3 replicates) 17
3-2. Particle Size Analyses for Composite Sample from Plots 2, 4, 6 and 8 17
3-3. Associations between Elements in Soil Samples Analyzed by Electron Microprobe 17
3-4. AOD and CBD Extraction Results for Plot 2, 4, 6, and 8 Composite Soils (values in
parenthesis are standard deviations for 3 replicates) 17
3-5. FTIR Peaks in Clay Fractions from Plots 2, 4, 6, and 8 18
3-6. XRD Analysis Results 18
4-1. Summary of In Vitro Parameters Used in Different Models and Proposed W-PBET 31
4-2. Lead Bioaccessibility and Bioavailability Values Based on W-PBET and Bird Feeding Studies;
Pb and P Concentrations in the Soils and Blood Pb Values are from Heinz et al. (2004) 32
4-3. Correlation Coefficients between W-PBET Pb and In Vivo Pb (N = 32, p < 0.05) 32
5-1. Metal Concentrations (Means and Ranges) in the Lower Coeur d'Alene Basin Study Area 40
6-1. Simulated Pore Water Concentrations Used as Inputs for Aqueous Speciation and Solubility
Modeling in Soils 58
6-2. Reactions and Equilibrium Constants for All Aqueous Species Considered (Complete
Thermodynamic Database Used Was from Schecher, 1998) 59
6-3. Reactions and Equilibrium Constants for All Minerals Considered (Complete Thermodynamic
Database Used Was from Schecher, 1998) 60
IX
-------
Acronyms and Abbreviations
ABA absolute bioavailability
Al aluminum
ANOVA analysis of variances
AOD ammonium oxalate
As arsenic
C carbon
Ca calcium
CBD citrate-bicarbonate-dithionite
Cd cadmium
CERCLA Comprehensive Environmental Response, Compensation, and Liability Act
Cl chlorine
DOE U.S. Department of Energy
DTPA diethylene triamine pentaacetic acid
EDS energy dispersive spectrum
EH oxidation reduction potential
EMPA electron microprobe analysis
EPA U.S. Environmental Protection Agency
Fe iron
FTIR Fourier transform infrared spectrometer
GI gastrointestinal
HC1 hydrochloric acid
ICP-AES inductively coupled plasma atomic emission spectrometer
IVB in vitro bioaccessibility
Mn manganese
MSE MSE Technology Applications, Inc.
MWTP Mine Waste Technology Program
N normal
N2 nitrogen
NaCl sodium chloride
NIST National Institute of Standards and Technology
NRMRL National Risk Management Research Laboratory
ORP oxidation-reduction potential
P phosphorus
p probability
Pb lead
PBET physiologically based extraction test
PbB blood lead
pe negative logio of electron activity
pH negative logic of hydrogen ion concentration
QA quality assurance
QAPP quality assurance project plan
rpm revolutions per minute
RSD relative standard deviation
S sulfur
Si silicon
-------
Acronyms and Abbreviations (Cont'd)
WDS wavelength dispersive spectrum
W-PBET waterfowl physiologically based extraction test
XRD X-ray diffraction
Zn zinc
XI
-------
Acknowledgments
This document was prepared by MSB Technology Applications, Inc. (MSB) for the U.S. Environmental
Protection Agency's (EPA) Mine Waste Technology Program (MWTP) and the U.S. Department of
Energy's (DOE) Environmental Management Consolidated Business Center. Ms. Diana Bless is EPA's
MWTP Project Officer, while Mr. Dave Hicks is DOE's Technical Program Officer. Ms. Helen Joyce is
MSB's MWTP Program Manager. Ms. Norma Lewis was the EPA Project Manager for this project.
Ms. Suzzann Nordwick was the MSB MWTP Project Manager. Dr. Daniel G. Strawn was the Project
Director from the University of Idaho, Department of Plant, Soil and Entomological Sciences.
xn
-------
Executive Summary
The Mine Waste Technology Program (MWTP), Activity III, Project 38, Linking Waterfowl with
Contaminant Speciation in Riparian Soils was implemented by the U.S. Environmental Protection
Agency (EPA) and jointly administered by EPA and the U.S. Department of Energy (DOE).
The two major components of this project were to:
- evaluate mineralology and contaminant speciation in phosphorus (P)-treated and untreated soils;
and
- evaluate a physiologically based extraction test for determining lead (Pb) bioaccessibility in
P-treated and untreated soils.
Soil samples from the Coeur d'Alene River Basin were analyzed for mineralogy and metal contaminant
speciation. Both P-treated soils and untreated soils were examined to determine the effect of
P-amendment on metal speciation. Other studies have suggested P-amendments lead to precipitation of
poorly soluble Pb phosphate minerals. No evidence was found for this behavior in this study. Instead,
P appears to associate with iron (Fe)-bearing minerals in the soil, whereas Pb associates predominantly
with manganese (Mn)-bearing phases.
Due to variations in soil physicochemical properties, species physiology, and contaminant speciation, Pb
toxicity is difficult to evaluate without conducting in vivo dose-response studies. However, such tests are
expensive and time consuming, making them unrealistic to use in assessment and management of
contaminated environments. One possible alternative is to develop a physiologically based extraction test
(PBET) that can be used to measure relative bioaccessibility. The development and correlation of a
PBET test designed to measure the bioaccessibility of Pb to waterfowl (W-PBET) is discussed in this
report. The W-PBET results showed a positive correlation with tissue Pb levels from a bird feeding
study. The W-PBET test was applied to investigate remediation success in contaminated soils from the
Coeur d'Alene River Basin, Idaho. The W-PBET Pb concentrations were positively correlated with the
bird feeding study results, exhibiting a logarithmic relationship. W-PBET concentrations for cadmium,
zinc, and Mn contaminants present in the soils were evaluated. W-PBET results for these contaminants
varied, depending on site conditions, soil amendment, and element. Results from this study indicate that
a W-PBET extraction test can be used to assess relative changes in bioaccessibility and, therefore, is a
valuable test to manage and remediate contaminated wetland soils.
ES-1
-------
1. Introduction
1.1 Project Description
This report summarizes the results of Mine
Waste Technology Program (MWTP) Activity
III, Project 38, Linking Waterfowl with
Contaminant Speciation in Riparian Soils,
implemented and funded by the U.S.
Environmental Protection Agency (EPA) and
jointly administered by EPA and the U.S.
Department of Energy (DOE). This report
encompasses the following four areas.
Mineral and Contaminant Characterization
in Soils from the Coeur d'Alene River Basin
Lead Bioaccessibility to Waterfowl in the
Lower Coeur d'Alene Basin Part 1:
Development of a Physiologically Based
Extraction Test for Waterfowl
Lead Bioaccessibility to Water in the Lower
Coeur d'Alene Basin Part 2: Seasonal
Effect on Metal Bioaccessibility
Geochemical Modeling using PHREEQCi
software from the U.S. Geological Survey
This report is summarized from a document
prepared by the University of Idaho's
Department of Plant, Soil, and Entomological
Sciences that was submitted to MSE Technology
Applications, Inc. (MSE) as the University of
Idaho's final deliverable for this project (Strawn,
2006; see Appendix A). The University of
Idaho's role on this project was to perform
laboratory and field testing and report on results.
MSB's role was to provide project direction,
oversight of the University of Idaho, reporting,
and interface with EPA.
This project was a follow-on to a previous study
completed by University of Idaho. In the
previous study, the ability of phosphate
amendments to reduce the bioavailability of lead
(Pb) to waterfowl was investigated by the Idaho
Department of Environmental Quality and the
U.S. Fish and Wildlife Service. The Coeur
d'Alene Basin Commission and EPA Region 10
jointly funded this investigation.
1.2 Background
The Coeur d'Alene mining district is rich in
economically viable minerals and has yielded
significant quantities of silver, Pb, zinc (Zn), and
other metals. This mining region has produced
in excess of one billion ounces of silver, eight
and one-half million tons of Pb and three million
tons of Zn (Bennett 1989). However, because of
mining and mineral processing operations, soils,
sediments, and waters of the Coeur d'Alene
River Basin have been heavily contaminated.
Subsequently, the Coeur d'Alene Basin (Figure
1-1) was placed on the Superfund National
Priority List in 1984. Mill tailings from more
than 90 mines, including America's largest
underground mine (Bunker Hill) and deepest
mine (Star-Morning), were released into the
South Fork of the Coeur d'Alene River and its
tributaries (Bennett 1989). It is estimated that
56 million metric tons of mill tailings have been
deposited in the river (Long 1998a). Dumping
into the river was discontinued in 1968 when
mandates required tailing storage or return of
tailings to the mines.
Dredged tailings were commonly used for local
construction fill materials, brick manufacturing,
and railroad ballast, which led to the spread of
the contamination into populated areas (Davis
1993). Precipitation and flooding events have
moved tailings into lakes and wetlands along the
river.
Recovery efforts since 1900 have reclaimed
approximately 6 million metric tons of deposited
tailings from creeks and dumps (Mitchell and
Bennett 1983). In the 1930s, the Mine Owners
Association dredged a portion of the Coeur
d'Alene River near Cataldo Mission Flats and
deposited the collected tailings on the nearby
floodplain (Cassner 1991). However, unknown
amounts of tailings still reside in the Coeur
d'Alene River (Mitchell and Bennett 1983).
-------
Wildlife habitats and recreational facilities
common along the river and its wetlands
increase the environmental significance of
mining contaminants present. Animal
communities use the river basin's lakes,
wetlands, and riparian corridors as breeding
areas, feeding areas, and migratory flight path
stopovers.
Studies have shown that fish and fowl caught in
these areas for the purpose of consumption have
high levels of trace metals. Many camping
locations, bike trails, and other recreation sites
occur in contaminated areas. A prime concern
for human exposure is ingestion of soils within
these recreation sites, especially during dry and
dusty conditions, as well as contamination from
drinking contaminated waters.
1.3 Scope of Work
Project 38 was an investigation to determine
contaminant reaction processes in previously
treated soils. The project focused on gaining
insight into phosphorous (P)-Pb interactions in
riparian soils using spectroscopic and
microscopic techniques.
The reactions involving Pb and other metals of
regulatory concern, P-containing soil
amendments, and solid-phase soil components
were evaluated.
1.4 Goals and Objectives
The project objectives were to determine the
reaction mechanisms of Pb in P-amended soils
and relate this information to the
bioavailability of Pb as indicated by the
waterfowl study results.
The goal of this study was to characterize the
mineralogy and contaminant speciation in soil
samples from field sites in the Coeur d'Alene
River Basin. Elemental concentration in the
soils was measured as a function of particle size,
and elements were mapped using an electron
microprobe. Bulk mineralogy was characterized
using x-ray diffraction, Fourier transform
infrared spectrometry (FTIR), and selective
extraction. Assessment of P-amendments on Pb
partitioning was evaluated to determine if
P-enhanced in situ Pb immobilization in the
soils was occurring.
-------
franklin D. ftwsevert Lite
(Columbia Mm)
0 510 15 NORTH
Approximate Scale In Miles
Northern Rocky Mountains Physiographic Region
Figure 1-1. Coeur d'Alene Basin location map.
-------
2. Technologies
The University of Idaho's role on this project
was to perform laboratory and field testing and
report on results. MSB's role was to provide
project direction, oversight of the University of
Idaho, reporting, and interface with EPA.
2.1 Physicochemical Characterization
Tools
This study characterized the mineralogy and
contaminant speciation in soil samples from
field sites. Elemental concentration in the soils
was measured as a function of particle size, and
elements were mapped using an electron
microprobe. Bulk mineralogy was characterized
using x-ray diffraction, FTIR, and selective
extraction. An assessment of P-amendments on
Pb in soils was evaluated.
2.1.1 Mineralogical Analysis
Experiments using advanced spectroscopic and
microscopic techniques were conducted. Soil
samples were collected and analyzed using
redox preservation techniques with
spectroscopic and microscopic analytical
instrumentation.
2.1.2 Chemical Cycling Analysis
Mechanistic data (i.e., pH and Eh) were collected
to determine how seasonal changes affected soil
mineralogy, Pb and P speciation, and
bioavailability characteristics.
2.1.3 Thermodynamic Database
The experimental and mechanistic data were
used along with a thermodynamic database to
generate aqueous phase stability diagrams and to
develop the model of Pb behavior at the
waterfowl plots.
2.2 Lead Bioavailability versus
Bioaccessibility Assessment Tools
Contaminant bioavailability is the ratio of
absorbed dose to ingested dose. For example,
30 micrograms (|o,g) of Pb measured in the
bloodstream following ingestion of 100 |o,g Pb in
soil represents an absolute bioavailability (ABA)
of 30%. Contaminant in vitro bioaccessibility
(IVB) indicates the potential for a substance to
be taken up into the bloodstream. For example,
525 |o,g Pb measured in simulated gastric fluid
contacting soils containing 2,250 |o,g Pb
represents an IVB of about 23%.
Because of its relative simplicity and lower cost,
the IVB method was considered ideal for site-
specific screening of contaminant
bioavailability. However, a generally acceptable
correlation between the ABA and IVB results
must be demonstrated before this approach can
occur. In the present case, this involved:
- a waterfowl feeding study to estimate Pb
bioavailability in floodplain soils (along
the Coeur d'Alene River); versus
- development of an in vitro method that
simulates Pb bioaccessibility in the
gastrointestinal tract of waterfowl.
MWTP Activity III, Project 38 focused on the
latter effort. However, interpretation of the IVB
results required some background on the
waterfowl feeding study performed by the U.S.
Geological Survey's Patuxent Wildlife Research
Center. The respective methodologies are
summarized below.
2.2.1 Waterfowl Feeding Study
The general study design is shown in Table 2-1
(Heinz et al, 2004). Male, 2-week old mallard
ducks were kept outdoors in 1-square meter pens
and given feed and fresh water ad libitum over
an 8-week period. Venous blood samples were
collected at the end of the feeding period, prior
to humane euthanasia. Samples of blood, liver,
and kidney from each bird were prepared and
analyzed for their respective Pb levels. ABAs
were calculated by dividing in vivo tissue
concentrations by normalized Pb levels in diet,
for each of the eight groups.
-------
2.2.2 Lead Bioaccessibility Estimation
Dr. D. G. Strawn developed a physiologically
based extraction test (PBET) that simulates Pb
behavior in the gastrointestinal tract of
waterfowl (W-PBET). Development and
application of the W-PBET to Coeur d'Alene
floodplain soils are discussed in Sections 4 and
5, respectively, of this report. Additional details
are presented in his final report (Strawn, 2006),
which is attached in CD-form to this report as
Appendix A.
2.2.3 Data Correlation
The physicochemical and biological-related
information were correlated with each other so
as to produce preliminary assessments
regarding:
- how P-treatment of Pb-contaminated
soils affected Pb speciation and
bioavailability under varying
environmental conditions; and
- the credibility of the W-PBET results
being used as surrogates for waterfowl
feeding studies.
The first issue is addressed in Sections 3 and 6,
while the latter is addressed in Sections 4 and 5,
of this report.
Table 2-1. General Study Design for the Waterfowl Feeding Study
Group
1
2
3
4
5
6
7
8
Number of
Animals
10
10
10
10
10
10
10
10
Sediment Source
Round Lake
Harrison Slough
Harrison Slough
Black Rock Slough
Black Rock Slough
Bull Run Lake
Bull Run Lake
Bull Run Lake
Phosphate
Amendment
No
No
Yes
No
Yes
No
Yes
No
Where Aged a
Lab
Lab
Lab
Lab
Field
Lab
Lab
Field
Average Concentration in Feed
(ppm, dry weight basis)
Pb P
2.9 87
507 75
488 1,248
535 85
458 2,232
791 53
757 1,224
683 2,556
Note: a Water-saturated soils were allowed to react for 5 months (i.e., to form pyromorphite) prior to use in the feeding study.
Source: Heinz et al. 2004.
-------
3. Mineral and Contaminant Characterization in Soils from the
Coeur d'Alene River Basin
3.1 Sampling
Soil samples were collected from two sites
located in the Coeur d'Alene River Basin: the
northwest shore of Bull Run Lake and the
northeast site of the Black Rock Slough. These
sites are located near Rose Lake within Operable
Unit-3 of the Bunker Hill Superfund site (Figure
1-1). Figures 3-la and 3-lb present photographs
(2003) of the test sites. As part of a previous
effort by the University of Idaho (see
Introduction for more details), different soil
amendments were used to treat the three plots
from each site. These were:
- liquid phosphorus fertilizer with lime;
- ground fishbone apatite; and
- lime.
The fourth plot was untreated. A schematic of
the plots is shown in Figure 3-2.
Four of the eight plots were selected, measured,
and staked in the spring of 2003 to the following
specifications.
Plots 2, 4, and 6 measured 20 feet by 20 feet
with a buffer of 1 foot on all sides. These
plots consisted of 15 subplots (3 rows with 5
plots each).
Plot 8 measured 20 feet by 25 feet with a
buffer of 1 foot on the north, west, and south
side that consisted of 21 subplots (3 rows
with 7 plots each).
Samples were collected randomly from the
subplots specified above using a 20-centimeter
(cm) long, 5-cm diameter stainless steel sampler
with a plastic sleeve insert. Core samples were
submerged in liquid nitrogen (N2), sealed,
placed on ice and transported to the laboratory.
Soils were air-dried and crushed to passing pore
size of 1 millimeter (mm).
3.2 Analysis
Total metal concentrations were determined
using EPA method 3052. An electron
microprobe analysis (BMPA) was used to
provide the energy dispersive spectrum (EDS)
and wavelength dispersive spectrum (WDS)
images and graphs with a high degree of spatial
precision and sensitivity that corresponds to the
soil particle elemental concentration. Analytical
results are summarized in Section 3.3 and the
complete data package can be found in
Appendix A, the University of Idaho's final
deliverable for this project (Strawn, 2006).
3.2.1 Electron Microprobe Analysis
Three samples each from the amended Plots 2
and 6 and unamended Plots 4 and 8 were taken
in August 2003. Thin sections were made using
soil from the top 5 cm of each of the triplicate
cores and dried in the oven at 100 degrees
Celsius (°C). The soil, approximately 5 cm3,
was vacuum impregnated with an acrylic resin,
cut into thin sections, and mounted on
petrographic slides. The thin sections were
ground to a thickness between 250 micrometers
(|im) and 1 mm, and polished using 6-(im, 3-
(im, and 0.05-(im grits to achieve an acceptable
finish.
The 12 thin sections were randomly scanned
using a Cameca Camebax electron microprobe,
located at the Washington State University
Geology Department. During the scanning, in-
depth analysis of three to six areas was carried
out using a 4-micron beam, accelerating voltage
of 15 kilo electron volt (keV), and beam current
of 12 nanoamperes (nA). The detailed analysis
involved taking an electron backscatter image of
the thin section, creating a single WDS element
map of the same region for five elements [iron
(Fe), manganese (Mn), Pb, P, and silicon (Si)],
and generating an EDS portrait of six to twelve
distinct points within the area. The EDS portrait
provides a relative measure of elemental
-------
concentrations within the analysis area. The size
of the EDS peaks is a qualitative indication of
what elements are present.
3.2.2 X-Ray Diffraction
X-ray diffraction (XRD) was done on composite
samples to determine the dominant mineralogy
and crystalline structure of the soil samples.
Citrate-bicarbonate-dithionite (CBD) and
ammonium oxalate (AOD) treatments were used
to remove amorphous coatings and free Fe
oxides that act as cementing agents. Both
untreated and AOD and CBD treated samples
were run on the XRD using EVA software to
collect data and identify samples. The clay-
sized fraction from Plots 2, 4, 6, and 8 were also
analyzed on XRD.
Particle size analysis was performed on soil
composites from Plots 2, 4, 6, and 8.
Approximately 14 grams (g) of soil were added
to 60 milliliters (mL) of triple distilled water in
four 100-mL plastic centrifuge tubes. The four
soil-water mixtures were homogenized then
centrifuged at 750 revolutions per minute (rpm)
for approximately 2 minutes and 54 seconds to
separate clay-sized particles from silt and sand-
sized particles. The clay-containing supernatant
was decanted into a 500-mL graduated cylinder.
This procedure was repeated until the
suspensions in the 100-mL centrifuge tubes were
visibly free of clay-sized particles. The soil-clay
percentage was determined by massing two
oven-dried 10-mL aliquots sampled from the
thoroughly mixed clay-water solutions.
The remaining soil-water mixture was passed
through a 325-mesh sieve to separate the silt and
sand-sized particles. The sand-sized material
remaining in the 325-mesh was dried in an oven
at 70 °C. The dried sand-sized particles were
screened in a nest of sieves. Silt passing through
the nest of sieves was collected and added to the
total silt mass of the composite sample. The silt-
sized material that passed through the 325-mesh
sieve was allowed to settle and the silt-free
water was poured off. The remaining material
was dried in the oven at 70 °C and then
weighed.
Iron and Mn were extracted using AOD and
sodium CBD procedures. AOD is used to
remove Fe and Mn oxides while CBD is used to
reduce and extract Fe and Mn oxides. For AOD
extraction, triplicate 0.05-g subsamples from
composites 2, 4, 6, and 8 were placed in separate
100-mL plastic centrifuge tubes to which 60 mL
of 0.2 molar (M) ammonium oxalate [(NFL,^
C2O4] was added. The samples were covered to
exclude light and placed on a shaking table at
280 rpm, and allowed to mix thoroughly for 4
hours. After shaking, the samples were
centrifuged at 1,200 rpm for 15 minutes and 30
mL of extractant was collected. The extractant
was diluted with deionized water and stored in
polypropylene containers in preparation for
inductively coupled plasma atomic emission
spectrometer (ICP-AES) analysis.
For CBD extraction, triplicate 0.05-g
subsamples of composites 2, 4, 6, and 8 were
placed into 12 separate 100-mL centrifuge tubes
along with 45 mL of 0.3-Msodium citrate
(C6H5Na3O4'2H2O) and 5 mL of l-Msodium
bicarbonate. The samples were agitated at 15
rpm in a water bath of 80 °C for a 5-minute
temperature equilibration, after which 1 g of
reagent-grade sodium dithionite (Na2S2O4) was
stirred into the samples. Stirring of the samples
was performed continuously for 1 minute and
then intermittently approximately every 5
minutes for a total of 15 minutes. After 15
minutes, 1 g of sodium dithionite was added to
the samples. The samples were stirred
intermittently for 10 minutes, removed from the
water bath, allowed to cool to room temperature,
and centrifuged at 1,200 rpm for approximately
15 minutes. After centrifuging, 30 mL of the
extractant was collected, diluted 1:10 in
deionized water, and stored in polypropylene
containers in preparation for ICP-AES analysis.
3.3 Results Summary
Total elemental composition is shown in Table
3-1. Raw data can be found in the University of
-------
Idaho's final deliverable for this project (Strawn
2006; Appendix A). Plots 2 and 4 on Bull Run
Lake have higher concentrations of
contaminants than the plots near Black Rock
Slough (Plots 6 and 8). There are two
possibilities for this difference as follows.
The elevation difference between the two
sites allows for variable sediment
deposition. The Bull Run Lake sites are at a
lower elevation thus receiving more
contaminated sediment.
The difference in elevation also creates
different water table inundation periods,
creating variable biogeochemistry, which
affects the mobility of the contaminants.
Particle size for Plots 6 and 8 were silt loam.
Plots 2 and 4 had very fine sandy loam particles.
Size classifications are shown in Table 3-2. The
very fine sand fraction provided 67.8% or
greater of total sands in all samples and is not
shown in the table. Raw data can be found in
Appendix A, University of Idaho's final
deliverable for this project (Strawn, 2006).
Particle size differences were due to water
velocity and sedimentation rate, which are
impacted by elevation. Thus, fine particles will
preferentially settle at the high elevation sites
near Black Rock Slough and coarser particles
will settle at the lower elevation sites near Bull
Run Lake.
3.3.1 Electron Microprobe Analysis
Electron microprobe analysis was done on all
plots. The results are summarized in Table 3-3.
The WDS images and EDS plots are shown in
Appendix A, University of Idaho's final
deliverable for this project (Strawn, 2006).
Associations between elements in soil samples
were determined by visually estimating the
percentage of common elemental coverage
between WDS images. A high correlation was
defined as 75% to 100% mutual elemental
coverage in the WDS image, moderate
correlation had 50% to 74% mutual coverage,
and weak correlation had 25% to 49% mutual
coverage. Mutual coverage of less than 25%
was considered not visually correlated.
Qualitative analyses of the WDS images
revealed that greater than 50% of the scans
contained moderate to high correlations between
Fe/Mn and Fe/P. However, there was a poor
correlation between Mn/P, indicating that the P
preferentially associates with Fe not associated
with Mn. Closer examination of the EMPA
element maps suggests that Fe and P are most
strongly associated to the exterior surfaces of
larger mineral particles such as quartz. These
results are shown in Appendix A, University of
Idaho's final deliverable for this project (Strawn,
2006).
High correlations were observed between Pb and
Mn in 11% of the images, and moderate
correlations were observed in 30% of the
images. This suggests that the Pb has a
preferential association with Mn minerals over
Fe containing minerals, even if the Fe-bearing
mineral contained Mn. Only a small fraction of
the images showed correlation between Pb/P. It
is concluded that Pb is primarily associated with
Mn oxides, while P is associated with Fe oxides.
The bulk of the Si in the soil samples is not
associated with the other elements analyzed.
The overlap between Si and other elements most
likely occurs because Si is present in clay
minerals, which also have the other elements
associated with their structure or absorbed on
their surfaces.
3.3.2 A OD and CBD Extractable Iron and
Manganese Results
AOD extractable Fe comprised 54.3% to 76.8%
of the total Fe, indicating that most of the Fe in
the soils is poorly crystalline. Plots 2 and 4
show the total Fe and amount of extractable Fe
is greater than in Plots 6 and 8. This is because
of the higher rate of sediment deposition on
these plots compared to Plots 6 and 8. AOD
extractable Fe and Mn from Plot 4 are
-------
significantly greater than CBD extractable Fe
and Mn. This suggests that there is a significant
fraction of nonreducible Fe and Mn in the soil
from Plot 4. Fe(II) or Mn(II) adsorbed on
poorly crystalline minerals such as ferrihydrite
would be a possible reason for this observation.
Minerals such as Fe(II) and Mn(II) carbonates
may also be extracted with AOD but not CBD.
3.3.3 FTIR Analysis
FTIR spectra were collected from the clay-size
fractions of the four soils before and after
treatment with AOD and CBD. Results are
presented in Figures 3-3 through 3-5 and Table
3-4. The FTIR spectra have distinct bands for
kaolinite, quartz, and soil organic matter as
shown in Table 3-5. Distinct changes in the
spectra were observed when the soils were
extracted with AOD and CBD that appear to
correspond to the soil organic matter fraction.
3.3.4 XRD Analysis
To determine the mineral phases, XRD was run
on the less than 2-|o,m fractions of P-treated and
untreated soils. The soils were extracted with a
solution of CBD, a common extractant that
selectively removes the reducible free Fe and
Mn minerals. To enhance the detection
capabilities of Fe minerals, the XRD data from
the extracted sample was subtracted from the
non-extracted sample XRD data (differential
XRD). The resulting peaks are from the
minerals extracted by CBD. XRD from the
clay-size fraction of the four plots are presented
in Figures 3-6 through 3-9 and the results are
summarized in Table 3-6. Results from the
differential XRD are shown in Figures 3-10 and
3-11.
XRD analysis suggests that the minerals present
in the soils are quartz, mica, chlorite
(clinochlore), siderite, lepidocrocite, and poorly
crystalline goethite and ferrihydrite. No P or Pb
minerals were detected. The lack of detection of
these minerals indicates that:
- they are too poorly crystalline; and/or
- their concentration is below the
detection limit of the instrument.
Mica is a common primary mineral that
weathers to secondary layer silicates such as
chlorite and vermiculite. The secondary clay
minerals can have a significant contribution to
cation adsorption in the soils. Poorly crystalline
Fe oxides have large surface areas that
correspond to large sorption capacities for
metals and anions. Sorption capacity on oxides
is pH dependent. Siderite is a ferrous carbonate
that is not stable in oxidizing environments. The
redox status of the soils varies from oxic to
anoxic, depending on the level of the water
table, which is dependent on seasonal runoff and
flooding conditions. The presence of siderite in
the soils is most likely detrital because siderite is
a common mineral in the ore containing rocks,
and would require long periods of reducing
conditions to be diagenetic. The soils from Bull
Run Lake had much stronger XRD peaks for
siderite than the soil at Black Rock Slough,
which corresponds to the frequency of
inundation. Lepidocrocite is an Fe oxide
commonly observed in soils in which ferrous Fe
is oxidized. Plots 2 and 4 did not have XRD
peaks for lepidocrocite. The lack of
lepidocrocite on these plots may be a result of
the more dynamic redox environment that does
not allow for stable Fe oxides such as goethite
and lepidocrocite to form, but instead favors
meta-stable poorly crystalline oxides such as
ferrihydrite.
3.4 Conclusions
The research conducted on site mineralogy and
speciation has found no conclusive evidence that
P-amendments promoted the formation of poorly
soluble Pb-P mineral phases. However, the
results show that P is preferentially absorbed to
Fe oxide minerals and Pb is preferentially
associated with Mn oxide minerals. The fate of
P is important when considering amendment
rates to form poorly soluble Pb-P minerals.
Additional information regarding soil organic
carbon types and distribution would enhance the
understanding of this process.
-------
The selective extraction results and the XRD
analysis showed that highly reactive Fe and Mn
oxide phases and siderite were present in the
soils. Such information is important for
predicting reaction processes in the soil because
temporal and ecosystem processes impact the
stability of the Fe and Mn minerals, which will
impact contaminant release and P availability for
reacting with Pb or other metals, or leaching into
the surface water.
Based on the results of this research, a
conceptual model was developed for Pb
speciation and reactivity in the wetlands. This
model can be used to predict Pb bioavailability,
transport availability, temporal fluxes as a
function of water table and inundation, and
impacts of remediation. A generalized system
model is presented in Figure 3-12. Information
on mineral and contaminant speciation can be
input into this model to predict processes for
reactions between the various phases. This type
of predictive model is needed to develop
improved management and remediation
strategies, and develop new experiments that
will allow for quantitative analysis of
contaminant availability.
,,
Figure 3-la. 2003 photograph of Bull Run Lake test site near Rose Lake, Idaho.
10
-------
".
Figure 3-lb. 2003 photograph of Black Rock Slough test site near Rose Lake, Idaho.
O
0
0
:1.
Figure 3-2. Plot schematic.
11
-------
0)
u
a
CO
-O
cc
4000 3500 3000 2500 2000 1500 1000 500
wavenumber (cm"1)
Figure 3-3. FTIR spectra of clay-size fraction of soils from Plot 2, 4, 6, and 8.
c
ra
_Q
i_
O
CO
CO
4000
3500
3000
2500
2000
1500
1000
500
wavenumber (cm"
Figure 3-4. FTIR spectra of AOD-treated soil samples (clay-size fraction).
12
-------
c
CO
-8
o
to
_o
CD
4000 3500 3000 2500 2000 1500 1000 500
wavenumber (cm"1)
Figure 3-5. FTIR spectra of CBD-treated soil samples (clay-size fraction).
2-T heta - Scale
Figure 3-6. XRD analysis of clay sample from site 2, showing stick patterns of the mineral set (kaolinite, muscovite,
quartz, siderite, clinochlore, and lepidocrocite).
13
-------
2-Theta - Scale
Figure 3-7. XRD analysis of clay sample from site 4, showing stick patterns of the mineral set (kaolinite, muscovite,
quartz, siderite, clinochlore, and lepidocrocite).
Figure 3-8. XRD analysis of clay sample from site 6, showing stick patterns of the mineral set (kaolinite, muscovite,
quartz, and siderite).
14
-------
Figure 3-9. XRD analysis of clay sample from site 8, showing stick patterns of the mineral set (kaolinite, muscovite,
quartz, and siderite).
G F G F
10 15 20 25 30 35 40 45 50 55 60 65
composite site 2
composite site 4
Figure 3-10. XRD data with peaks for goethite (G) and ferrihydrite (F) indicated.
15
-------
25
30
35
40 45
Degree 2 Theta
50
55
60
65
Figure 3-11. Differential XRD for composite sample 4. Peaks for goethite (G) and ferrihydrite (F) indicated.
Fluxes
Geochemical System
GasPh
C02, 02
Solid Surfaces
>Oxides (redox)
Clays
Sulfides (redox)
Carbonates
Organic Matter (redox)
Pb-Minerals
Pb-phosphates
-Pb-Mn/Fe oxides {redox)
Pb-carbonates
Pb(ll) Aqueous Species
Dissolved Metals
_rBio-available
Biological ^
activity
> Pb flux
Metal flux
*^ "Phosphate flux
Figure 3-12. Diagram illustrating biogeochemical cycling of Pb in the environment.
16
-------
Table 3-1. Elemental Analysis Results of Composite Soils from Study Plots 2, 4, 6, and 8 (values in parenthesis are
standard deviation of 3 replicates)
Plot As
Cd
Fe Mn
P Pb
Sulfur (S)
Zn
milligrams per kilogram (mg/kg)
80.7
2 (4.4)
136
4 (8.3)
37.9
6 (2.6)
55.9
8 (0.8)
30.2
(1.9)
16.4
(0.4)
11.2
(0.1)
9.40
(0.4)
78,600 5,738.7
(742) (161)
84,800 7,312.2
(1,060) (165)
40,200 1,440
(138) (47.6)
47,800 2,750
(1,350) (113)
24,800 5,180
(1,070) (191)
597 4,500
(59.6) (56.9)
16,400 3,560
(234) (37.4)
1,320 3,780
(10.1) (110)
1,738.6
(74.3)
1,841.2
(54.9)
432.1
(18.7)
457.2
(8.1)
2,350
(60.0)
2,840
(39.9)
769
(5.4)
1,090
(22.9)
Table 3-2. Particle Size Analyses for Composite Sample from Plots 2, 4, 6 and 8
Plot 2 Composite
Plot 4 Composite
Plot 6 Composite
Plot 8 Composite
Sand
58.3%
59.7%
35.6%
26.6%
Silt
35.0%
35.3%
55.3%
63.6%
Clay
6.64%
5.06%
9.14%
9.82%
Texture Classification
Very Fine Sandy Loam
Very Fine Sandy Loam
Silt Loam
Silt Loam
Table 3-3. Associations between Elements in Soil Samples Analyzed by Electron Microprobe
Association
Mn-Fe
P-Fe
Pb-Mn
Pb-Fe
Fe-Si
Pb-P
P-Mn
Sample Count1
(High correlation)
23
20
10
5
2
1
0
Percentage Scans
(High correlation)
28.4 %
24.7 %
12.3 %
6.2 %
2.5 %
1.25%
0%
Sample Count1
(Moderate correlation)
34
22
24
15
17
9
5
Percentage Scans
(Moderate correlation)
42.0 %
27.2 %
29.6 %
18.5%
21.0%
11.1%
6.2 %
1 Total of 81 analyses on 12 thin sections.
Table 3-4. AOD and CBD Extraction Results for Plot 2, 4, 6, and 8 Composite Soils (values in parenthesis are standard
deviations for 3 replicates)
Plot
2
4
6
8
AODFe
(mg/kg)
60,400 (2,740)
50,000(1,440)
24,000(1,130)
26,000(491)
AODMn
(mg/kg)
4,070(153)
4,364(141)
1,130(155)
2,410(122)
CBDFe
(mg/kg)
57,100 (3,650)
29,100 (740)
31,000(1,920)
34,000 (337)
CBDMn
(mg/kg)
3,570 (464)
2,170 (72.4)
1,220(63.6)
2,510(46.6)
17
-------
Table 3-5. FTIR Peaks in Clay Fractions from Plots 2, 4, 6, and 8
Peak Location
Mineral
3696
3620
3300
1636 (not in CBD treated)
1594 (CBD treated only)
1396 (CBD treated only)
1030
914
800
780
750
695
530
470
420
Kaolinite
Kaolinite
Water adsorbed on soil organic matter
Water adsorbed on soil organic matter
Soil organic matter
Soil organic matter
Kaolinite
Kaolinite
Quartz
Quartz
Kaolinite
Quartz
Kaolinite
Kaolinite
Kaolinite
Table 3-6. XRD Analysis Results
Minerals Present Based on Fit
(plots)
Other Minerals Queried
Quartz (2, 4, 6, 8)
Muscovite (2, 4, 6, 8)
Clinochlore (6, 8)
Siderite (2, 4, 6, 8)
Kaolinite (2, 4, 6, 8)
Lepidocrocite (6, 8)
Pyromorphite [Pb5(PO4)3Cl]
Vivianite [Fe3(PO4)2-8(H2O)]
Chloropyromorphite [Pb5(PO4)3Cl]
Goethite [a-FeO(OH)]
Hematite [Fe2O3]
Siderite [FeCO3]
Akaganeite [Fe3+O(OH,Cl)]
Maghemite [y-Fe2O3]
Ferrihydrite [5Fe2O3-9H2O]
Tenorite [CuO]
Corkite [PbFe3(OH)6SO4PO4]
Anglesite [PbSO4]
Galena [PbS]
Beudantite [PbFe3AsO4SO4(OH)6]
Plumbojarosite [PbFe6((OH)3SO4)4]
18
-------
4. Lead Bioaccessibility to Waterfowl in the Lower Coeur d'Alene Basin
Part 1: Development of a Physiologically Based Extraction Test for
Waterfowl
4.1 Introduction
Mining and smelting activities in the Silver
Valley Region of Idaho from the latter part of
the 19th and through much of the 20th century
have caused extensive heavy metal
contamination in the Coeur d'Alene River basin.
Metals in mining and milling wastes were
carried downstream and deposited in the
floodplains on approximately 18,000 acres in the
Lower Coeur d'Alene River Basin. About 280
migratory and nesting bird species, mammals,
reptiles (snakes, turtles), and amphibians inhabit
the Lower Coeur d'Alene Basin (Ridolfi 1993).
Heavy metals cause harm to humans and
wildlife. One alarmingly apparent example is
the lead poisoning of migrating waterfowl that
stop over in the Coeur d'Alene River Basin.
The majority of Pb poisoned waterfowl in the
Coeur d'Alene Basin are tundra swans, Canada
geese, and 14 other species (Sileo, Creekmore et
al. 2001).
The Lower Coeur d'Alene River Basin provides
feeding, resting and reproductive habitat.
Contamination of the Coeur d'Alene River
sediments from mine tailings has been identified
as the main source of waterfowl Pb poisoning
(Blus, Henny et al. 1991; Sileo, Creekmore et al.
2001). After soil ingestion, contaminants can be
partially or totally released from the soil matrix
during digestion and absorbed in the
bloodstream (Oomen, Hack et al. 2002). Lead
affects gastrointestinal epithelium, kidney, red
blood cells, bone marrow, and nervous and
reproductive systems. Clinical signs of Pb
poisoning in waterfowl include severe pectoral
muscle atrophy and bile stained feces, greenish
diarrhea, excessive amount of bile present in the
gall bladder, impaction of gastrointestinal tract
with food leading to starvation, up to 40% loss
in original body weight, erosion of the gizzard
lining, loss of vision, convulsions, coma and
death (Kendall and Driver 1982).
Due to the risks of Pb poisoning to wildlife and
humans in the Lower Coeur d'Alene River
Basin, and the vast area that needs to be
remediated, addition of P to the soils has been
proposed as an in situ remediation strategy.
Application of P-amendments changes the Pb
chemistry through formation of sparingly
soluble Pb phosphates (Davis, Drexler et al.
1993; Ruby, Davis et al. 1994; Zhang, Ryan et
al. 1997; Yang, Mosby et al. 2001). Several
studies have demonstrated decreased
(bio)availability of Pb minerals in the P-treated
(abundant) soils (Davis, Drexler et al. 1993;
Ruby, Davis et al. 1994; Zhang, Ryan et al.
1997; Yang, Mosby et al. 2001). However, due
to the variable environmental conditions and
dynamic nature of soil biogeochemistry an
assessment of the in-situ remediation strategy
must be done on a case-by-case basis, and must
take into account the environmental factors
controlling contaminant speciation (e.g.,
reduction and oxidation cycling).
There are several different approaches for
measuring bioavailability. An in vivo (in living
organism) test uses an animal to measure
absolute bioavailability and toxicity. An in vitro
(outside living organism) test can be used as a
PBET that incorporates gastrointestinal tract
parameters representative of a particular species.
Initially, the PBET model was designed to
simulate the human gastrointestinal tract, which
includes stomach and intestinal phases (Ruby,
Davis et al. 1993; Ruby, Davis et al. 1996;
Medlin 1997; Rodriguez and Basta 1999; Basta
and Gradwohl 2000; Oomen, Hack et al. 2002;
Schroder, Basta et al. 2003). Absolute
bioavailability is the amount of a substance
absorbed into the organism's tissue via a
particular route of exposure (gastrointestinal)
divided by the total amount administered (U.S.
EPA 1999). In vitro bioavailability
(bioaccessibility) is defined as the solubility of
19
-------
soil Pb in simulated stomach and intestinal
solutions over total Pb in the soil (Berti and
Cunningham 1997). The PBET differs from
other soil extraction tests {e.g., toxicity
characteristic leaching procedure (TCLP),
Mehlich, etc.] because it incorporates
physiological parameters from the target species,
therefore making it a more representative test for
bioavailability.
Soil particle size, mineralogy, Pb speciation, and
food are among factors that influence Pb
bioavailability (Steele, Beck et al. 1990).
Processes regulating interactions between
different metal species and their bioavailability
values include solubility, adsorption,
complexation, redox reactions, and biological
uptake (Samiullah 1990). Thus it is critical to
know Pb speciation to evaluate Pb
bioavailability. Traina and Laperche (1999)
reported that the toxicity of a metal is directly
proportional to the activity of the free ion, and
the most toxic solid will be that which supports
the largest equilibrium activity of the metal.
This indicates that the Pb minerals with the
lowest solubility will be the least poisonous to
waterfowl. Bioavailability of Pb minerals has
been assessed by PBET in several studies to
determine which minerals contribute to higher
metal bioavailability and pose the greatest
toxicity potential (Davis, Drexler et al. 1993;
Ruby, Davis et al. 1994; Ruby, Schoof et al.
1999; Yang, Mosby et al. 2001). For example,
Ruby et al. (1999) reported that Pb
bioaccessibility increases in minerals in the
order: galena
-------
phase) and 6.2 (intestine phase) are used in the
W-PBET model. The effect of pH on metal
extractability in the simulated gizzard for pH
values of 2.0, 2.6, and 3.2 were measured.
4.3 Soil Mass and Fluid Volume
In this study the solid to solution ratio was
chosen based on the waterfowl's daily ingestion
of soil, which was derived from in vivo studies
(Heinz, Hoffman, et al 2004) and 50 mL of
gastric solution, which was the estimate used by
Levengood and Skowron (2001). A non-
breeding mallard eats between 70-100 g of food
on a dry-weight basis per day and sediments
constitute 12% of the diet (Heinz, Hoffman, et al
2004). Therefore, the ducks ate approximately
8.4 g of soil per day, and the estimated soil to
solution ratio was 8.4 g to 50 mL = 0.168 g mL"1
(1:5.95). In this study, the effect of soil to
solution ratio (1:6, 1:8.3, 1:100 and 1:200) on
W-PBET metal bioaccessibility was tested.
4.4. Stomach Mixing
The gizzard exhibits regular rhythmic
contractions. Peristaltic and segmenting
movements comprise the mixing behavior in the
bird's intestine (Sturkie 1976). An oscillating
water bath at 250 rpm was used to simulate
mixing for this test.
4.5 Soil Particle Size
Development of PBET models for humans
considered soil particle sizes of < 250 jam
because particles of this size and smaller would
adhere to a child's hands, and could be ingested
(Duggan, et al. 1985; Ruby, et al. 1996;
Rodriguez and Basta 1999). Several ongoing
studies use soils with particle size < 500 jam to
measure bioavailability to ecological receptors
such as the shrew and American Robin (Ruby
2003). In this study soil particles less than 1
mm were used because this is the size fraction
used by Heinz, et al. (2004) in a waterfowl
feeding study. Smaller particles have greater
ratios of surface area to volume, hence, are more
soluble, which may result in greater Pb
bioavailability (Sparks 1989; Ruby, et al. 1992).
Waterfowl can contain grit at an average of 45 g
in the gizzard Klasing 1998), increasing the
grinding effect. Grinding is not simulated in the
centrifuge tubes when mixing in the water bath
in the W-PBET test. Therefore, the effect of
particle size on bioaccessibility was tested.
4.6 Stomach Emptying Rate and Small
Intestinal Transit Time
In 1999, Rodriguez and Basta concluded that the
length of time to perform the stomach phase and
intestinal phase for humans was not clearly
described in literature. In their study, they found
that arsenic (As) concentrations in samples taken
every 60 minutes remained constant over 3
hours.
The length of time that food materials spend in
the gizzard depends on particle size. Small
particles and liquid components pass through in
minutes, whereas hard grains may remain in the
gizzard for several hours. According to Klasing
(1998), the mean retention time required for
digesta to move through the GI tract in
herbivorous birds is 50-300 minutes. In
chickens, turkeys, and geese, food spends about
50% of the time in the stomach, which means
that stomach incubation time is about 25-150
minutes. In this study the effect of incubation
times of 30, 60, and 150 minutes on metal
extractable concentrations in the simulated
gizzard were tested.
4.7 Temperature
Because dissolution reactions are dependent on
temperature, a significant temperature influence
on the rate and equilibrium status of the
reactions occurring in the extraction test was
expected. In the PBET, the temperature is set to
mimic a human (37 °C). Waterfowl body
temperature is 42 °C and was used in the
W-PBET test (Levengood and Skowron 2001).
4.8 Gastrointestinal Fluids
In 2001, Levengood and Skowron examined
concentrations of heavy metals in the gizzard
contents of 18 mallards. Gizzard contents were
21
-------
transferred into 50 mL of simulated gastric juice
containing 1 normal (N) sodium chloride
(NaCl), 10 grams per liter (g/L) of pepsin, and
hydrochloric acid (HC1) to adjust the pH to 2.0.
These are the gizzard fluid parameters used in
the W-PBET model, except pH is adjusted to
2.6. The same intestinal solution containing bile
salts and pancreatin as in the in vitro model by
Rodriguez and Basta (1999) was used. Across
species, the small intestine is considerably less
variable than other organs because the diverse
physical constitution of different foods is
reduced to a relatively uniform fluid suspension,
or chyme, by the action of the proventriculus
and gizzard (Klasing 1998). However, different
bile concentrations and bile salts from either
porcine or bovine origin may induce different
bioaccessibility values for the different models
(Oomen, et al. 2002). A summary of the
physiologically based extraction test parameters
for humans and waterfowl are presented in Table
4-1 along with the model developed for this
study.
4.9 Soils
Soil samples used in measuring method
reproducibility, accuracy, and sensitivity
analysis were collected from a soil remediation
test located on the northwest shore of Bull Run
Lake in the Lower Coeur d'Alene Basin (Figure
3-1). This site includes a control plot
(unamended) and P-amended plot to test the
immobilization of Pb. Soils collected from the
control plot were used in method validation.
Samples were collected using a random
sampling from a grid overlaid on the plots using
a 20-cm long 5-cm diameter stainless steel
sampler with a plastic sleeve insert. Core
samples were submerged in liquid N2, sealed,
placed on ice, and transported to the laboratory
where they were kept at -5 °C. Soils were air-
dried and gently crushed and sieved to passing
1-mm pore size. Total metal concentration was
measured on the soils using a hydrofluoric
acid/aqua regia digest as outlined in EPA
Method 3052.
Soils fed to mallards in the bird feeding study
were used in the W-PBET model to investigate
relations between in vitro Pb and in vivo Pb.
Lead-contaminated soil samples from the Coeur
d'Alene River Basin (Harrison Slough, Black
Rock Slough, and Bull Run lake soils) in Idaho
were P-amended in either laboratory incubations
or field trials (Heinz, et al. 2004; Table 4-1).
The soils from the Bull Run Lake site were
amended in both the laboratory and field. A
reference soil sample from Round Lake in the
St. Joe River in Idaho that had relatively low Pb
concentrations was compared to the three Pb-
contaminated sites in the Coeur d'Alene River
Basin in Idaho. The amendments consisted of
phosphoric acid, lime to raise the pH of the soils,
and potassium chloride to enhance
chloropyromorphite [Pb5(PO4)3Cl] formation.
The soils aged in the laboratory were thoroughly
mixed under water in a commercial stainless
steel mixing bowl and remained under the water
continuously (Heinz, et al., 2004). The soils in
the field were amended to a depth of 12 inches
and rototilled. After aging the soils in the
laboratory and field for 5 months, they were
homogenized, dried, and screened through a 1-
mm sieve. Unamended and amended soils were
combined with the duck maintenance diet and
pelletized (Heinz, et al., 2004). All of the
experimental diets contained 12% soil. Table 4-
2 summarizes the results of Pb concentrations in
the tissues of mallards fed experimental diets.
Raw data on W-PBET extractable gizzard Pb are
shown in Appendix A, the University of Idaho's
final deliverable for this project (Strawn, 2006).
Soil particle size analysis was conducted on the
soils by first dispersing the soil aggregates and
separating them using sedimentation (Gee and
Bauder 1986). The W-PBET test was conducted
on eight soil samples from the bird feeding study
four separate times. These results are shown in
Table 4-2. Ten percent of filtrates were run as
duplicates on ICP-AES. Blanks and standard
soils were run through the experiment.
22
-------
4.10 W-PBET Procedure
A two-step sequential extraction consisting of
the gastric and intestinal phases, as two separate
measurements of gastrointestinal availability
was used for the W-PBET. This approach is a
modified version of the PBET model developed
by Ruby etal. (1996).
4.10.1 Gizzard Phase
The gizzard solution was made up of 1 N NaCl
and 10 g/L pepsin (from porcine stomach
mucosa) and acidified to a pH 2.6 with HC1
(Kimball and Munir 1971). Thirty mL of the
gizzard solution was combined with 3.6 g of
contaminated soil in a 50-mL polycarbonate
centrifuge tube. The tube was degassed with
high purity N2, sealed, and placed in a water
bath at 42 °C. Samples were mixed in the water
bath at 250 rpm. Temperature and pH for all
solutions was taken prior to adding the soil.
Following incubation of one hour, the samples
were removed centrifuged and filtered.
Measurements of pH taken before and after
centrifuging did not appear to be that different,
therefore, pH was measured only after
centrifuging. Samples were centrifuged for 24
minutes at 12,000 rpm and the supernatant was
filtered through a 25-mm syringe filter with a
0.2-|o,m membrane following pH measurement.
Because the proteins and salts may cause a high
background effect and filter clogging during
analysis, the samples were diluted 1:10 in
deionized water. The filtrate was analyzed for
calcium (Ca), cadmium (Cd), P, Pb, Zn and Mn
using ICP-AES. Detection limits for the gizzard
and intestine phase Pb on the ICP-AES were
0.01 milligrams per liter (mg/L).
4.10.2 Intestinal Phase
Following the gizzard phase, a separate set of
un-centrifuged samples was adjusted to a pH of
6.2 by the addition of sodium bicarbonate. Bile
salts and pancreatin (from porcine pancreas)
were added in the amount of 0.35% and 0.035%,
respectively (Rodriguez and Basta, 1999).
Samples were mixed in the water bath at 250
rpm. Following incubation for two hours, the
samples were removed, centrifuged, filtered, and
the pH was measured. All other aspects of the
sample treatment and analysis were the same as
the gizzard phase.
4.11 Effect of W-PBET Parameters on
Metal Extractability
Sensitivity analysis was conducted on the
gizzard phase to determine the effect of pH,
grinding, soil to solution ratio, and incubation
time on Pb extractability in the simulated
gizzard. Bull Run unamended soil samples were
run at pH of 2.0, 2.6, and 3.2 through the W-
PBET gizzard phase. Another W-PBET
experiment was conducted on soils to test
incubation time of 30, 60, and 150 minutes. All
other parameters are shown in Table 4-1.
Grinding effect was tested on soils with particle
sizes of < 1 mm and < 0.25 mm. Soil-to-
solution effect on W-PBET metal
bioaccessibility was investigated at 1:6, 1:8.3,
1:100, and 1:200 (g/mL). All samples were run
in triplicates. Details of the analytical results are
provided in Appendix A, the University of
Idaho's final deliverable for this project (Strawn,
2006).
4.12 Data Analysis
Note: The reported statistical analyses for this
work were performed using Statistical Analysis
Software (SAS) Version 8.2. However, details
about the specific code and model used were not
fully documented. An EPA review of the
following section found that the information
provided was insufficient to verify the statistical
analysis. With this understanding, specific
results should be interpreted and used with
caution.
W-PBET metal bioaccessibility was calculated
as the ratio of metal concentration in the
extracted phase (mg/kg) over total Pb
concentration in the soil (mg/kg). In vivo Pb
bioavailability was calculated as a ratio of Pb
concentration in the tissue (mg/kg, wet weight)
over total Pb concentration in the diet (mg/kg).
23
-------
Statistical analyses were performed using
Statistical Analysis System Version 8.2. Least
significant difference t-tests were used to
separate means. Pearson and Spearman
correlation coefficients were used to determine
if W-PBET Pb results were correlated with bird
feeding results, and to determine if extractability
of the different soil metals were correlated with
each other. Linear regression was performed for
metal gizzard extractabilities and W-PBET
parameters.
4.13 Results and Discussion
Reproducibility of Pb extractability in the W-
PBET gizzard phase was high [relative standard
deviation (RSD) = 4.3%]. However,
reproducibility of Pb extractability in the
intestine extractions was lower (RSD = 17%).
The low precision in the Pb concentrations in the
simulated intestine extractions were most likely
due to the concentrations being near the ICP-
AES detection limit (0.01 mg/L). Results from
spiked solutions carried through the extraction
experiments indicated that the gizzard phase
recovered an average of 90% ± 8% of the spiked
Pb, while the intestine phase recovered an
average of 73% ± 7% of the spiked Pb. The low
recovery for the intestine phase suggests that a
fraction of the soluble Pb is lost in this
extraction, possibly due to precipitation of Pb
carbonate minerals. Although such a process
may be indicative of processes occurring in the
digestion system of waterfowl, the exact reason
for the low recovery is unclear and, therefore,
adds uncertainty to the intestine-phase extraction
results. Because of this observation, and the fact
that the intestine extraction concentrations are
near or below the detection limit, the results and
discussion presented below focus on the gizzard
phase.
4.13.1 Sensitivity Analyses
One of the governing factors of Pb extractability
in the simulated gizzard is pH. Results for Pb
extractability in the simulated gizzard at
different pH values indicate linear relations
between pH and Pb concentration in the gizzard
phase (Figure 4-1). The concentration of Pb in
the gizzard extraction doubles as pH decreases
from 3.0 to 2.0. Because conditions in a bird
stomach vary depending on food presence and
bird speciation, an average pH value of 2.6 was
used in the W-PBET experiments. The linear
relationship between pH and extractable Pb
indicates that pH should not affect the
correlation between W-PBET Pb and in vivo Pb.
Incubation time (30, 60, and 150 minutes) did
not create a significant difference in Pb
concentrations in the gizzard as shown in Figure
4-2. This is consistent with the findings of other
PBET experiments (Rodriguez and Basta, 1999;
Hettiarachchi, et al. 2000). Since incubation
time (kinetics) does not control Pb extractability
in the gizzard, the dissolution or desorption of
Pb must reach equilibrium within the 60-minute
time frame of the experiment.
Pb concentrations in the gizzard extractions
from soils with particle sizes < 1 mm and
< 0.250 mm are significantly different as shown
in Figure 4.3. However, the difference is small:
1501.4 ± 53.6 mg/kg Pb in the simulated gizzard
from particle size soil less than 1 mm, and
1669.5 ± 31.7 mg/kg Pb in the simulated gizzard
from particle size soil less than 0.250 mm (i.e.,
10% difference). Bull Run Lake soils are very
fine sandy loam soils. Previous studies
conducted in the laboratory indicated that Pb
was predominantly associated with the clay
minerals with size < 0.002 mm. This is
significantly smaller than the tested particle size
of < 0.250 mm and < 1 mm, explaining the small
difference in particle size effect on Pb
extractability. Because the gizzard mainly
grinds larger particles, the relative differences in
bioaccessible Pb were minimally impacted by
grinding effects.
Soil to solution ratio in the simulated gizzard
was investigated due to uncertainty about its true
value in the waterfowl digestion system. In
general, an increase in soil-solution ratio causes
a decrease in Pb extractability as shown in
Figure 4-4.
24
-------
There was not a notable difference in Pb
bioaccessibility for soil to solution ratios 1:100
and 1:200; however, there were differences
noted between Pb bioaccessibility for soil to
solution ratios 1:6 and 1:8.3.
The relationship between Pb extractability and
soil to solution ratio in the simulated gizzard
was linear (R2=0.96) as shown in Figure 4-4.
Strong linear relations between Pb extractability
and soil-to-solution ratios indicate that different
soil-to-solution ratio values used in W-PBET
and PBET models should not affect metal
bioaccessibility results in comparative studies.
However, differences are significant in studies
that are designed to calculate absolute
bioavailability.
4.13.2 W-PBET Lead and In Vivo Lead
Comparison
W-PBET and bird feeding results indicating that
P-amendments significantly reduce Pb
bioavailability are shown in Table 4-2.
However, previous studies have suggested that
reduced Pb concentrations in amended soils with
1% P present hazards to waterfowl (Heinz et al.
2004). The relationship between Pb
concentrations in the W-PBET gizzard
extraction and Pb concentrations in the tissues is
logarithmic as shown in Figure 4-5.
Correlations of the W-PBET Pb concentrations
and Pb concentrations in the different tissues
(blood, kidney and liver) were similar. Both
Pearson and Spearman coefficients show the
highest correlation between log Pb in the W-
PBET gizzard and Pb concentrations in the
tissues, and the lowest correlations between Pb
bioaccessibility and Pb bioavailability. The
statistical results are shown in Table 4-3. When
the in vitro tissue and W-PBET gizzard Pb
concentrations were normalized by the total
concentration of Pb in the diet and in the soil,
respectively, the correlations were similar to the
non-normalized, except for the blood Pb data,
which had no significant correlation according
to the Pearson correlation test. Both
bioavailability and bioaccessibility have the
same trend for Pb in the amended and
unamended soil samples.
The most significant difference between W-
PBET and bird feeding tests is that the Harrison
Slough soil had greater bioaccessible Pb values
compared to other soils, while the in vivo test
did not have as large a difference for Pb
bioavailability in Harrison Slough soils versus
other soils. This difference between the two
tests is likely a result of discrepancies between
the in vivo and W-PBET gastrointestinal
physical parameters and biochemistry that are
affected differently by the varying soil
characteristics. All soils had similar particle size
distributions and total Pb concentrations,
eliminating the possibility of surface area
differences as the reason for the differences in
the W-PBET and in vivo results. Thus, it is
concluded that the differences are due to
differences in Pb speciation or soil mineralogy,
and that this difference does not impact in vivo
bioavailability. Soil mineralogy can impact the
amount of Pb in solution because different
minerals will maintain varying solution
concentrations of Pb in the simulated digest
solution. This difference highlights the
importance of understanding how soil variability
can impact bioavailability, and the need for tests
that can measure such variation.
4.13.3 W-PBET Results for Lead, Zinc,
Cadmium, and Manganese
Concentrations of Pb, Zn, Cd, and Mn in the
W-PBET gizzard extractions from the Lower
Coeur d'Alene Basin amended and unamended
soils were analyzed. In the Lower Coeur
d'Alene River, Pb, Zn, and Cd are present at
elevated levels and threaten wildlife (LeJeune, et
al. 2000). High concentrations of Mn were
present, which can be toxic because of the trace
metals that readily absorb on Mn oxides
(McKenzie, 1980; Hettiarachchi, et al, 2002).
W-PBET results for Cd, Zn, and Pb gizzard
extractability were correlated to each other in the
unamended Harrison Slough, Black Rock, and
Bull Run Lake soils using Pearson correlation
coefficients: RPb/cd = 0.82, RPb/Zn = 0.96,
25
-------
= 0.93, probability (p) < 0.01. Soils from
different locations in the Lower Coeur d'Alene
Basin had different metal bioaccessibility,
indicating that the speciation is different and
metal bioaccessibility is site-specific as shown
in Figure 4-6. Different reduction values were
observed in metals bioavailability to earthworms
in the P-amended soils from different locations
reported by Maenpaa et al. (2002). This study
concluded that soil characteristics other than P-
amendments affect metals bioavailability to
earthworms.
According to W-PBET results, only Pb showed
a significant reduction in bioaccessibility in all
P-amended soils. This indicates that P-
amendments immobilized Pb species. Many
studies have investigated the decrease in Pb
bioavailability in P-amended soils through
formation of Pb phosphates, such as
pyromorphite (Ruby et al, 1994; Laperche et al,
1997; Hettiarachchi et al 2000; Melamed et al
2003). In solutions with several metals present,
the phase with the lowest solubility precipitates
from solution before the more soluble metals
such as Cd, Zn, and Mn least soluble metals
(Cao et al 2003). Reaction kinetics also plays a
role. In 2003, Oomen et al. reported that
pyromorphite formation is a rapid process and
the reactions between available Pb and
phosphate can take place in the acidic conditions
of the simulated gastrointestinal fluid and result
in formation of pyromorphite in vivo. Lead
phosphates are considered to be insoluble.
However, Oomen et al. (2003) used
voltammetry to measure Pb species in solution
and observed that lead phosphate complexes are
soluble in the simulated chyme of the human
digestive system, and could therefore be a
source of Pb2+ that is available for transport
across the intestinal epithelium. This suggests
that poorly soluble lead phosphate minerals may
not be completely non-reactive in the digestive
system.
Phosphate amendments are primarily used to
immobilize Pb, but they can also stabilize other
metals (Chen et al. 1997; Maenpaa, et al. 2002).
The availability of Cd and Zn has been studied
in apatite-treated soils and solutions and it was
determined that the aqueous Cd and Zn
concentrations decreased in the presence of
apatite (Chen et al. 1997; Cao et al. 2003). Cao
et al. reported in 2003 that different mechanisms
are responsible for decreased Zn and Cd
solubility in the presence of apatite: ion
exchange at the surface of hydroxyapatite;
surface complexation; precipitation of
amorphous to poorly crystalline mixed-metal
phosphate; and, metal substitution for Ca in
hydroxyapatite during recrystallization.
The W-PBET gizzard extraction phase showed no
significant difference between P-amended and
unamended soils in Harrison Slough and Black
Rock soils for Cd and Zn. However, there was a
significant reduction in Cd and Zn gizzard
extractability in the Bull Run Lake soils
P-amended in the field as shown in Figure 4-6.
Maenpaa et al. (2002) did not observe significant
Pb, Zn, and Cd bioavailability reductions to
earthworms in the soils with lower P rate
amendments (600 mg P/kg dry weight).
However, at higher P-amendment rates (5,000
mg/kg dry weight) there was significant reduction
in Pb, Cd, and Zn earthworm bioavailability. The
field-amended soils had significantly higher P-
amendments; however, the Black Rock Slough
field-amended soils did not show a significant
difference in Cd and Zn bioaccessibility,
discounting this as the sole reason for the
decreased bioaccessibility in the Bull Run Lake
field-amended soils. It is hypothesized that the
differences are due to the dramatically different
environments that are present between the two
sites. P-amendment application, incubation,
water inundation, mixing, and soil characteristics
could account for the different metal availabilities
between the field- and lab-aged samples (Heinz et
al. 2004). Although they are only separated by
approximately 100 meters, the Bull Run Lake
soils are located on a lateral lake shore and
subjected to different flooding cycles than the
Black Rock Slough soils, which are located at a
slightly higher elevation and subjected to flooding
for only short times.
26
-------
The bioaccessibility of Cd and Zn behaved
similarly in all soils as shown in Figure 4-6.
This is likely due to these elements lying in the
same group on the periodic table, which means
they have similar chemical properties. There
was a linear correlation between Cd and Zn in
the P-amended and unamended soils as shown in
Figure 4-7. The similarities in release in the
gizzard extract indicate that Cd and Zn exist as
the same species in the soils, and react similarly
with P-amendments.
4.14 Discussion and Conclusions
W-PBET gizzard phase demonstrated high Pb
extraction reproducibility and accuracy. The
intestine phase has been excluded as Pb
concentrations in this phase were near the ICP-
AES detection limit (0.01 mg/L), which leads to
low reproducibility. The W-PBET parameters
on Pb extractability in the simulated waterfowl
gastrointestinal tract showed that pH had the
most significant impact on Pb bioaccessibility.
Results showed linear relations between pH and
Pb extractability in the gizzard phase (R2 =
0.97). In the gizzard phase, incubation time did
not affect Pb extractability, indicating that Pb is
at equilibrium and that soil grinding had only a
small effect on Pb extractability. There was a
negative linear relationship between soil to
solution ratio and Pb extractability in the
simulated gizzard.
Although W-PBET was designed to simulate the
waterfowl digestive tract, it must be emphasized
that extractable Pb should be viewed in a
relative context. The use of the predicted Pb
bioaccessibility for absolute bioavailability
predictions is weakened by the many
assumptions within W-PBET model and the
difficulty in precisely simulating bio-uptake in
the GI system. Despite these limitations, the W-
PBET Pb bioaccessibility model developed
during this project was positively correlated with
bird feeding results for contaminated and in situ
remediated soils from the Lower Coeur d'Alene
River Basin.
There was a significant decrease in Pb
bioavailability/bioaccessibility in all of the P-
amended soils. These results show that
phosphate has a different effect on Cd, Zn, and
Mn than on Pb. Cd and Zn showed a significant
decrease in gizzard extractability only in the
Bull Run Lake soils that were P-amended in the
field. Similarities were noted between the
behavior of Zn and Cd extractability in the
unamended and amended soils, suggesting that
they have similar speciation and their
availability is governed by the same mechanisms
in the P-amended soils. Mn bioaccessibility was
variable between the different soils and
treatments. W-PBET gizzard phase results
showed that metal extractability in the soils was
site-specific.
Because the geochemistry of Pb and other
metals in the soils is dynamic, it is critical to
have an assessment tool that will allow
scientists, managers, and engineers to evaluate
how environmental variables, and remediation
and management strategies might impact the Pb
bioavailability. The W-PBET model is a cost
effective method to accomplish this.
27
-------
'o
W
O
DO ,§,
*!
(0
N
0
1600 n
1200
800
400
0
1
k
^\
i
1234
PH
Figure 4-1. pH effect on Pb extractability in the gizzard. Error bars represent one
standard deviation of triplicates (R2 = 0.97).
_ 1640
g 1600
s I 156°
^ E
S 1520
1480
re
N
N
1400
50 100 150
Time (min)
200
Figure 4-2. Incubation time effect on Pb solubility in the gizzard phase. Error bars
represent one standard deviation of triplicates.
28
-------
1800
(/)
O) 1700
00 £,
1600
1500
1400
N
N
1300
< 0.250
Particle Size (mm)
Figure 4-3. Effect of grinding on extractable Pb in the simulated gizzard. Error bars
represent one standard deviation of triplicates.
^ 5000
Q_
o 4000
H 1> 3000
O B)
I- S 2000
uj ^
£ 1000
0 0.05 0.1 0.15 0.2
Soil to Fluid ratio (g/ml)
Figure 4-4. Relationship between extractable metal in the simulated gizzard and soil to
fluid ratio in the simulated gizzard solution (R2 = 0.96).
29
-------
4 -,
Q.
"S 3
ro
N
N , ,
b o> 2
l_
mo)
P -1
a. ^"
^ 0
>
IS
1
^
0
|i 1600 -,
. ^ "3)
t E
y^ ~ 12°°
*X^ £
fcX* ro 800
^^ N
^^ N
^^ fc 400
00
a.
5 o -<
$
t
I
* (b)
^ 1 V ~ *i 1
2468 0246
Blood Pb(mg/kg) Blood Pb (mg/kg)
Figure 4-5. Log (a) and linear (b) correlations between Pb concentrations in the simulated gizzard
concentrations
c
1600 -,
!> 1200
W-PBET
Gizzard Pb (me
*>. 00
o o
o o o
in the blood.
ZH Unamended I I P-amended, field ^^M P-amended,
j. 600 -,
J> 500 JL^
A ti4o°- n XL
FI 1 5 3°° - nk
s 2o° " r
««.. ii m ii
i i
8
andPb
lab
i
Harrison Black Bull Run Harrison Black Bull Run
Slough Rock Lake Slough Rock Lake
20 n
1500
tj I
1200
900
600
300
n
"B 16
Pi H!
m £ 12
T i
]] i II ;
T
Lnr
u n 1 1 1 v iii
Harrison Black Bull Run Harrison Black Bull Run
Slough Rock Lake Slough Rock Lake
Figure 4-6. Lead, Zn, Mn, and Cd release in the W-PBET gizzard extractions from the Lower Coeur
d'Alene Basin soils. Error bars represent one standard deviation (N = 4).
30
-------
c
N
"
N
N
>
t £
00
0.
600
500
400
300
200
100
0
0 10 20
W-PBET Gizzard Cd (mg/kg)
Figure 4-7. Correlation between Zn and Cd extractability in the W-PBET gizzard phase
from the P-amended and unamended Lower Coeur d'Alene River soils (R2 = 0.96).
Table 4-1. Summary of In Vitro Parameters Used in Different Models and Proposed W-PBET
Parameter
PBET Model
(Ruby et. al., 1996)
TVG Model
(Rodriguez and
Basta, 1999)
Gizzard Simulation
(Levengood and
Skowron, 2001)
W-PBET
Experiment Design
(this study)
Gastric Solution
Target Organism
PH
NaCl
Pepsin
Citrate
Malate
Lactic Acid
Acetic Acid
Fluid Solution
Amount of Soil Added
Temperature
Food Added
Incubation Time
Soil: Solution Ratio
Human
1.3; 2.5; 4.0
None
1.0% (1.25 g)
0.05%
0.05%
0.5%
0.5%
40 mL
0.4 g
37 °C
No
1 hour
1:160 (assuming
density of 1 .6 g/cm3
for the test soil)
Human
1.8
0.15 M
0.10%
None
None
None
None
600 mL
4g
37 °C
Yes
1 hour
1:150 (assuming
density of 1 .0 g/cm
for the test soil)
Waterfowl
2.0
IN
10g/l
None
None
None
None
50 mL
Gizzard Content
42 °C
Yes
1 hour
Gizzard content: 50
mL of simulated
gastric juice
Waterfowl
2.0-3.2
IN
10g/l
None
None
None
None
30 mL
3.6 g
42 °C
No
1 hour (or until
equilibrium is
established)
6 g:50mL (based on
waterfowl bird
feeding study)
Intestinal Solution
PH
Pancreatin
Bile Extract
Incubation Time
5.5
0.018% (20 mg)
0.05% (70 mg)
4 hour
7.0
0.035% (0.21g)
0.35% (2. 10 g)
1 hour
-
-
-
_
5.2-7.2
0.035%
0.35%
2 hour
31
-------
Table 4-2. Lead Bioaccessibility and Unavailability Values Based on W-PBET and Bird Feeding Studies; Pb and P
Concentrations in the Soils and Blood Pb Values are from Heinz et al. (2004)
Samples
Treatments
Pb
P
mg/kg dry weight
Round Lake
Harrison
Slough
Harrison
Slough
Black Rock
Slough
Black Rock
Slough
Bull Run
Lake
Bull Run
Lake
Bull Run
Lake
None
None
Amend, Lab
None
Amend,
Field
None
Amend, Lab
Amend,
Field
21 + 1.9
4,520 + 68
4,370+21
5,390+40
4,070 + 164
6,990 + 125
6,910 + 61
6,100 + 68
723+5
628+21
10,400+20
708 + 10
18,600+440
440 + 15
10,200+66
21,300+209
W-PBET
Gizzard-Pb
mg/kg
BDL
1,258 + 811
45.5+4
662 + 79
12 + 1
854 + 71
26 + 3
22+4
Bioaccess- _, , _, In Vivo
.,.,., Blood Pb . ., , ....
ibility Bioavailabihty
(blood)
%tt mg/kg
wet weight
0.08
28 5.1+0.30
1.04 2.9+0.32
13 52+0.46
0.3 2.3+028
12.2 6.4 + 0.56
0.4 3.8 + 0.33
0.4 2.3+026
%§
-
1.0
0.6
0.97
0.5
0.8
0.5
0.34
t Standard deviations for N = 4
tt Percentage is W-PBET gizzard extractable Pb normalized by soil Pb (mg/kg)
§ Percentage is in vivo tissue Pb normalized by diet Pb (mg/kg)
BDL - below detection limit
Table 4-3. Correlation Coefficients between W-PBET Pb and In Vivo Pb (N = 32, p < 0.05)
Parameter
Blood Pb (mg/kg)
Liver Pb (mg/kg)
Kidney Pb (mg/kg)
W-PBET Gizzard
Pb
(mg/kg)
0.88f 0.78n
0.93 0.78
0.94 0.82
W-PBET
Log Gizzard Pb
(mg/kg)
0.88 0.93
0.94 0.95
0.94 0.88
Parameter
Blood Pb/diet Pb
Liver Pb/diet Pb
Kidney Pb/diet Pb
W-PBET Gizzard Pb
Soil Pb
0.78 0.31§
0.81 0.59
0.81 0.69
f Spearman correlation coefficient
f f Pearson correlation coefficient
§ Correlation is not significant (p > 0.05)
32
-------
5. Lead Bioaccessibility to Waterfowl in the Lower Coeur d'Alene River
Basin Part 2: Seasonal Effect on Metal Bioaccessibility
5.1 Introduction
To assess a potential remediation strategy for Pb
poisoning to wildlife and humans in the Lower
Coeur d'Alene River Basin, P-amendment trials
were conducted (TerraGraphics Environmental
Engineering 2003; Heinz, Hoffman et al. 2004).
Several studies have demonstrated decreased
availability of Pb minerals in P-treated soils
(Davis, Drexler et al. 1993; Ruby, Davis et al.
1994; Zhang, Ryan et al. 1997; Yang, Mosby et
al. 2001). An in vitro, physiologically based
extraction test that incorporates gastrointestinal
tract parameters representative of waterfowl was
developed and calibrated to measure Pb
bioavailability to waterfowl. PBET models for
humans (Medlin 1997; Rodriguez and Basta
1999; Basta and Gradwohl 2000; Oomen, Hack
et al. 2002; Schroder, Basta et al. 2003) were
modified to take into account waterfowl
parameters, based on bird physiology (Sturkie
1976; King and McLelland 1979; Sturkie 1986;
Klasing 1998; Levengood and Skowron 2001).
The W-PBET model was positively correlated
with bird feeding studies described by Heinz et
al. (2004), and both investigations (in vivo and
W-PBET) showed that Pb bioavailability was
significantly reduced in the P-amended soils.
Thus, we concluded that the developed W-PBET
model can be used to measure relative changes
in bioavailability with various treatments and
under specific conditions. Such an in vitro test
for waterfowl is useful because it is less
expensive, simpler, and more easily reproduced
than a bird feeding study. As a result of these
benefits, the W-PBET model can be used to
assess site-specific remediation strategies and
relative bioavailability, and has potential to be
used as a regulatory tool to assess the
effectiveness of a particular remediation
strategy.
In this study, Pb bioaccessibility was examined
in soils from the Coeur d'Alene River Basin as a
function of seasonal changes using the W-PBET
model. Soils in contaminated wetlands undergo
temporal fluctuations in water inundation,
resulting in fluctuations in the redox potential.
Changes in redox status of the soils can affect
the availability and mobility of metals, and
consequently their bioavailability. Thus, to
account for influences of reduction and
oxidation on metal bioavailability, it is important
to investigate soils collected during different
times of the year. Iron and Mn geochemistry in
wetlands is particularly interesting because these
elements are redox reactive and have high
surface areas for interactions with both P and Pb
and, therefore, dynamic changes in the Fe and
Mn speciation will impact Pb bioavailability.
Manganese-lead oxide and Fe-Pb oxide can be
formed in soils by a combination of geochemical
or bacterially-mediated reactions (Davis et al.
1993). Oxygen depletion in flooded soils may
cause a successive reduction of Mn oxides and
Fe oxides, thereby releasing contaminants
associated with them (Hem 1978; Matsunga et
al. 1993), and increasing heavy metal
bioavailability. Beyer and Day (2004) estimated
exposure of mute swans to metals from
contaminated sediments in Chesapeake Bay,
USA. Exposure to Pb at the reference site was
found to be correlated with Mn and Fe.
Although Pb is the main element of focus in
many studies on waterfowl toxicity, in this study
we also report on trends in extractability of Zn,
Cd, Mn, and Fe as well.
5.1 Soil Sampling
Soils were sampled from two field sites. One
site is located on the northwest shore of Bull
Run Lake, and the other one is on the northwest
side of Black Rock Slough (Figure 3-1). Each
site contained an unamended (control) plot (25
feet by 30 feet) and a plot amended with
phosphoric acid, lime, and potassium chloride
(Heinz et al 2004). Amendments were applied
and tilled to a depth of 1 foot in April 2001. The
two sites are approximately 200 feet apart.
33
-------
Black Rock Slough soils are water saturated for
shorter periods compared to Bull Run Lake
soils.
Samples from the P-fertilizer amended soils and
the control plots were collected on May 14,
August 7 and October 30, 2003 using a random
sampling from a grid overlaid on the plots as
shown in Figure 3-2. Three cells from each plot
were sampled using a 20-cm long 5-cm diameter
split core stainless steel sampler with a plastic
sleeve insert. Core samples were immediately
submerged in liquid N2, sealed in airtight
nitrogen purged bags, placed on ice, and
transported back to the laboratory where they
were kept at -5 °C. A combination reference
electrode was used to measure redox state. The
measured potentials of the samples were
corrected to the standard H-electrode using
theoretical redox potential of potassium ferric -
ferrocyanide and the measured potential of
potassium ferric-ferrocyanide solution relative to
the reference electrode. The pH was measured
using a combination pH electrode. Prior to
extraction, the frozen soil cores were freeze-
dried and gently crushed and sieved to passing
1-mm pore size. Total elemental concentrations
in the soils were determined using EPA Method
3050. The complete results are shown in
Appendix A, the University of Idaho's final
deliverable for this project (Strawn, 2006).
5.2 W-PBET Experiment
To measure Pb bioaccessibility, W-PBET
gizzard phase extraction was conducted on the
soil samples. Each soil sample was run in
duplicate, and 10% of the samples were run in
triplicate. Blanks and a standard soil (soil used
in all extractions) were run in all extractions.
The gizzard solution consisted of 1 N NaCl and
10 g/L pepsin from porcine stomach mucosa
acidified to pH 2.6 with HC1 (Kimball and
Munir 1971). Thirty mL of the gizzard solution
was combined with 3.6 g of contaminated soil in
a 50-mL polycarbonate centrifuge tube. The
tube was degassed with high purity N2, sealed,
and placed in a water bath at 42 °C. Samples
were mixed in the water bath at 250 rpm. All
solutions were analyzed for pH and temperature
prior to adding to the soil. Following incubation
of 1 hour, the samples were removed,
centrifuged, the pH measured, and the mixture
was filtered. A test was conducted on pH
stability; results indicated that the final pH
ranged from 3 to 3.5. The samples were diluted
1:10 in deionized water and centrifuged for 24
minutes at 12,000 rpm, through a 25-mm syringe
filter with a 0.2 um membrane filter. The filtrate
was analyzed for Cd, Pb, Zn, Fe, and Mn using
ICP-AES. National Institute of Standards and
Technology (NIST) traceable multi-element
standards were used to assure accuracy in
measuring metal concentrations. Ten percent of
the extracts were run in duplicate on ICP-AES.
All analytical results are provided in Appendix
A, the University of Idaho's final deliverable for
this project (Strawn, 2006).
5.3 Data Analysis
Note: The reported statistical analyses for this
work were performed using Statistical Analysis
Software (SAS) Version 8.2. However, details
about the specific code and model used were not
fully documented. An EPA review of the
following section found that the information
provided was insufficient to verify the statistical
analysis. With this understanding, specific
results should be interpreted and used with
caution.
Element bioaccessibility values were calculated
by normalizing the W-PBET extracted Pb using
the total Pb concentration in the soil. Data
analysis was conducted using Statistical
Analysis System Version 8.2. Least significant
difference was applied to separate means. Each
sample site contains unamended and amended
plots and within each site, there was a
completely randomized design with three
replicates within two plots, sampled across time.
Pooled-repeated measures analysis of variances
(ANOVA) was used and the model was run
separately for each element. Correlation
analysis was run between Pb, Cd, Zn, and Mn
bioaccessibility values in the P-amended and
34
-------
unamended soils, between metal bioaccessibility
values and soil pH, and between total metal
concentrations in the soils and soil pH. The
results from an inferential test were identified as
statistically significant if the p-value of the test
statistic was less than 0.05.
5.4 Results and Discussion
Lead, Zn, Mn, Cd, and Fe concentrations in the
Lower Coeur d'Alene Basin exceed common
ranges of metal concentrations for soils as
shown in Table 5-1. Phosphorus concentrations
in the unamended soils were low, suggesting
that P may be a limiting element for
precipitation of poorly soluble metal P minerals
in the soils. The average pH value for amended
soil samples was 3.6 ± 0.4 (standard deviation)
at the 0-5 cm depth. The pH for unamended soil
samples was 4.9 ± 0.7 at the 0 to 5-cm depth.
The P treatment decreased the average pH of the
soils by 1.3 units, and the lime added to the soils
was not sufficient to neutralize the pH.
Soil pH can have a significant affect on metal
mobility and bioavailability. Generally, the
highest concentrations of available metals are
found in soils with low pH (Iskandar and
Kirkham 2001). However, Ruby et al. (1996)
observed that acidic pH decreased Pb
bioavailability due to formation of the Pb
minerals anglesite and Pb jarosite, which are
stable in acidic soils. These phases should be
stable in the simulated gastrointestinal
conditions as well (Ruby, Schoof et al. 1999).
Chen et al. (1997) investigated pH effects on
metal removal by apatite. They found that
effects of pH on aqueous Pb sorption by the
apatite were not significant, but formation of
solid reaction products (pyromorphite) were pH
dependent. There were no correlations between
metal (Pb, Zn, Cd, and Mn) bioaccessibility and
pH in either unamended or P-amended soils, or
between total elemental concentrations in the
soils and soil pH. The lack of any correlation
within treated and untreated soils indicates that a
pH decrease of ~1 unit did not affect metal
bioaccessibility or total soil concentrations.
Small seasonal changes in pH values also did
not affect metal bioaccessibility. The small
range of soil pH and the fact that effects of pH
change may have been superceded by reactions
with the phosphate are possible reasons for the
lack of correlations between pH and heavy metal
bioaccessibility in the soils.
Redox state of soils collected in August and
October 2003 was oxic. Redox conditions of
soils collected in May 2003 ranged from suboxic
to oxic conditions as shown in Appendix A, the
University of Idaho's final deliverable for this
project (Strawn, 2006). The pH and Eh
conditions shown in Figure 5-1 were favorable
for dissolution of Pb sulfides and carbonates, as
well as desorption of Pb from mineral surfaces,
making it available for pyromorphite formation
in the P-amended soils.
Pb concentrations in the W-PBET gizzard and
total Pb concentration in the unamended and
amended soils were not correlated. However, in
vivo studies on waterfowl have shown high
correlation between Pb in the blood and Pb in
the soils (Wixson and Davies 1993; Beyer,
Conner et al. 1994).The lack of correlation
between total and bioaccessible Pb in this study,
and the variable Pb bioaccessibility between the
two sites suggests that Pb speciation, not total
Pb concentration in the soils, controls Pb
bioaccessibility. Other items that might
influence bioaccessibility were not part of this
study.
Metal bioaccessibility of the control and P-
amended soils collected at different times are
shown in Figure 5-2. Iron and As extractability
in the simulated gizzard from freeze-dried soils
collected at different times were below the
detection limit (approximately 0.01 mg/L) and
are thus not reported. Lead, Cd, and Zn
bioaccessibility decreased in the P-amended
soils. Other investigations have observed a
reduction in Pb, Cd, and Zn aqueous
concentrations and bioavailability in P-amended
soils (e.g., Maenpaa et al. 2002). Different
binding mechanisms of Pb, Cd, and Zn to P or
other minerals control their solubility in the
35
-------
simulated gastrointestinal tract. Previous studies
determined that the disappearance of Zn and Cd
from aqueous solutions with apatite addition was
due to sorption reactions rather than
precipitation reactions, and that the speciation of
the Zn and Cd was distinct from Pb. This
hypothesis is a possible explanation for the
greater decrease in Pb bioaccessibility compared
to Cd and Zn bioaccessibility in the P-amended
soils.
Phosphorus-amendments increased Mn
bioaccessibility. This increase could be due to
Mn phosphate minerals (MnHPO4, Mn3(PO4)2)
formed in the P-amended soils that have
increased solubility in the acidic conditions of
the simulated gizzard compared to the Mn
oxides, causing higher Mn bioaccessibility
(Lindsay 1979). In 2000, Hettiarachchi et al.
reported the effects of P and Mn oxide on
bioavailable Pb in five contaminated soils. That
study concluded that Mn oxides are strong
sorbents of both Pb and P, and that both soil
characteristics and Mn and P speciation affect
Mn solubility in the gizzard and Mn redox state.
Surface precipitation of comparatively insoluble
Pb phosphate on Mn minerals (encapsulation)
restricts dissolution of Mn oxides because Pb
phosphate is more stable in a reduced acidic
environment. The increased solubility from P
amendment in this study does not support that
hypothesis. Seaman et al. (2001) observed a
decrease in Mn solubility in contaminated soils
when hydroxyapatite was added. However,
similar to our soils, there was an increase in Mn
bioaccessibility in P-amended soils, suggesting
that P amendments do not restrict Mn solubility
in the acidic gizzard.
Statistical analyses indicated that the Pb, Zn, and
Mn bioaccessibility was not significantly
different at the three sampling times (p > 0.05),
but there was a significant difference between P-
amended and unamended sites as shown in
Figure 5-2. This suggests that seasonal
influences on Pb, Zn, and Mn bioavailability in
these soils are minimal. However, the redox
state of samples collected in May was not low
enough to represent reducing conditions, and
only the Bull Run unamended plot showed
suboxic conditions. The 2003 spring runoff was
below average, minimizing soil saturation
duration, therefore limiting the onset of reducing
conditions. Additionally, although the soils
were purged with N2 and preserved in cold
temperatures, redox state may not have been
completely preserved.
Another explanation for the lack of seasonal
difference in heavy metal bioaccessibility is that
reductive mineral dissolution and subsequent
heavy metal release may be followed by
precipitation with P, carbonates, or sulfides.
This process would be highly likely in the P-
amended soils where phosphate is present in
excess. Silviera and Sommers (1977) found that
diethylene triamine pentaacetic acid (DTPA)
extractable Pb, which simulates plant available
Pb, remained constant with time in a water-
saturated soil-sludge system during 28 days of
incubation. Bostick et al. reported in 2001 that
Zn speciation in contaminated seasonal wetlands
near the Coeur d'Alene River in northern Idaho
is dictated by water depth and redox potential.
The data show that Zn is associated with the
hydroxide phases in dry, oxidized soils, and with
sulfides and carbonates in flooded systems. This
indicates that Zn sorption is a dynamic process
influenced by environmental changes. As
indicated above, the conditions on wetland sites
this sampling season were not reducing, and
therefore may not have created enough phase
transformation for significant temporal changes
in Zn, Mn, or Pb bioaccessibility.
Cadmium bioaccessibility was significantly
lower in the P-amended plots compared to the
unamended plots, as shown in Figure 5-2. There
was no seasonal Cd bioaccessibility variability
within the two P-treated sites, and the trends in
Cd bioaccessibility were similar between the
two sites. However, the unamended plot from
Black Rock Slough had significantly lower Cd
bioaccessibility in August than in May and
October. Additionally, using data from both
sites in ANOVA suggested that the August
36
-------
sampling event had significantly lower Cd
bioaccessibility than October or May samples.
The decrease in Cd bioaccessibility in August
indicates that the least bioavailable Cd phases
are formed in summer in the unamended soils.
The redox state of the soils did not change
significantly between the three sampling
periods. Thus, factors other than redox state are
responsible for lower Cd bioaccessibility in
August, such as biological activity, temperature,
or other undetermined fluxes.
Bioaccessibility was positively correlated for Cd
and Pb (RPearson=0.67, p < 0.01), and Cd and Zn
(Rpearson=0.73, p < 0.01) in the P-amended and
unamended soils. Cd is more bioaccessible in
the plots compared to Pb bioaccessibility as
shown in Figure 5-2. Pb solubility is controlled
by poorly soluble mineral phases that include
phosphate, sulfate, carbonate, and chloride
anions. Cadmium forms fewer poorly soluble
complexes in soils, and is more mobile than the
other metals.
These results did not show a temporal effect on
metal bioaccessibility. One possible reason for
this lack of change in bioaccessibility is that the
soils were not sufficiently reduced. Another
limitation is that purging soils with N2, storing
them frozen, and freeze-drying the soil samples
may not have fully preserved the redox state.
Previous studies have demonstrated oxygenation
and drying of the soils can affect contaminant
chemistry (e.g., Bostick et al. 2001).
5.5 Conclusions
Findings from this study showed that there were
no seasonal effects on Pb, Mn, and Zn
bioaccessibility in the test plot soils. Only Cd
showed lower bioaccessibility in August
compared to May and October. The lack of any
seasonal differences can be explained by the
minimal seasonal change observed in soil redox
potential. Pb, Cd and Zn bioaccessibility values
significantly decreased in the P-amended soils
compared to the unamended soils.
Bioaccessibility reduction was the highest for
Pb, possibly through formation of sparingly
soluble Pb PO4", such as pyromorphite-like
minerals. Cd and Zn either precipitated or
formed surface complexes with P minerals. Mn
bioaccessibility increased in the P-amended
soils. This indicates that Pb phosphate, formed
in P-amended soils, did not restrict Mn solubility
in acid solution of the simulated gizzard. There
were significant differences between the two
sites' Pb, Mn. and Zn bioaccessibility values.
This observation can be explained by site-
specific differences in metal speciation, flooding
time, water depth, microbial activity, and
vegetation.
37
-------
IS=10'3 M, ICO3=10'2 M, IC1= 10'3 M, IP= 1O'6 M, aPb2+ =10"'
1
0.8
0.6
0.4
Pb2+
O2
H7O
Pyromorphite
Pb5(PO4)3Cl
-0.6
-0.8
0 2 4 6 8 10 12 14
PH
Figure 5-1. Hypothesized Eh-pH stability diagram for Pb at the test plots. Assumed
aqueous concentrations are listed at top.
38
-------
May
August
October
(a)
(b)
7 30
I25
1 20
'55
§ 15
§ 10
m 5
Q- n
Bull-P Bull
Black- Black
P
80
g.
£ 60
$ 40
u
u
TO
5 20
o
0
, I,
Plot
Bull-P Bull Black- Black
P
Plot
(c)
(A
8
o
re
.2
m
N
30
25
20
is
10
5
fil
If
I
Bull-P Bull Black- Black
P
Plot
Bull-P Bull Black- Black
P
Plot
Figure 5-2. W-PBET bioaccessibility of Pb (a), Cd (b), Zn (c) and Mn(d) in the soils collected from Bull Run Lake and
Black Rock Slough soils at different times. Plots Bull-P and Black-P are P-amended; Plots Bull and Black are
unamended. Error bars represent one standard deviation from discrete samples within a plot (N = 3).
39
-------
Table 5-1. Metal Concentrations (Means and Ranges) in the Lower Coeur d'Alene Basin Study Area
Common
ranges for
soils*
(mg/kg)
amended
(mg/kg)
P-cunGnd-Gcl
(vr\ a l\fa\
v & &/
Pb
10
(2-200)
6,035
(4,100-
12,000)
4,958
(3,200-
6,800)
Cd
0.06
(0.01-
n T\
U./J
16
(5-29)
25
(12-51)
Zn
50
(10-300)
2041
(570-
3,800)
1793
(580-
5,000)
Ca
13,700
(7,000-
500,000)
1,405
(448-
2,100)
1,326
(671-
1,900)
Mn
600
(20-
3,000)
5,731
(2,000-
9,700)
4,053
(500-
9,900)
Fe
38,000
(7,000-
550,000)
73,557
(29,000-
100,339)
64,084
(31,000-
103,301)
P
600
(200-
5,000)
849
(380-
1,500)
21,062
(14,000-
30,000)
As
5
(1-50)
87
(19-
143)
67
(15-
126)
S
700
(30-
10,000)
1,532
(392-
3,200)
1,309
(297-
2,800)
* Data from Lindsay 1979
40
-------
6. Geochemical Modeling
6.1 Introduction
Soils in the Coeur d'Alene River Basin are
located in seasonal wetlands. The cycling of
flooding and drying makes the biogeochemical
processes occurring in these soils dynamic. The
soils in these wetlands contain high
concentrations of the Pb, Fe, Mn, Zn, Cd, and
As. Because speciation controls availability for
transport and biouptake in the environment, a
clear understanding of how seasonal cycling
impacts speciation is required. Geochemical
modeling is one approach that can be used to
make predictions of speciation and aqueous
concentrations.
The objective of the geochemical modeling is to
use aqueous concentrations and mineralogy of
elements and species of interest for the Coeur
d'Alene Basin to model the system so that
prediction of Pb solubility can be determined.
Results from the following tasks will be
presented:
Predict speciation of Pb and Fe in soils.
Predict speciation of Pb and Fe in P-
amended soils.
Develop redox diagrams for Pb and Fe
species using input parameters relevant to
Coeur d'Alene system.
Evaluate Cd and Zn geochemical reactions
relevant to Coeur d'Alene soils.
6.2 Methods
The general approach for geochemical modeling
assumes that the system is at equilibrium and
that the solid phase controlling speciation is the
species that has the lowest solubility, unless
information is known regarding formation of
other solid phases. In dynamic systems such as
seasonal wetlands, the assumption of
equilibrium may not be accurate, particularly for
solid phases and redox reactions. However,
modeling the equilibrium phases in systems is
still valuable because it allows for prediction of
the lowest energy state of the system with
respect to characterized pure mineral species;
such results serve as a basis to better understand
the processes that control aqueous
concentrations. For aqueous reactions the
assumption of equilibrium is likely accurate
because reactions are generally rapid.
Modeling geochemical reactions uses a
systematic approach. Summarized below is the
approach as applied to the soils in the Lower
Coeur d'Alene River Basin.
System - Soils in the Lower Coeur d'Alene
River Basin.
Phases - Solid, liquid, gas.
Inputs - Solid phases, aqueous concentration
of ions, redox potential, total inorganic
carbon (C), temperature. The inputs are
listed in Table 6-1. Data were taken from
several sources to create a typical pore water
composition for the geochemical modeling.
Species - Species are defined by the inputs;
the geochemical program uses a database to
search all forms of the input species. The
database is based on the MINTEQ database
developed by the EPA.
Reactions - Reactions define species
transformations and are used together with
equilibrium constants to model the system.
Reactions and equilibrium constants for all
species presented in graphs in this report are
listed in Tables 6-2 and 6-3.
Output - Output is determined by the
modeler. Output was generated as aqueous
speciation, saturation index, and stability
diagrams for solid phases. Output is defined
by dependent and independent variables;
dependent variables are controlled by inputs.
For this system, independent variables were
pH, temperature, redox potential, and P
concentration.
41
-------
The above are easily managed by a computer
program. Modeling in this report was done
using the U.S. Geological Survey program
PHREEQCi, Version 2. PHREEQCi is an
iterative model that mathematically distributes
aqueous constituent data, [i.e., pH, electron
potential (pe) plus major and element of interest
ion concentrations], among thermodynamic
mass action expressions. Geochemist's
Workbench was used to develop stability
diagrams. MINEQL+ was used to develop
solubility diagrams.
6.3 Results of Geochemical Modeling for
Pb and Fe in Soils
Data from Table 6-1 was input into the program
PHREEQCi to predict aqueous speciation and
solubility of Pb as a function of pH and redox
potential. Figure 6-1 shows the aqueous
concentration as a function of pH at 14.3 °C in
oxic soils. The predominant species below pH
6.5 is Pb2+; if pH increases past 6.5, Pb
carbonate aqueous will become the dominant
species in solution. Total Pb concentration was
controlled by input and no solids were allowed
to precipitate. Modeling did not include
complexation with dissolved organic acids,
which can be significant.
Saturation indices for the system as a function of
pH and redox potential are reported in Figures
6-2 through 6-4. A saturation index above zero
indicates that the mineral is oversaturated with
respect to the system conditions. In this system
control precipitation was not allowed, thus each
mineral species can be evaluated based on
aqueous species and concentrations independent
of each other. This is an advantage as kinetic
controls on mineral formation are not known,
and often the least soluble mineral will not be
the mineral controlling the aqueous
concentration. Under oxidizing conditions,
plumbogummite and chloropyromorphite are
saturated in the system, while
hydroxypyromorphite is not as shown in Figure
6-2. As the system becomes reducing, aqueous
Pb2+ species concentration decreases due to the
formation of Pb-sulfide complexes. This causes
the saturation index for plumbogummite and
hydroxypyromorphite to be less than zero below
pH 6 in the most reducing conditions, while
galena is saturated in this pH range. The
saturation index (SI) is defined as the logarithm
of the ion activity product divided by the
reaction equilibrium constant. Negative values
indicate undersaturation with respect to a
particular solid phase, positive values indicate
oversaturation, and a value of zero indicates
equilibrium. Analysis of the Pb in the soil pore
waters suggests that under most conditions the
soil pore water is saturated with respect to lead
phosphate minerals. When the soils become
reduced, the soil pore water becomes under
saturated with respect to lead phosphate;
however, and total dissolved Pb will be
controlled by Pb-sulfides. Expected aqueous
concentrations controlled by the Pb phosphate
minerals are shown in Figure 6-5. The systems
shown on the graph are defined as follows.
HPM - aqueous Pb and phosphate
concentration controlled by
hydroxypyromorphite.
CPM - aqueous Pb, chlorine (Cl) and
phosphate concentration controlled by
chloropyromorphite.
CPM (strengite, ferrihydrite) - aqueous Pb
and Cl concentration controlled by
chloropyromorphite, and phosphate
concentration controlled by solubility of
strengite and soil ferrihydrite
CPM (field) - aqueous Pb concentration
controlled by chloropyromorphite.
Cl" and phosphate" concentrations are given
in Table 6-1 and based on typical field
concentrations.
PGM (strengite, gibbsite, ferrihydrite) -
aqueous Pb concentration controlled by
plumbogummite, and phosphate
concentration controlled by solubility of
strengite and soil ferrihydrite, and aluminum
(Al) concentration controlled by gibbsite.
42
-------
In all systems solid phases were set as fixed,
temperature = 25 °C.
Monitoring of the pore water indicated that the
aqueous Pb concentrations in the P-amended and
untreated plots at the two sites ranged from
below detection limits (0.002 mg/L) to 0.04
mg/L. The complete data set for the soil pore
waters collected from the experimental plots is
presented in Figure 6-5. Soil solutions appear to
fall within the expected range for solutions in
equilibrium with poorly soluble Pb phosphate
minerals. Therefore, it is expected that the
dissolved Pb concentration in the soils will be
relatively low because the concentration is
controlled by minerals that have relatively low
solubility. The effects of adding phosphate are
further discussed below.
The soil water temperatures ranged from 5 to
22 °C. Temperature can increase or decrease
mineral solubility, and thus impacts aqueous
concentrations of metals. Chloropyromorphite
solubility as a function of temperature is shown
in Figure 6-6. For every 1 °C change in
solubility there is an absolute 0.02 change in log
PbT concentration. Chloropyromorphite has a
retrograde solubility indicating that at the lowest
soil water temperatures solubility is increased.
The geochemical modeling analysis presented in
this study was done at 14.3 °C; deviations due to
temperature fluctuations are expected to be
minimal.
Iron minerals are important solid phases in the
Coeur d'Alene soils because they provide
reactive surfaces for the adsorption of Pb and
other contaminants. Below pH 6, the oxidized
system is only slightly saturated with respect to
hematite and magnetite as shown in Figure 6-7.
However, the kinetics in the soils are not
favorable for the formation of these minerals.
Analysis by selective extraction and differential
XRD suggests that goethite and ferrihydrite are
the dominant Fe minerals in the system. The
fact that the soil waters are unsaturated with
respect to these minerals suggests that the soil
minerals have variable solubility and/or the
conditions used for the model are not at
equilibrium; most likely both scenarios are true.
The Fe oxides in the soil are dominated by
ferrihydrite. Ferrihydrite is a poorly crystalline
metastable mineral. Given time it will convert
to crystalline goethite or hematite minerals.
However, because the soils in this study are
dynamic with respect to fluxes of ions and redox
conditions, equilibrium is not expected, and thus
ferrihydrite minerals can persist. The lack of
saturation in the soil pore-water system is
consistent with this condition.
Under reducing conditions, the soil pore waters
are saturated with respect to pyrite below pH 6
as shown in Figure 6-8 and Figure 6-9.
However, the transitory nature of redox in these
systems may inhibit the formation of slowly
precipitating Fe sulfide minerals, and instead
favor formation of poorly crystalline Fe sulfide
phases, such as mackinawite. It is suspected,
that the addition of P to soils will promote the
formation of strengite in oxidizing conditions
and vivianite under reducing. This is illustrated
in the stability diagram (Figure 6-10).
Figure 6-11 shows the effect of phosphate
concentration on mineral stability for two
aqueous Pb activities. At pH values below 6 and
hydrogen phosphate (HPO42~) activities above
10"7 Chloropyromorphite is the stable mineral
phase. The log pKa2 for phosphate is 6.79, thus
HPO42" concentrations are much lower than the
dihydrogen phosphate (H2PO4~) concentrations.
The different phosphate speciation will affect
the magnitude of the Y-axis variables in Figure
6-11, but not the relative stability field
relationships. From Figure 6-11 it is apparent
that with a pH below 6, phosphate
concentrations promotes the formation of
Chloropyromorphite. A more quantitative
analysis is presented in Figure 6-12. The red
box represents the minimum and maximum field
of aqueous Pb and phosphate concentrations
observed in the soil water sampling study at pH
= 5.5 by Terra Graphics Environmental
Engineering Inc. 2003a. The arrow on the
43
-------
bottom of the figure indicates that increasing
phosphate in the soil solution will cause the soil
to become increasingly saturated with respect to
poorly soluble Pb phosphate minerals. Based on
the model, the lower left hand region is
undersaturated with respect to Pb phosphate
minerals, suggesting that adding P will increase
stability of Pb in the soils. However, this model
assumes that dissolved phosphate is controlled
by Ca phosphate minerals. If Ca is limiting, or
Fe concentrations are high (i.e., low pH), then
adsorption to Fe oxides or
dissolution/precipitation of Fe phosphate
minerals will control aqueous P concentrations.
Figure 6-13 shows a full soil stability diagram
for lead phosphate minerals. The box represents
observed aqueous concentrations of Pb and pH
observed in the field plots. This diagram shows
similar trends as Figure 6-12 with respect to Pb
speciation and mineral stability. For the
solubility lines to be lowered, the available
phosphate and Cl" must be increased. In a soil
with excess concentrations of Fe-oxide, this will
take large quantities of phosphate amendment,
which may pose additional unwanted impacts
(e.g., decreased soil pH, excessive soil
aggregation and cementation, and increased risk
of nutrient loading into the surface waters).
A general redox stability diagram for Pb
minerals is shown in Figure 6-14. This diagram
shows the stability fields for Pb minerals as a
function of pH and Eh. Based on the redox
potentials observed in the field trials,
chloropyromorphite is the most stable mineral.
However, in soils that have longer saturation
times, redox potentials have been observed that
are suboxic and anoxic; these redox potentials
would favor the formation of galena in the soils.
Galena is a poorly soluble Pb-sulfide mineral. A
redox stability diagram specific to the soil pore
water system described in Table 6-1 is shown in
Figure 6-15. This diagram indicates there are
three Pb minerals present in pH range of 3.5 to
6; galena, chloropyromorphite, and
plumbogummite depending on the redox
conditions. Transformation from galena to
either plumbogummite or chloropyromorphite is
a function of redox potential, while
transformation between the two PbPO4" minerals
is pH dependent. All three minerals have low
solubility.
6.4 Evaluation Cd and Zn Solubility
Saturation indices for Cd and Zn minerals in the
systems are shown in Table 6-1 and Table 6-2
and Figure 6-16 and Figure 6-17, respectively.
Zinc silicates and phosphates are the only
minerals saturated in the models. Under
reducing conditions, sphalerite becomes
saturated. Bostick et al. (2001) investigated
speciation of Zn in Coeur d'Alene wetland soils
and confirmed that under reducing conditions
sphalerite was present, as well as carbonate
minerals. All Cd minerals tested were
unsaturated under oxidizing conditions;
however, under reducing conditions the Cd-
sulfide mineral greenockite is saturated. From
this it is concluded that dissolved Cd and Zn
under oxidizing conditions are prevalent in the
soil plots for most of the year and are primarily
controlled by adsorption reactions on mineral
surfaces. However, under reducing conditions
Cd and Zn solubility is dramatically reduced by
precipitation of sulfide phases.
6.5 Summary
This modeling has provided results that predict
speciation in soil pore water from the soils
studied in this project. Additionally, an analysis
of the effect of P and redox on Pb solubility was
conducted. The modeling suggests that in the
O OO
soils, the aqueous speciation is dominated by
Pb2+ ions. However, aqueous organic acids were
not included in the model, which would have a
significant impact on partitioning in the aqueous
phase. The models predicted that under all field
conditions Pb solubility is controlled by the
minerals plumbogummite, chloropyromorphite,
or galena. Because these minerals have low
solubility, aqueous Pb concentrations will be
maintained at low levels, regardless of redox
potential. However, Fe minerals are dissolving
in the soils, and may provide a new flux of Pb to
the soil water that can be transported out of the
44
-------
soil into surface and ground waters before
equilibrium with the Pb-solid phases is possible.
Another important factor for modeling Pb
availability is the quantification of interactions
of mineral surfaces with aqueous species.
Sorption of aqueous anions and cations often
control dissolved concentrations. For example,
adsorption of P on mineral surfaces may limit its
availability for reaction with Pb to form poorly
soluble minerals. This example is particularly
relevant in the soils studied as they have high Fe
contents and a low pH, which are favorable
conditions for anion adsorption.
Additionally, although the aqueous phase is
predicted to be controlled by a poorly soluble
phase, equilibrium is rare in soils, particularly
wetland soils, where fluxes are dramatic. It is
recommended that additional research be done
to characterize kinetics, adsorption, and
interaction of metals with organic acids to allow
for a more thorough analysis of the solubility
and speciation of Pb and other contaminant
minerals. Improved understanding of
biogeochemical reactions will allow for
development of more accurate models for
predicting availability for transport and
bio-uptake.
45
-------
Aqueous Pb Species (pe=3.5, T=14.3 C)
1.E+00
-»-PbCI+
-t-PbCI2
PbOH+
Pb(OH)2
Pb(OH)3-
Pb(CO3)2
Figure 6-1. Aqueous Pb speciation as a function of pH, Input data are listed in Table 6.1. No solids
were allowed to precipitate.
20
0
-20
-40
w -60
-80
-100
-120
-140
-CIPyromorphite
- HydroxyPyromorphite
Plumbogummite
Galena
- Cerrusite
8
pH
10
12
14
Figure 6-2. Saturation index for Pb minerals as a function of pH. System parameters are defined in
Tables 6-1 and 6-2 (pe = 3.5).
46
-------
-20 -
w -40 -
-60 -
-80 -
-100
-CIPyromorphite
-HxyPyromorphite
Plumbogummite
Galena
-Cerrusite
8
pH
10
12
14
Figure 6-3. Saturation index for Pb minerals as a function of pH, System parameters are defined in
Tables 6-1 and 6-2 (pe = 0).
Pb Mineral Saturation (pe=-2.6, T=14.3 C)
-CIPyromorphite
- HxyPyromorphite
Plumbogummite
Galena
Figure 6-4. Saturation index for Pb minerals as a function of pH. System parameters are defined in
Tables 6-1 and 6-2 (pe = -2.6).
47
-------
CPM (strengite,
ferrihydrite)
PGM (strengite,
ibbsite, ferrihydrite)
PM (field conditions)
1.E-12
Figure 6-5. Aqueous Pb concentrations as a function of pH controlled by several Pb-phosphate minerals
and observed Pb concentrations in P-amended and non-amended field sites.
O)
-6.90
-7.00
-7.10
-7.20
-7.30
-7.40
-7.50
0
10 15 20
Temperature (°C)
25
30
Figure 6-6. Total dissolved Pb concentrations as a function of temperature controlled by chloropyromorphite
dissolution.
48
-------
-»- Pyrite
--Siderite
Ferrihydrite
-*- Goethite
-*- Hematite
-- Lepidocrocite
i Maghemite
Magnetite
Manganite
Vivianite
Strengite
Figure 6-7. Saturation index for Fe minerals as a function of pH, System parameters are defined in Table 6-
1 and Table 6-2 (pe = 3.5).
Sorbate Mineral Saturation (pe=0, T=14.3 C)
-20 -
-40 -
-60 -
-80 -
-100
-»- Pyrite
--Siderite
Ferrihydrite
Goethite
-*- Hematite
-- Lepidocrocite
iMaghemite
Magnetite
Manganite
Vivianite
Strengite
10
12
14
pH
Figure 6-8. Saturation index for Fe minerals as a function of pH. System parameters are defined in Table 6-
1 and Table 6-2 (pe = 0).
49
-------
10
12
PH
-- Pyrite
--Siderite
Ferrihydrite
-*-Goethite
-*- Hematite
-- Lepidocrocite
iMaghemite
Magnetite
Manganite
Vivianite
Strengite
14
Figure 6-9. Saturation index for Fe minerals as a function of pH. System parameters are defined in Table 6-1 and
Table 6-2 (pe = -2.6).
50
-------
0)
Q_
I I
Figure 6-10. Redox stability diagram for Fe, T = 15 °C, P = 1.013 bars, aFe= ir4'301, acl = 10~3 405, aHCo3-= 10~2'499,
aHpo4--= 10~2'824, aSO4_.= 10~2'807; Suppressed: goethite, hematite, magnetite.
51
-------
PLUMBOGUMMITE,
PbAI3(P04UOH)_.H2O
PYROMORPHI i L
Pb5(P04)3 Cl
PbAI3(PO4XOH)6SO4
/ [Corkite, PbFe3 (P04)(OH)6S04
X,
CERUSSITE
PbCO3
10
11
M1 '
Figure 6-11. Stability diagram for Pb minerals as a function of TJPO4^ concentration and pH (Nriagu,
1984). Calculated for as042- = ancoa- = 10~3, aAuf = 10"6. Solid lines are for apb2+ = 10"6; dashed lines are for
52
-------
20 18 16
pH+pH2PO
H2P04
Figure 6-12. Activity ratio/product diagram showing the relative stability of Pb bearing minerals as
a function of pH, H2PO4- activity, and Pb activity. HAP is hydroxyl apatite, CPM is
chloropyromorphite, HPM is hydroxypyromorphite, PGM is plumbogummite, CER is cerussite,
HCER is hydrocerussite, ALA is alamosite, and DCPD is di-calcium phosphate dehydrate. Chloride
is fixed at 10"3 M at pH 8, Ca is controlled by calcite mineral, and Al is controlled by gibbsite
mineral. Figure is from Essington et al. (2004).
53
-------
-4
s
-6
-7
-8
-9
-10
-11
K Kaolinite
G Gibbsite
Q Quartz
S Soil-Si
Strengite
-TCP i \
<0
Soil-Fe
1
4 5
Soil-Ca \ Calcite \\>\ \j
1 i
6
1 i K \ 1 \\
789
PH
\\ 1
1O
Figure 6-13. The solubility of various Pb silicates and phosphates compared to cerussite when phosphate is
controlled by various solid phases, as indicated above x-axis, and CO2(g) is 0.003 atm. From Lindsay (1979).
54
-------
1
0.8
0.6
0.4
~ 0.2
0
-0.2
-0.4
-0.6 -]
-0.8
Pb
2-
O, £C1=10-JM,£P=
Pyromorphite
Pb5(P04)jCl
0 2 4 6 8 10 12 14
PH
Figure 6-14. Stability diagram for Pb minerals as a function of redox potential and pH, adapted from
Nriagu (1984).
55
-------
20
15
10
CD
-5
-10
Pb
i i i
Ihloropyromorphite
PbCO,
Galena
2 4 6 8 10 12 14
pH
Figure 6-15. Redox stability diagram specific to soil pore water conditions given in Table 6-1.
56
-------
Cd Mineral Saturation (pe=3.5, T=14.3 C)
10 -i
- Greenockite
-Monteponite
Cd(OH)2
CdOHCI
-CdSiOS
-Greenockite pe=-2.6
Figure 6-16. Saturation index for Cd minerals as a function of pH, System parameters are defined
in Table 1 and Table 2 (pe = 3.5, except as noted).
Zn Mineral Saturation (pe=3.5, T=14.3 C)
10
5 -
0 -
-5 -
-10 -
-15 -
-20
-»-Zincite
--Zincosite
Zn(OH)2
Zn3(PO4)2:4H2O
-*-ZnCO3:H2O
--ZnO
-i-ZnSi03
Sphalerite
-Sphalerite pe=-2.6
10
12
14
PH
Figure 6-17. Saturation index for Zn minerals as a function of pH. System parameters are defined in
Table 6-1 and Table 6-2 (pe = 3.5, except as noted).
57
-------
Table 6-1. Simulated Pore Water Concentrations Used as Inputs for Aqueous
Speciation and Solubility Modeling in Soils
Input
Temperature
PH
pe
Ca
Sodium
Magnesium
Mn
Fe
Copper
As
Pb
Cd
Zn
Al
Si
Cl
P
S
c
Value
14. 3 C
5.6, varied
varied
0.274 millimole per
liter (mmol/L)
0.648 mmol/L
0.852 mmol/L
1.89|imol/L
0.56 |imol/L
0.01 |imol/L
0.214 |imol/L
9.65*10->mol/L
0.018 |imol/L
42.2 |imol/L
0.19|imol/L
140.0 |imol/L
389 |imol/L
1530|imol/L
1560|imol/L
3160|imol/L
Reference
1
1
1
1
1
2
2
2
1
1
1
1
2
3
1
1
1
1
1 Terra Graphics Environmental Engineering Inc., 2003
2 Paulson, 2001
3 Balistrierietal.,2003a, b
58
-------
Table 6-2. Reactions and Equilibrium Constants for All Aqueous Species Considered (Complete Thermodynamic
Database Used Was from Schecher, 1998)
Aqueous Species
PbSO4
Pb(SO4)2-2
PbCO3
PbHCO3+
Pb(CO3)2-2
PbCl+
PbCl2
PbOH+
Pb(OH)2
Pb(OH)3-
Pb(OH)4-2
Pb(HS)2
ZnSO4
Zn(SO4)2'2
ZnCO3
Zn(CO3)2'2
ZnHCO3+
ZnCl+
ZnCl2
ZnOH+
Zn(OH)2
Zn(OH)3-
Zn(OH)4-2
Zn(HS)2
CdSO4
Cd(SO4)2'2
CdCO3
CdHCO3+
CdCl+
CdCl2
CdOH+
Cd(OH)2
Cd(OH)3-
Cd(OH)4'2
Cd(HS)2
Reaction
Pb+2 + SO4'2 = PbSO4
Pb+2 + 2SO4'2 = Pb(SO4)2-2
Pb+2 + CO3'2 = PbCO3
Pb+2 + CO3'2 + H+ = PbHCO3+
Pb+2 + 2CO3'2 = Pb(CO3)2-2
Pb+2 + Cl" = PbCl+
Pb+2 + 2C1' = PbCl2
Pb+2 + H2O = PbOH+ + If
Pb+2 + 2H2O = Pb(OH)2 + 2H+
Pb+2 + 3H2O = Pb(OH)3- + 3H+
Pb+2+ 4H2O = Pb(OHV2 + 4H+
Pb+2 + 2HS" = Pb(HS)2
Zn+2 + SO4'2 = ZnSO4
Zn+2+ 2SCV2 = Zn(SO4)2'2
Zn+2 + CO3'2 = ZnCO3
Zn+2 + 2CO3'2 = Zn(CO3)2'2
Zn+2 + CO3'2 + H+ = ZnHCO3+
Zn+2 + Cl" = ZnCl+
Zn+2 + 2C1" = ZnCl2
Zn+2 + H2O = ZnOIf + H+
Zn+2 + 2H2O = Zn(OH)2 + 2H+
Zn+2 + 3H2O = Zn(OH)3" + 3H+
Zn+2 + 4H2O = Zn(OH)4'2 + 4H+
Zn+2 + 2HS" = Zn(HS)2
Cd+2 + SO4'2 = CdSO4
Cd+2 + 2SO4'2 = Cd(SO4)2-2
Cd+2 + CO3'2 = CdCO3
Cd+2 + CO3'2 + H+ = CdHCO3+
Cd+2 + Cl" = CdCl+
Cd+2 + 2C1" = CdCl2
Cd+2 + H2O = CdOH+ + If
Cd+2 + 2H2O = Cd(OH)2 + 2If
Cd+2 + 3H2O = Cd(OH)3" + 3If
Cd+2 + 4H2O = Cd(OHV2 + 4If
Cd+2 + 2HS" = Cd(HS)2
logK
2.75
3.47
7.24
13.2
10.64
1.6
1.8
-7.71
-17.12
-28.06
-36.99
15.27
2.37
3.28
5.3
9.63
12.4
0.43
0.45
-8.96
-16.90
-28.20
-41.99
14.94
2.46
3.5
5.399
12.4
1.98
2.6
-10.08
-20.35
-33.3
-47.35
16.53
59
-------
Table 6-3. Reactions and Equilibrium Constants for All Minerals Considered (Complete Thermodynamic Database
Used Was from Schecher, 1998)
Minerals
Pyrite
Siderite
Ferrihydrite
Goethite
Strengite
Hematite
Lepidocrocite
Maghemite
Magnetite
Manganite
Vivianite
Chloropyromorphite
Hydroxylpyromorphite
Galena
Cerussite
Plumbogummite
Zincite
Zincosite
Zn(OH)2
Zn3(PO4)2:4H2O
ZnC03:H20
ZnO
ZnSiOS
Sphalerite
Greenockite
Monteponite
Cd(OH)2
CdOHCl
CdSi03
Reaction
FeS2 + 2H+ + 2e' = Fe+2 + 2HS"
FeC03 = Fe+2 + CO3'2
Fe(OH)3 + 3H+ = Fe+3 + 3H2O
FeOOH + 3H+ = Fe+3 + 2H2O
FeP04:2H20 = Fe+3 + PO4'3 + 2H2O
Fe203 + 6H+ = 2Fe+3 + 3H2O
FeOOH + 3H+ = Fe+3 + 2H2O
Fe203 + 6H+ = 2Fe+3 + 3H2O
Fe304 + 8H+ = 2Fe+3 + Fe+2 + 4H2O
MnOOH + 3H+ = Mn+3+ 2H2O
Fe3(P04)2:8H20 = 3Fe+2 + 2PO4'3+ 8H2O
Pb5(P04)3Cl = 5Pb+2 + 3P04'3 + Cl"
Pb5(P04)30H + H+ = 5Pb+2 + 3PO4'3 + H2O
PbS + If = Pb+2 + HS-
PbC03 = Pb+2 + C03'2
PbAl3(PO4)2(OH)5:H2O + 5H+ =
Pb+2 + 3A1+3 + 2P04'3 + 6H20
ZnO + 2H+ = Zn+2 + H2O
ZnS04 = Zn+2 + SO4'2
Zn(OH)2 + 2H+ = Zn+2 + 2H2O
Zn3(P04)2:4H20 = 3Zn+2 + 2PO4'3 + 4H2O
ZnC03:H20 = Zn+2 + CO3'2 + H2O
ZnO + 2H+ = Zn+2 + H2O
ZnSi03 + 2H+ + H20 = Zn+2 + H4SiO4
ZnS + H+ = Zn+2 + HS'
CdS + H+ = Cd+2 + HS-
CdO + 2H+ = Cd+2 + H20
Cd(OH)2 + 2H+ = Cd+2 + 2H2O
CdOHCl + H+ = Cd+2 + H20 + Cl'
CdSi03 + H20 + 2IT = Cd+2 + H4SiO4
logK
-18.48
-10.55
4.891
-14.48
-26.4
-30.84
1.371
6.386
3.737
-0.24
-36
-84.43
-62.79
-15.13
-13.13
-32.79
11.14
3.01
12.2
-32.04
-10.26
11.31
2.93
-11.62
-15.93
15.12
13.73
3.52
9.06
60
-------
7. Summary of Quality Assurance Activities
7.1 Introduction
The specific details of the quality assurance
(QA) aspects for this project were addressed in a
previously prepared and EPA-endorsed
document entitled Quality Assurance Project
Plan - Geochemical Modeling for Linking
Waterfowl Contaminant Speciation in Riparian
Soils for Mine Waste Technology Program
Activity III, Project 38. The portion of the
project that the MWTP focused on was the
geochemical modeling. Analytical data
presented for other portions of the project was
part of a larger effort for EPA Region 10, the
Idaho Department of Environmental Quality,
and the U.S. Fish and Wildlife Service. MSB
included additional information and results from
early portion of the project in this report to
present the broader context of the project and the
ultimate "big picture" objective of reducing the
bioavailability of lead to reduce impacts of
waterfowl in the region.
The main purpose of the quality assurance
project plan (QAPP) was to assure that the
model developed to evaluate P-Pb soil
interactions used appropriate thermodynamic
data with respect to mineralogical stability. The
objective of the geochemical modeling effort
was to find reaction mechanisms of Pb in
P-amended soils in environments resembling the
specific aqueous elemental concentrations and
mineral species found in the Lower Coeur
d'Alene River Basin.
The QAPP stated that PHREEQCI and
Geochemist's Workbench software packages
would be utilized to perform the modeling.
PHREEQCI is publicly available from the U.S.
Geological Survey, while Geochemist's
Workbench is commercially available from
RockWare USA, Inc.
7.2 Quality Assurance Assessment
Quality assurance assessment activities for
geochemical modeling were performed by MSE
and were documented in a memo dated January
12, 2006, as required in the QAPP.
In part, MSB's assessment included telephone
conversations and email exchanges with the
principal investigator. It was determined that
most of the modeling was conducted before the
QAPP was finalized. However, MSE personnel
did review the modeling inputs prior to the
modeling effort to help ensure that the modeling
effort was congruent with project objectives
outlined in the EPA-approved project work plan.
In addition to the two software packages
identified in the QAPP, the MINEQL+
commercially available software produced by
Environmental Research Software, Inc. was also
used, mainly to develop solubility curves. This
software also used the MINTEQ thermodynamic
database that was specified in the QAPP.
To simulate the specific aqueous elemental
concentrations characteristic of the Lower Coeur
d'Alene River Basin for modeling purposes, a
representative pore water composition was
assembled from several separate documented
sources and presented in the QAPP. As part of
the QA assessment, it was noted that this
composition had a charge imbalance with a
relative percent difference of 275% as the ratio
of cations to anions was about 3:11
milliequivalents per liter. The QA assessment
findings noted that an equal charge balance is
not a requirement for theoretical modeling as it
would be carried through all the calculations;
however, the charge imbalance could have been
an indication to question the validity of the input
chemistry.
The QAPP required that supporting
documentation be maintained as to the data
inputs for each model output. The QA
assessment findings noted that although specific
input files were not saved, there was essentially
only one input file that represented the single
pore water composition characteristic of the
Lower Coeur d'Alene River Basin.
61
-------
In the summary of the QA assessment
documentation, it was noted that the original
reason for preparing a QAPP was to ensure that
any new modifications to the thermodynamic
databases were tracked and could be associated
with the model results. At the start of the
project, it had been anticipated that
thermodynamic data for additional Pb species
would be obtained from the literature and added
to the database. It was further anticipated that
modification of the values contained with the
default databases might be performed in an
attempt to calibrate the model to field results.
However, these potential changes to the
thermodynamic databases did not become
necessary. The QA assessment concluded that
since no data was added to the databases and no
data was modified in an attempt to calibrate the
model results, the project was essentially
reduced to a standard geochemical modeling
effort, for which, typically, no QAPP would be
needed or prepared.
62
-------
8. Conclusions and Recommendations
8.1 Conclusions
8.1.1 Mineralogical Analyses
The EMPA/XRD investigations conducted on
test sites(s) and element speciation found no
conclusive evidence that phosphoric acid/lime
(P)-treatments enhanced formation of poorly
soluble Pb-P mineral phases. However, the
results indicate that P is preferentially absorbed
to Fe-oxide minerals, while Pb is preferentially
associated with Mn-oxide minerals. Thus, these
highly reactive Fe/Mn-oxide phases will affect
Pb contaminant release as leachable species;
they will also influence P availability for
reaching with Pb or other metallic contaminants
ofconcern.
8.1.2 Metals Bioaccessibility to Waterfowl
The W-PBET gizzard phase results
demonstrated high Pb extraction accuracy (90%
± 8% spike recovery) and precision (4.3%
relative standard deviation). Data from the
intestinal phase were near the ICP-AES method
detection limit of 0.01 mg/L, which led to low
reproducibility of the results. Despite
limitations posed by model assumptions and its
implementation, the gizzard phase results were
positively correlated with bird feeding results for
contaminated and in situ remediated soils from
the Lower Coeur d'Alene River Basin. The
Spearman and Pearson correlation coefficients
for log-scale gizzard Pb versus blood Pb were
0.88 and 0.93, respectively.
The addition of 1.0 to 2.0 weight percent
phosphoric acid to the test site soils resulted in
statistically significant (p < 0.05) reductions in
Pb levels in blood, liver, and kidney. Such P-
treatment also lowers bioavailable- and
bioaccessible-Pb levels, although such
reductions are probably affected by site-specific
differences in Pb speciation or mineralogy. The
lack of any seasonal differences in
bioaccessibility of Pb, Mn, or Zn may be due to
minimal changes observed in soil redox
potential. Only Cd showed lower
bioaccessibility in August (2003) compared to
May and October. Thus, factors other than
oxidation-reduction potential (ORP) (e.g.,
temperature, biological activity) must exert
seasonal influences on Cd bioaccessibility.
Finally, the P-treatment induced reductions in
tissue-Pb levels observed during this study may
not be completely protective to many waterfowl
species. The lowering of blood lead (PbB)
levels from 5.0 to 2.5 |o,g/L is indeed
environmentally significant; however, severe
chemical signs of Pb toxicity can occur at PbB
levels < 2.0 ng/L (Beyer, 2000; Pain, 1996).
8.1.3 Geochemical Modeling
The PHREEQCi and other modeling results
suggest that P treatment removes Pb+2 ions via
formation of poorly soluble Pb-phosphate
species, including chloropyromorphite.
However, the effects of organo-lead complex
formation, plus PO4"3 absorption to mineral (e.g.,
Fe-oxide) surfaces, on the above reaction were
not addressed in this study. Furthermore, long-
term seasonal variability in ORP and/or pH
conditions probably exerts more intense and
transient effects on Pb speciation and Pb
bioavailability than indicated by these modeling
efforts.
8.2 Recommendations
Follow-on work should include:
- periodic assessment of the long-term
effectiveness of phosphoric acid
treatment of Pb-contaminated soils; and
- refinements to the geochemical model.
Annual screening of composite samples (from
the untreated and P-treated plots) for Pb
bioaccessibility (using W-PBET) would provide
cost-effective insight into potential changes in
contaminant bioavailability to waterfowl over
time. This effort could be supplemented every 4
years with another waterfowl feeding study, so
63
-------
as to recalibrate the W-PBET results. These Finally, additional research to characterize
combined data sets would coincide with the 5- kinetics, adsorption, and interaction of metals
year Comprehensive Environmental Response, with organic (humic/fulvic) acids would allow a
Compensation, and Liability Act (CERCLA) more thorough analysis of the solubility and
remedy review process assumed to occur at such speciation of Pb and other metallic contaminants
sites within the Coeur d'Alene River Basin. of concern. This activity, along with better
quantitation of interactions between mineral
surfaces with aqueous metal and P-species,
would result in more accurate models for
predicting contaminant availability for transport
and uptake into environmental receptors.
64
-------
9. References
Balistrieri, L. S., S. E. Box, et al. 2003.
Modeling Precipitation and Sorption of
Elements during Mixing of River Water and
Porewater in the Coeur d'Alene River Basin.
Environmental Science and Technology 37:
4694-4701.
Berti, W.R., and S.D. Cunningham. 1997.
In-place inactivation of Pb in Pb-
contaminated soils. Environmental Science
and Technology 31:1359-1364
Bennett, E.H., Siems, P. L., Constantopoulos, J.
T. 1989. The geology and history of the Coeur
d'Alene mining district, Idaho, p. 137-156, In V.
E. Chamberlain, Breckenridge, R. M.,
Bonnichsen, B., ed. Guidebook to the geology of
northern and western Idaho and surrounding
area, Vol. 28, Bulletin 28 ed. Idaho Geological
Survey, Moscow, ID
Beyer, W. N., D. K. Audet, et al. 2000.
"Relation of Waterfowl Poisoning to Sediment
Lead Concentrations in the Coeur d'Alene River
Basin", Ecotoxicology 9:207-218
Beyer, W.N., E.E. Conner, and S. Gerould.
1994. Estimates of soil ingestion by wildlife.
Journal of Wildlife Management 58:375-382.
Blus, J.L., C.J. Henny, D.J. Hoffman, and R.A.
Grove. 1991. Lead toxicosis in tundra swans
near a mining and smelting complex in Northern
Idaho. Archives of Environmental
Contamination and Toxicology. 21:549-555
Bostick, B.C., C.M. Hansel, M.J. La Force, and
S. Fendorf. 2001. Seasonal fluctuations in Zinc
speciation within a contaminated wetland.
Environmental Science and Technology
35:3823-3829.
Cao, R.X., L.Q. Ma, M. Chen, S.P. Singh, and
W.G. Harris. 2003. Phosphate-induced metal
immobilization in a contaminated site.
Environmental Pollution 122:19-28.
Cassner, N.A. 1991 Toxic River: politics and
Coeur d'Alene mining pollution in the 1930's
Idaho Yesterdays 35:2-19.
Chen, X. B., J. V. Wright, et al. 1997. Effects of
pH on heavy metal sorption on the
mineralapatite. Environmental Science and
Technology 31: 624-631.
Davis, A., J.W. Drexler, R. M.V., and A.
Nicholson. 1993. Micromineralogy of mine
wastes in relation to lead bioavailability, Butte,
Montana. Environmental Science and
Technology 27:1415 -1425.
Duggan, M.J., M.J. Inkskip, S.A. Rundle, and
J.S. Moorcroft. 1985. Pb in playground dust and
on the hands of schoolchildren. Science of the
Total Environment 44:65-79.
Essington, M.E., J.E. Foss, and Y. Roh. 2004.
The soil mineralogy of lead at Horaces Villa.
Soil Science Society of America Journal 68:979-
993.
Gee, G.W., and J.W. Bauder. 1986. Particle-size
analysis., In A. Klute, ed. Methods of soil
analysis., 2nd. ed. SSSA, Maddison, Wisconsin
Heinz, G.H., D.J. Hoffman, and D.J. Audet.
2004. Phosphorus amendment reduces
bioavailability of lead to mallards ingesting
contaminated sediments. Archives of
Environmental Contamination and Toxicology.
46:534-541.
Hettiarachchi, G.M., G.M. Pierzynski, and M.D.
Ransom. 2000. In situ stabilization of soil lead
using phosphorus and manganese oxide.
Environmental Science and Technology
34:4614-4619.
65
-------
Iskandar, I. K., and M. B. Kirkham. Trace
Elements in Soil Bioavailabilitv. Flux, and
Transfer. Boca Raton, Fla: Lewis Publishers,
2001.
Kendall, R.J., and C.J. Driver. 1982. Lead
poisoning in swans in Washington State. Journal
of Wildlife Diseases 18:385-387.
Kimball, W.H., and Z.A. Munir. 1971. The
corrosion of lead in a simulated waterfowl
gizzard. Journal of Wildlife Management
35:360-365.
Klasing, K.C. 1998. Comparative avian
nutrition. Cab International, New York
Laperche, V., T.J. Logan, P. Gaddam, and S.J.
Traina. 1997. Effect of apatite amendments on
plant uptake of lead from contaminated soil.
Environmental Science and Technology
31:2745-2753.
LeJeune, K., T. Podrabsky, J. Lipton, D. Cacela,
and a. et. 2000. Report of injury assessment and
injury determination: Coeur d'Alene Basin
natural resource damage assessment. Prepared
by Status Consulting Inc. for United States
Department of the Interior, Fish and Wildlife
Service, United States Department of
Agriculture, Forest Service Coeur d'Alene Tribe,
Boulder, Colorado.
Levengood, J.M., and L.M. Skowron. 2001. Use
of a simulated gizzard to measure bioavailability
of metals and other elements to waterfowl.
Ecotoxicology 10:299-304.
Lindsay, W.L. 1979. Chemical equilibria in
soils. John Wiley and Sons, New York.
Long, K.R. 1998a. Grade and tonnage models
for Coeur d' Alene-type polymetallic veins.
Open File Report 98-583. U.S. Geological
Survey, Tucson
Maenpaa, K.A., J.V.K. Kukkonen, and M.J.
Lydy. 2002. Remediation of heavy metal-
contaminated soils using phosphorus: evaluation
of bioavailability using an earthworm assay.
Archives of Environmental Contamination and
Toxicology. 43:389-398.
McKenzie, R.M. 1980. The adsorption of lead
and other heavy metals on oxides of manganese
and iron. Australian Journal of Soil Research
18:61-73.
Melamed, R., X. Cao, M. Chen, and L.Q. Ma.
2003. Field assessment of lead immobilization in
a contaminated soil after phosphate application.
Science of the Total Environment 305:117-127
Mitchell, V.E., Bennett, E.H. 1983 Production
statistics for the Coeur d'Alene mining district,
Shoshone County, Idaho; 1884-1890. Technical
Report 83-3. Idaho Geological Survey.
Nriagu, J. O. 1984. Formation and stability of
base metal phosphates in soils and sediments.
Phosphate Minerals. J. O. Nriagu and P. B.
Moore. New York, Springer-Verlag: 318-329.
Oomen, A.G., A. Hack, M. Minekus, E.
Zeijdner, C. Cornelis, G. Schoeters, W.
Verstraete, T. Van De Wiele, J. Wragg, C.J.
Rompelberg, A. Sips, and J. Van Wijnen. 2002.
Comparison of five in vitro digestion models to
study the bioaccessibility of soil contaminants.
Environmental Science and Technology
36:3326-3334.
Oomen, A.G., J. Tolls, A.J.A.M. Sips, and
M.A.G.T. Van den Hoop. 2003. Lead speciation
in artificial human digestive fluid. Archives of
Environmental Contamination and Toxicology.
44:107-115.
Pain, D.J. 1996. "Lead in Waterfowl", Chapter
10 (pp. 251-264) In Beyer, W.N. et al. (Eds.),
Environmental Contaminants in Wildlife:
Interpreting Tissue Concentrations, Lewis
Publishers, Boca Raton, Florida.
66
-------
Paulson, A. J. 2001. Biogeochemical removal of
Zn and Cd in the Coeur d'Alene river Idaho,
USA, downstream of a mining district. The
Science of the Total Environment 278: 31-44.
Ridolfi. 1993. Confirmation of exposure of
natural resources to hazardous substances in the
Coeur d'Alene Basin of northern Idaho. Ridolfi
Engineers and Associates, Inc., Seattle, WA
Rodriguez, R.R., and N.T. Basta. 1999. An in
vitro gastrointestinal method to estimate
bioavailable arsenic in contaminated soils and
solid media. Environmental Science and
Technology 33:642-649.
Ruby, M.V., A. Davis, J.H. Kempton, J.W.
Drexler, and P.D. Bergstrom. 1992. Lead
bioavailability: dissolution kinetics under
simulated gastric conditions. Environmental
Science and Technology 26:1242.
Ruby, M.V., A. Davis, R. Schoof, S. Eberle, and
C.M. Sellstone. 1996. Estimation of lead and
arsenic bioavailability using a physiologically
based extraction test. Environmental Science
and Technology 30:422-430.
Ruby, M. V., R. Schoof, et al. 1999. Advances
in evaluating the oral bioavailability of
inorganics in soil for use in human health risk
assessment. Environmental Science and
Technology 33: 3697-3705.
Ruby, M.V. 2003. Application of in vitro
extraction tests to estimate lead bioavailability
from soil. EPA Bioavailable Workshop, Tampa,
Florida
Ruby, M.V., Davis, A., Nicholson, A. 1994. In
situ formation of lead phosphate in soils as a
method to immobilize lead. Environmental
Science and Technology 28:646-654
Schecher, W. 1998. MINEQL+ version 4.5.
Hallowell, ME, Environmental Research
Software.
Seaman, J.C., J.S. Arey, and P.M. Bertsch. 2001.
Immobilization of nickel and other metals in
contaminated sediments by hydroxylapatite
addition. J. Environ. Qual. 30:460-469.
Sileo, L., L.H. Creekmore, D.J. Audet, M.R.
Snyder, C.U. Meteyer, J.C. Franson, L.N.
Locke, M.R. Smith, and D.L. Finley. 2001. Lead
poisoning of waterfowl by contaminated
sediment in the Coeur d'Alene River. Archives
of Environmental Contamination and
Toxicology. 41:364-368.
Silviera, D.J., and L.E. Sommers. 1977.
Extractability of copper, zinc, cadmium and lead
in soils incubated with sewage sludge. Journal of
Environmental Quality 6:47-52.
Sparks, D.S. 1989. Kinetics of soil chemical
processes. Academic Press Inc, San Diego
Strawn, D.G. 2005. University of Idaho, Final
Report Contaminant Speciation in Riparian
Soils, for Mine Waste Technology Program,
Activity III, Project 38. Complete copy in
Appendix A.
Sturkie, P.D. 1986. Avian physiology. 4th ed.
Springer-Verlag, New York, Herdelberg, Berlin
TerraGraphics Environmental Engineering Inc.
2003a. Soil amendment studies at Bull Run and
Black Rock Slough Coeur d'Alene basin. Final
Data Summary Memorandum, Moscow, ID.
TerraGraphics Environmental Engineering, Inc.
2003b. Data summary memorandum: Soil
amendment studies at Bull Run and Black Rock
Slough, Coeur d'Alene basin. Final Report,
Moscow, ID.
Wixson, G.W., and B.E. Davies, (eds.) 1993.
Lead in soil: recommended guidelines. Science
Reviews, Northwood.
67
-------
Yang, J., D.E. Mosby, S.W. Casteel, and R.W. Zhang, P.C., J.A. Ryan, and L.T. Bryndzia.
Blanchar. 2001. Lead immobilization using 1997. Pyromorphite formation from goethite
phosphoric acid in a smelter-contaminated urban adsorbed lead. Environmental Science and
soil. Environmental Science and Technology Technology 31:2673-2678
35:3553-3559
68
-------
Appendix A: D.G. Strawn's Final Report to MSE,
Dated January 26, 2006
-------
Table A.I. Raw elemental composition data (mg kg"1) for soils in Table 1.1, showing three replicates of each soil composite and the
wavelength used for each element.
Sample
ID
2(a) Avg
Stddev
2(b) Avg
Stddev
2(c) Avg
Stddev
2 Avg.
StDev
4(a) Avg
Stddev
4(b)Avg
Stddev
4(c) Avg
Stddev
4 Avg.
StDev
6(a) Avg
Stddev
6(b)Avg
Stddev
6(c) Avg
Stddev
6 Avg.
StDev
As
189.042
77.129
0.0156
79.348
0.0212
85.591
0.0110
80.6893
4.3876
126.027
0.0245
139.433
0.0178
141.241
0.0074
135.5669
8.3111
40.650
0.0308
37.252
0.0164
35.654
0.0197
37.8519
2.5516
Cd
228.802
28.093
0.0014
30.832
0.0016
31.668
0.0038
30.1980
1.8701
16.199
0.0018
16.101
0.0014
16.814
0.0003
16.3714
0.3867
11.220
0.0015
11.065
0.0015
11.208
0.0002
11.1642
0.0860
Fe
239.562
77,986.074
1.0940
79,427.359
3.0370
78,399.582
2.5390
78,604.3383
742.1388
85,933.437
1.2190
84,538.376
1.6960
83,863.399
0.7681
84,778.4042
1,055.6867
40,103.567
1.7420
40,066.225
0.5197
40,321.730
0.7011
40,163.8408
138.0049
Mn
257.61
5,626.674
0.1128
5,922.587
0.2667
5,666.841
0.1861
5,738.7008
160.5120
7,332.293
0.0909
7,466.630
0.1803
7,137.643
0.0692
7,312.1888
165.4120
1,482.451
0.0654
1,388.245
0.0212
1,446.994
0.0293
1,439.2299
47.5805
P
178.768
23,256.561
0.5787
24,257.688
1.3990
24,837.866
1.4090
24,117.3719
799.9361
252,522.101
7.3380
280,033.370
12.5000
288,581.856
0.6260
273,712.4425
18,842.5604
17,079.977
0.7613
16,846.026
0.2928
16,977.848
0.6114
16,967.9505
117.2889
Pb
220.353
4,959.829
0.0526
5,318.134
0.2264
5,253.661
0.1705
5,177.2078
190.9960
4,568.383
0.0853
4,468.854
0.1002
4,470.803
0.0430
4,502.6800
56.9086
3,550.058
0.1943
3,526.490
0.0142
3,599.684
0.0100
3,558.7437
37.3619
S
182.034
1,656.133
0.0527
1,800.371
0.0318
1,759.414
0.1015
1,738.6394
74.3295
1,894.696
0.0313
1,843.993
0.0623
1,784.932
0.0766
1,841.2071
54.9348
453.682
0.0912
420.530
0.0224
421.941
0.0318
432.0510
18.7466
Si
251.612
237,680.771
3.7510
247,348.887
12.4400
242,913.180
5.8130
242,647.6126
4,839.5256
262,350.494
0.7848
261,401.557
4.3520
263,555.787
2.2400
262,435.9462
1,079.6542
290,851.554
10.8900
300,496.689
2.2880
296,677.215
3.3270
296,008.4858
4,857.2171
Zn
202.548
2,279.861
0.0729
2,395.281
0.1389
2,366.109
0.0942
2,347.0835
60.0161
2,831.513
0.0483
2,811.457
0.1260
2,888.425
0.0050
2,843.7986
39.9278
764.384
0.0331
767.936
0.0178
775.053
0.0067
769.1244
5.4326
A-2
-------
Table A. 1. Continued
Sample
ID
8(a) Avg
Stddev
8(b) Avg
Stddev
8(c) Avg
Stddev
8 Avg.
StDev
As
189.042
55.330
0.0113
56.764
0.0164
55.553
0.0052
55.8820
0.7718
Cd
228.802
9.560
0.0012
9.629
0.0013
8.965
0.0013
9.3848
0.3649
Fe 239.562
48,873.626
1.8260
48,328.912
1.0290
46,316.360
1.1270
47,839.6328
1,347.0149
Mn 257.61
2,840.659
0.1207
2,790.451
0.0691
2,625.677
0.0723
2,752.2625
112.4638
P 178.768
543.681
0.1347
705.570
0.0839
454.767
0.0898
568.0062
127.1587
Pb
220.353
3,862.637
0.1850
3,832.891
0.1394
3,659.263
0.0450
3,784.9306
109.8427
S 182.034
459.066
0.0330
464.191
0.0475
448.267
0.0294
457.1745
8.1290
Si 251.612
298,076.923
9.0440
301,326.260
4.9840
293,607.801
4.4390
297,670.3279
3,875.2604
Zn
202.548
1,096.703
0.0450
1,102.387
0.0170
1,060.130
0.0285
1,086.4069
22.9332
Table A.2. Raw data from particle size analysis of composite soil samples reported in Table 1.2.
Comp2
Very Fine
Sandy Loam
Comp 4
Very Fine
Sandy Loam
Comp 6
Silt Loam
Comp 8
Silt Loam
Units
g
%
g
%
g
%
g
%
Very
Coarse
Sand
0.039
0.27
0.021
0.15
0.049
0.34
0.009
0.06
Coarse
Sand
0.043
0.30
0.007
0.05
0.109
0.77
0.002
0.01
Medium
Sand
0.039
0.27
0.012
0.09
0.086
0.61
0.020
0.14
Fine
Sand
1.478
10.24
2.683
18.89
0.899
6.34
0.959
6.76
Very
Fine
Sand
6.821
47.25
5.750
40.48
3.905
27.51
2.790
19.66
Sand
Total
8.420
58.32
8.473
59.66
5.049
35.57
3.780
26.64
Silt
Total
5.059
35.04
5.012
35.29
7.847
55.29
9.017
63.55
Clay
Total
0.958
6.64
0.718
5.06
1.298
9.14
1.393
9.82
Total
14.437
98.67
14.202
99.18
14.194
98.82
14.190
99.19
Original
Total
14.632
14.319
14.364
14.305
A-3
-------
Table A.3. Electron Microprobe Elemental Associations:
Strongly associated = 4
Moderately associated = 3
Weakly associated = 2
No visual association = 1
Plot 2 Associations
Sample
P2C7
P2C7
P2C7
P2C7
P2C7
P2C7
P2C8
P2C8
P2C8
P2C8
P2C8
P2C8
P2C9
P2C9
P2C9
P2C9
P2C9
P2C9
Area of
Interest
(x,y)
308,231
346,230
360,310
369,291
441,181
447,145
303,178
314,272
376,249
427,161
439,161
482,255
312,123
320,109
348,105
372,114
394,083
428,243
Fe-Pb
2
2
2
2
3
2
1
2
2
3
2
1
3
2
2
2
2
2
Mn-Pb
4
2
2
2
3
1
1
1
2
4
4
1
2
1
2
2
2
2
P-Pb
O
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Fe-P
4
2
3
4
4
4
2
4
4
3
4
3
4
3
4
4
4
4
Mn-P
2
2
2
2
3
1
1
O
2
3
2
2
2
2
3
2
2
2
Mn-Fe
2
2
4
3
3
4
4
4
4
4
3
4
3
3
3
4
2
3
Fe-Si
1
2
2
2
3
1
1
2
2
1
2
1
2
2
2
1
2
2
A-4
-------
Table A. 3. Continued
Plot 4 Associations
Sample
P4C7
P4C7
P4C7
P4C7
P4C7
P4C7
P4C8
P4C8
P4C8
P4C8
P4C8
P4C8
P4C8
P4C8
P4C9
P4C9
P4C9
P4C9
P4C9
P4C9
Area of
Interest
(x,y)
333, 151
403, 199
428, 198
456, 153
485, 208
486, 202
354, 306
370,216
391,328
408, 221
424, 202
424, 217
470, 208
473, 203
319,289
338,313
443, 152
452, 298
459,210
487, 204
Fe-Pb
2
1
1
1
1
1
1
3
4
1
1
2
1
2
3
4
4
4
3
4
Mn-Pb
2
1
2
2
1
4
1
2
1
1
2
4
3
2
2
3
3
2
3
2
P-Pb
1
1
1
1
1
1
1
O
1
1
1
2
1
2
3
4
O
O
2
3
Fe-P
1
1
1
1
1
1
1
3
1
1
2
1
1
2
2
3
2
2
2
3
Mn-P
1
1
1
1
1
1
1
2
1
1
1
1
1
2
1
2
2
2
2
2
Mn-Fe
4
4
3
4
4
3
2
2
4
4
4
2
3
3
4
4
4
3
3
3
Fe-Si
2
1
3
1
1
2
2
2
2
3
4
2
3
2
2
3
3
2
3
2
A-5
-------
Table A. 3. Continued
Plot 6 Associations
Sample
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C7
P6C8
P6C8
P6C8
P6C8
P6C8
P6C9
P6C9
P6C9
P6C9
P6C9
Area of
Interest
(x,y)
312,242
344, 248
356,231
358,261
371,216
378, 276
398, 208
402,315
434, 278
465, 249
498, 110
354, 256
361, 147
399, 228
400, 208
454, 290
331,212
357, 180
395, 183
452, 188
482, 224
Fe-Pb
2
1
2
2
3
1
3
2
2
2
3
2
1
2
3
1
2
1
2
1
3
Mn-Pb
2
1
3
3
2
3
3
2
2
3
2
3
1
4
2
1
2
2
2
1
2
P-Pb
3
1
2
2
3
2
2
2
2
2
2
2
1
2
3
1
2
1
2
1
2
Fe-P
4
3
3
4
4
2
3
4
3
4
4
3
1
3
4
3
3
2
4
3
3
Mn-P
2
1
2
2
2
2
2
O
2
2
2
2
1
2
2
1
2
1
2
1
2
Mn-Fe
2
1
3
4
2
2
3
2
4
2
2
3
4
4
2
2
3
4
3
2
3
Fe-Si
2
3
2
3
3
2
2
2
2
2
2
2
1
2
2
2
3
2
3
2
2
A-6
-------
Table A. 3. Continued
Plot 8 Associations
Sample
P8C7
P8C7
P8C7
P8C7
P8C7
P8C7
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C8
P8C9
P8C9
P8C9
P8C9
P8C9
Area of
Interest
(x,y)
312, 164
325, 245
380, 269
398, 323
456, 196
490, 265
302, 323
328, 376
333,340
354, 225
361,241
395, 203
399, 204
413,208
429, 346
442, 252
472, 213
413, 154
448, 239
451,293
456, 227
484, 269
Fe-Pb
3
2
3
1
3
1
1
2
1
1
2
2
2
2
2
3
2
2
2
2
2
1
Mn-Pb
3
3
2
3
2
4
4
3
3
4
3
2
3
3
3
2
3
4
2
3
3
3
P-Pb
2
1
1
1
1
1
1
2
1
1
2
2
1
1
2
1
2
1
1
1
2
1
Fe-P
1
1
2
1
1
1
2
2
1
2
2
3
2
1
3
3
3
1
3
2
2
1
Mn-P
2
1
1
1
1
1
1
1
1
1
2
2
1
2
1
1
2
1
1
2
1
1
Mn-Fe
3
2
3
2
2
2
3
3
2
3
3
3
3
3
2
3
3
2
3
2
3
3
Fe-Si
2
2
2
2
2
3
2
2
3
3
4
3
2
2
2
3
2
2
1
2
A-7
-------
Table A.4. Raw data from ICP-AES analysis of AOD- and CBD-extracted soils shown
in Table 1.4, showing three replicates of each soil composite and the wavelength used
for each element.
Sample
ID
2(a) Avg
Stddev
2(b) Avg
Stddev
2(c) Avg
Stddev
2 Avg.
StDev
4(a) Avg
Stddev
4(b) Avg
Stddev
4(c) Avg
Stddev
4 Avg.
StDev
6 (a) Avg
Stddev
6 (b) Avg
Stddev
6 (c) Avg
Stddev
6 Avg.
StDev
8(a) Avg
Stddev
8(b) Avg
Stddev
8(c) Avg
Stddev
8 Avg.
StDev
AODFe
240.488
57,260.8696
0.4666
62,269.0058
0.1050
61,688.8889
0.2408
60,406.2548
2,739.3831
48,382.4701
0.0350
50,382.6715
0.0482
51,185.4545
0.1292
49,983.5320
1,443.4904
24,338.2550
0.1200
22,719.7183
0.0024
24,883.7545
0.0669
23,980.5760
1,125.4839
25,385.9779
0.1012
26,225.6055
0.2325
26,248.3271
0.0276
25,953.3035
491.4498
AODMn
257.610
4,033.9130
0.0302
3,937.3099
0.0059
4,236.8889
0.0127
4,069.3706
152.9046
4,276.4940
0.0034
4,527.0758
0.0078
4,288.1455
0.0087
4,363.9051
141.4300
1,074.3624
0.0027
1,014.0845
0.0003
1,307.4368
0.0026
1,131.9612
154.9262
2,268.4871
0.0063
2,485.9516
0.0204
2,473.6059
0.0018
2,409.3482
122.1454
CBDFe
238.204
58,904.5936
0.1752
59,547.9204
0.2211
52,934.7826
0.2085
57,129.0989
3,646.5990
29,774.3682
0.1359
28,297.0297
0.0952
29,103.6907
0.1285
29,058.3629
739.7116
32,686.0254
0.0725
28,892.1569
0.0342
31,320.5645
0.0784
30,966.2489
1,921.5916
34,396.0396
0.0832
33,916.9675
0.1066
33,745.2471
0.0906
34,019.4181
337.2755
CBDMn
259.373
4,064.4876
0.0124
3,503.6166
0.0130
3,143.1159
0.0120
3,570.4067
464.3028
2,103.7906
0.0094
2,151.4851
0.0071
2,246.0457
0.0092
2,167.1072
72.4028
1,155.1724
0.0025
1,282.3529
0.0015
1,221.7742
0.0026
1,219.7665
63.6140
2,538.6139
0.0052
2,454.8736
0.0077
2,532.3194
0.0064
2,508.6023
46.6367
A-8
-------
Appendix Images for Microprobe Analysis of Plots, 2, 4, 6, 8
Organized by plot, cell, and location on thin section. Each WDS image is 512 x 512 |j,m.
A-9
-------
Plot 2
2C7 - 308, 231
BSE Imae
: 1 agfig ",-;:-'
-..- , y -.
In
' m _^H
91 . B^fl .. v
-. mfm ' ' ' -
.'".':'-
iblfl
.,-'-' ! . . :
:.:,'. - . -,
'. BB^^^^^I
. " / K^H '
iblfl
.,-'-' ! . . :
:- ;'.' ' ., ' '-,'1 .
^^^^^1
a @ ' i s -
A-10
-------
Phosphorous(P)
Lead (Pb)
^\_
EDS Profiles by Analysis Point
Point 1
c:\e d 5-.ix3 2\g e n e s i s\g enspc.spc
Label A: O1junO4 P2C7 308 231 Point 1
J U^
1 00 2 00 1 III) 1 00 Stttt 6.00 7 00 1! Oil 9 00
A-ll
-------
Point 2
c:\edax32\genesis\genspc.spc
Label A: OljunOI P2C7 308 231 Point 2
1.00 2.00
3.00 4.00 5.00 6.00 7.00 8.00
Point 3
Label A: O1 junO4 P2C7 3OB 231 Point 3
A-12
-------
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: (HjunlM P2C7 3O8 231 Roint A
A 10 5 10 6 III 7 111
Point 5
Label A: II I J.II.IM P2C7 308 231 Point 5
1 10 2 10 3 10 1 111 5 10 6 10
Point 6
c:\edax32\genesis\genspc.spc
Label A: U I juiiUI P2C7 3O8 231 Point E
5.10 I. Ill
A-13
-------
Point 7
c:\edax32\genesis\genspc.spc
Label A: OljunO-1 PZC7 308 231 Point 7
I 111 2 10 j III 4 10 5 10 6 10 7 III 0 10 9 10
Point 8
Label A: OljunOI P2C7 308 231 Point 8
A-14
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: O1junO4 P2C7 3O8 231 Point 9
Point 10
c :\e d -a:<"J 2\g e n e s i s\g enspc.spc
Label A: O1 junO4 P2C7 308 231 Point 1 O
A-15
-------
P2C7 - 346, 230
BSE Imaj
A-16
-------
Silicon
EDS Scan Images by Point
Point 1
e::\c d a>c3 Z\g e n e s i s\,g enspc.spc
Label A: O1 junO4 P2C7 346 23O Point 1
A
1.00 2.00 3.00 4_00 5.00 ft nil 7.00 0.00 9.00
Point 2
e d sa>:3 Z\g e n e s i s\g enspc.spc
Label A: OljunOI F-ZC7 3/IG Z3O Point 2
1 nil 2.DO 3.OO 4 nil 5.DO 6.DO 7.DO 8.DO 9.1
A-17
-------
Point 3
Label A: (I I j.ii.iM PZC7 346 23O Point 3
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
Point 4
n e s i s\g enspc.spc
Label A: O1junO4 P2C7 346 23O Point
2.00 3.00 1_00 5_00 6_00 7_00 8_00 9.1
Point 5
s\g enspc.spc
Label A: OljunO 1 R2C71 3-1B 23O Point 5
2.UU 3_OO -1.UU b_UU
7.UU 8_OO U.I
A-18
-------
Point 6
c:\ed .-»;.[ ~.'\fj e n e s i r,\rj enspc.spc
Label A: n I junOI PZC7 346 Z3O Roint G
1.00 2_00
S 00 6_00
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: O1junD4 P2C7 3^16 23O Point 7
LOO 2 00 3_00 -1.00 5_
G_00 7_00
Point 8
c:\edax32\genesis\genspc.spc
Label A: M MM,." 1 P2C7 346 23O Point 8
1 00 2 00
A 00 5 00 6 00 7 00 0 00 9 00
A-19
-------
Point 9
c:\ed .-»;.[ ~.'\fj e n e s i r,\rj enspc.spc
Label A: O1junO4 PZC7 346 23O Point <
1.00 2_00 3 00 4.00 S 00 6_00 T.OO 8_
Point 10
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: Ol junD4 R2C7 346 Z3O Point 1 O
1.00 2.00 3.00 -4.00 5.00 6.00 7.00 8.00 9.1
A-20
-------
P2C7 - 360, 310
BSE Image
V*;V >.;:; '>
IBi
* * T ^
^
Lllr* %^v- S| 'C*r*£v ^
A-21
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c!\e d ax:3 2\g e n e s i s\g enspc.spc
UabelA: OljunOJ P2C7 36O 31 O Roint 1
I (IU 2_00 3_00 -4.00 "j..UU 6.00 7_00 8.00 9_l
Point 2
c:\ed a>c32\genesis\genspc.spc
Label A: O I junO4 P2C7 36O 31 D Point 2
1 00 2 00 3 00 4 00 5 00 G 00 7 00 8.00 91
A-22
-------
Point 3
c:\e d a>c3 2\g e n e s i s\g enspc.spc
Label A: O1junO4 F-ZC7 36O 3TO Point 3
1 00 2 00 3 00 4 00 5 OO 1,1111 7 DO O OO 9 OO
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: O1 junO4 P2C7 3BO 31 D Roint
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Point 5
Label A: O1 junOI P2C7 36O 31 O Point G
1 00 2.00 3 00 A 00 5 00 6 OO 7 00 B 00 9 OO
A-23
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: O1junO4 P2C7 3BO 31 U Point B
O
A
2-ttU 3.00 4.0O 5.OO G.DD 7.1
Point 7
Label A: O1junO4 P2C7 3BD 31 D Roint 7
Point 8
Label A: O1 junO-4 P2C7 3BO 31 O Point !
G_00 9_00
A-24
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: OljunO4 P2C7 3GO 31 O Point 9
1.00 2.00 3.00 4.00 5.00 £.00 7.00 8.00 9.00
Point 10
c:\edax32\genesis\genspc.spc
Label A: O1 junOI P2C7 36O 31 O Point 1 O
Si
,
\
1_DO 2.00 3 00
5_OO G 00 7_00 8_00 9_OO
A-25
-------
P2C7-441,181
BSE Image
A-26
-------
EDS Scan Images by Point
Point 1
Label A: 111 junlll P2C7 441 1 81 Point 1
j
090 1.70 2_50 3.'JO 4_1O 4_90 5_7O 6_50 730 S. 10
Point 2
e d ax3 2\g e n e s i s\g enspc. s p c
Label A: O1junO4 P2C7 .441 181 Point
D_9G i.70 2_50 3.30
4.90 5_7O e_50 730 8. 10
A-27
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: O 1 junO-4 P2C7 441 181 Point 3
>J
0.90 1.70 2.50 3.30 4.10 4.90 5.70 6.50 7.30 8.10
Point 4
e d ax 3 2\g e n e s i s\g enspc.spc
Label A: O1 junO4 P2C7 ^111 1 B1 Point
Hf ^ ^VSTvA^v^^^v^^^^
0_90 1.70 250 3_30
5_7O 6_50 7 JO 8_10
Point 5
cr:\c d ax 3 2\g e n e s i s\g enspc.spc
Label A: O1 junOI PZC7 441 181 Point 5
1-00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
A-28
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: O 1 junO-4 P2C7 441 181 Point G
2.00 3.00 4.00 5.00 6.00 7.00 8_00 9_00
Point 7
c:\edaK32\genesis\genspc.spc
Label A: 01junO4 P2C7 441 1 81 Point 7
All 'l
_J~J ^,
1 00 2 00 3 00 4 00 5 00 f: 00 7 00 0 00 9 00
Point 8
c:\e d ax3 2\p e n e s i s\g enspc. spc
I nil 2.00 3.00 4.00 '.nu 6.00 7.00 0.00 9.00
A-29
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: Ol jun04 P2C7 441 1 81 Point 3
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
Point 10
c:\edax32\genesis\genspc.spc
Label A: 01 junO4 P2C7 441 1 81 Point 1 0
1 00 2 00 3 00 4 00 5 00 f: 00 7 00 0 00 9 00
A-30
-------
P2C7 - 447,145
BSE Image
A-31
-------
Silicon
EDS Scan Images by Point
Point 1
c:\ed ax3 2\g e n e s i s\|] e n s p c. s p c
Label A: PZC7 X 444 Y-1 15 Point 111 marOI
O
I
1 nil 2.00 3.00 4.00 5 00 6.00 7.00 8.00 9 00 10 00 11.00 12.00
Point 2
c:\edax32\genesis\genspc.spc
Label A: PZC7 X-444 Y-1 15 Point 211 marOI
1 00 2 00 3.00 4 00 5 00 6_00 7.00 8.00 9 00 10.00 11 00 12 00
A-32
-------
Point 3
c:\edax32\genesis\cjenspc.spc
Label A: PZC7 X-444 Y-1 45 Point 311 marOI
II SI! I fill 2.40 3.20 4.00
A-33
-------
P2C7 - 369, 291
BSE Image
~
A-34
-------
EDS Scan Images by Point
Point 1
c:\e d a ~-T 3 Z\ tj e n e s i s\g e n s p c. s p c
Label A: OljunOI P2C7 369 291 Point 1
1 00 2.00 3_00 4 00 b.OU 6 00 7 00 0 00 9 00
Point 2
c:\e d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: iMj.n.lui P2C7 369 291 Point 2
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
A-35
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: O 1 junO-4 P2C7 369 29 I Point 3
si i TC
Al . / \ Pb
2.00 3.00 4.00 5.00 6.00 7.00 8 00 9 00
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: DljunOI PZC7 369 291 Point ^
L.
LOO 2.00 3.00 4.00 5_OO
-------
Point 6
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: O1junO4 PZC7 369 291 Roint 6
I.iJU 2_00 3_00 4.00 5_00 6_00 7_00 8_00 9_00
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: D1junO4 P2C7 369 291 Point ~7
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
Point 8
c:\edax32\genesis\genspc.spc
Label A: M MM,." 1 P2C7 369 291 Point 8
1 UIJ I 00 3 (II) 4 00 5 00 6 00 7 00 0 00 9 00
A-37
-------
Point 9
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: O1jun04 P2C7 369 291 Point 9
Point 10
c:\edax32\genesis\genspc.spc
Label A: OljunO't P2C7 369 291 Point 1 0
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
A-38
-------
P2C8 - 303,178
BSE Image
A-39
-------
Mg
OL
Silicon (Si)
EDS Scan Images by Point
Point 1
2.00 4.00 h Oil 8.00 10.00 \ y fin M 00
Point 2
Label A: 27mayO1 R2C8 3O3 1 78 Roint 2
2-00 -4-00
10-00 12-00 1-4-00
A-40
-------
Label A: 27mayO4 P2C8 3O3 1 78 Point 3
Point 3
Point 4
Rb
Pb
Label A: 27mayQ4 P2C8 3O3 1 78 Point 5
Point 5
_,
A-41
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 3O3 1 78 Point 6
Point 7
RZC8 3O3 1 78 Roint 7
2.00 3_00
5.00 6.00 7_00 8. 1
9 00 10.00 11.00 12.00 13.OO
Point 8
Label A: Z7mayD4 R2CB 3O3 1 78 Point 8
JL
1.00 2.00 3.00 4.00 5.00 6.00 7.1
9.00 10.00 11.00 12.00 13.00
A-42
-------
Point 9
Label A: Z7may04 PZC8 303 1 78 Point 9
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
Point 10
Label A: 27may01 P2C8 303 1 70 Point 1 0
A-43
-------
P2C8 - 314, 272
BSE Image
A-44
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: 27mayO4 P2C8 31 A 27Z Point 1
4.00 5.00 6.00 7.00
Point 2
Label A: 27mayOJl P2C8 31 4 272 Point 2
O
L
A-45
-------
Point 3
Label A: 27mayO4 P2C8 31 A 272 Point 3
1.20 2.20
9.20 10.20
Point 4
Label A: 27mayO4 P2C8 31 4 272 Point
A-46
-------
Point 5
Label A: Z7mayOJ PZCB 31 4 272 Point 5
Fe Co
1.00 2.00 3.00 4.00 5.00 6.00
9.00 10.00
Point 6
c:\edax32\genesis\genspc.spc
Label A: 27mayO4 P2C8 31 4 272 Point 6
i nil 2.00
4.DO 5.0» ft Illl 7.00 6.00 9.00 10.00
Point 7
Label A: Z7mayO4 PZCB 31 A Z7Z Point 7
2_OO 3.OO
7 na 8_ao 9.00 io_oo
A-47
-------
Point 8
Label A: 27maya.H P2C8 31 4 272 Point 8
A-48
-------
P2C8 - 376, 249
BSE Imaj
A-49
-------
EDS Scan Images by Point
Point 1
c:\e d .a x 3 2\g, e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 376 2*9 Point 1
_^ >\^
1.00 2.00
7.00 8.00 9.00 10.00 11.00 12.00 13.00
Point 2
Label A: 27mayQ4 P2C8 376 249 Point 2
A-50
-------
Point 3
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 27 may O 4 P2C8 376 Z49 Roint 3
Point 4
Label A: 27mayD4 P2C8 376 249 Point
Fe
Ml,
Mf,
Point 5
cr:\ tr d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: Z7mayO4 P2CB 376 249 Point 5
A-51
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 376 249 Point 6
1.00 2_00 3.00 4.00 5.00 6.00 7.1
9.00 10.00 11.00
Point 7
c:\e d ax3 2\p c n e s i s\g e n s p c. spc
LOO 2_00 3_00 4_OO 5_00 f. IHI 7_00 S! (Ill 9_00 10_OO 11.00
Point 8
Label A: Z7mayO4 RZCO 376 249 Roint 8
1.00 2.00 3.00 4.00 5.00 G.OO 7.00 O.OO 9.00 10.00 11.1
A-52
-------
P2C8 - 427,161
BSE Image
A-53
-------
EDS Scan Images by Point
Point 1
e:\edo>e32\genesis\genspc-spc
Label A: 27mayO4 P2C8 427 161 Point 1
Fe
Ml,
**j V,
1 00 200 3.00 4 00 5.00 600 7.DO 000 9 00 10-00 1100 1200 13.00
Point 2
c:\edax32\genesis\genspc.spc
Label A: 27may04 P2C8 127 161 Point 2
100 200 300 4 00 500 600 700 800 900 1000 1100 1200 1300
A-54
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 427 1 61 Point 3
1.00 2.00 3.00 4.00 5.00
8.00 9.00 10.00 11.00 12.00 13.1
Label A: Z7mayO4 PZC8 4Z7 1 61 Point A
Point 4
2.00 3.0O
5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00 13.00
Point 5
tr:\"C d ax 3 Z\g e n e s i s\g enspc.spc
Label A: 27mayD4 P2CB 427 1 Bl Point 5
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00 13.00
A-55
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 427 1 61 Point 6
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 R2C8 427 1 61 Point 7
-Jl
2.00 3.OQ
5.00 6_00 7_00
Point 8
e d ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 427 1 61 Point 8
A-56
-------
Point 9
e:\ed a>:3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 JZ7 1 61 Point 9
Al I
1.00 2.00 3.00 -1.00 5_00 G_00 T_00 S_00 9.00 10.00 11.00 12.00 13.1
Point 10
c:\e d ax3 Z\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C8 127 1 B1 Point 1 O
A-57
-------
P2C8 - 439,136
BSE Image
v
- * V> A - *l '
FMV"*
EL i L tf/' A^fe- A iL^
*
A-58
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc.spc
Label A: 27mayO4 P2C8 439 1 36 Point 1
Fe
O
Pb K
VP PS ... K ....
Pb
Pb
11.00 12.00 13.00
Point 2
c:\edax32\genesis\genspc.spc
Label A: 27mayO
-------
Point 3
Label A: 27mayO4 P2C8 439 1 36 Point 3
O
Ti
2.00 4.00 6.00 0.00 10.00 12.00 14.00 16.00
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc..spic
Label A: Z7mayO4 PZC8 433 1 36 Roint
l
Ca
Ca
K
2_00 4.00 6.00 0.00 10.00 12.00 14.00 lli.OO
Point 5
tr:\"C d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: 27mayO1 PZC8 439 1 36 Point 5
10.00 12.00 1-4.1
A-60
-------
Label A: 27mayO4 P2C8 439 1 36 Point 6
Point 6
1.60 2.40
3.20 4.00
Label A: Z7mayO4 RZCB 433 1 36 Roint 7
Point 7
Point 8
Label A: Z7mayD4 RZCB 439 1 36 Roint 8
A-61
-------
Point 9
Label A: 27mayO4 P2C8 439 1 36 Point 9
Pb
Pb
1.00 2.00 3.00 4.00 5.00 6.00
8.00 9.00
11.00 12.00 13.1
Point 10
Label A: 27may04 P2C8 439 1 36 Point 1 0
100 200 300 4 00 500 f. 00 700 000 9 00 1000 1100 1200 1300
A-62
-------
P2C8 - 482, 255
BSE Image
A-63
-------
EDS Scan Images by Point
Point 1
Label A: 27mayQ4 P2C8 482 255 Point 1
r.^
100 2.00 300 400 500 600 TOO 000 900 1000 1100
Point 2
Label A: 27mayO4 P2C8 482 2S5 Point 2
2.00 3.00
9.00 10.00
A-64
-------
Point 3
Label A: 27mayO4 P2C8 4B2 255 Point 3
5.00 6.00 7.00
9.00 10.00 11.00 12.00
Point 4
Label A: 27mayD4 PZC8 J1O2 Z55 Point A
Point 5
Label A: Z7mayO4 PZC8 482 Z55 Point 5
A-65
-------
Point 6
Label A: 27 may O 4 P2C8 4BZ 255 Roint G
2_00 3_00 -1 Liu -J..UU
9_00 IU.IJU
Point 7
Label A: 27mayO4 R2C8 482 255 Roint 7
Label A: 27mayO4 P2C8 482 Z55 Roint 8
4.00 5.00 6.00 7.OO
Point 8
o
Re
Mg
A-66
-------
P2C9 - 312,123
BSE Imaj
A-67
-------
EDS Scan Images by Point
Point 1
r,:\f~ft a
; i s\g enspc.spc
Label A: 27mayO4 P2C9 312 1 23 Point 1
Pb
Pb
Point 2
Label A: 27mayO4 P2C9 312 123 Point 2
12.00 13_l
A-68
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 31 Z 1 23 Point 3
Pb
As
Pb
Pb
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 PZC9 312 123 Point
Ba
Ca
Cd
Cd Cd
Pb
As
Pb
Pb
Point 5
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: Z7mayD4 P2C9 31 2 1 23 Point 5
Cd
Cd C
Cd Cd
Pb
Pb
12.00 13.00
A-69
-------
Point 6
c:\ed ax:3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 PZC9 31 2 1 Z3 Point 6
i.,jyUJ '\
S
P
VA _
K
K Ba
Cd
Cd
Cd Ca
Cd Cd Ba
Ti Ti
Ba
Pb
As
Pb
Pb
2.00
3.00
4.00
9.00 10.00 11.00 12.00
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 27may04 P2C9 31 2 1 23 Point 7
Pb
As
Pb
Pb
A-70
-------
P2C9 - 320,109
BSE Imaj
^^^^i- .1
. . 7:
A-71
-------
EDS Scan Images by Point
Point 1
c:\e ft a
n e s i s\g e n s p c. s p c
Label A: Z/mayO-l P2C9 32O 1 O9 Point 1
2 00 3.00
Label A: 27mayO4 P2C9 32O 1 O9 Point 2
9.00 10 00
12-00 13.00
Point 2
s i s\g enspc.spc
Si
Cd
Cd
-L
I In
.-J
e_00 7.00
10 00 11.00
Pb
Pb
12.00 13_l
A-72
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 27mayO4 P2C9 32O 1 O9 Point 3
Pb
As
Pb
Pb
9.00 10.00 11.00 12.00
Point 4
n e s i s\g enspc..spic
Label A: Z7mayO4 PZC9 3ZO 1 O9 Point A
vSxAj
Pb
As
Pb
Pb
10.00 11.00
Point 5
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayD4 P2C9 3ZO 1 O9 Point 5
Pb
As
Pb
Pb
12.00 13.00
A-73
-------
Point 6
g e n e s i s\g enspc.spc
Label A: 27n
P2C9 3ZO 1 O3 Roint G
A-74
-------
P2C9 - 348,105
BSE Image
A-75
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: Z7mayO4 P2C9 348 1 O5 Point 1
9 00 10.00
Point 2
c :\eda>:
g e n s p c. spc
Label A: Z7mayO4 P2C9 348 1 O5 Point 2
A-76
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 348 1 O5 Point 3
Pb
As
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc.spc
PZC9 34B 1 O5 Roint A
1,
1
0 f. ' | K Ba
f\ l\ \ Cd Ti Ti
1 M9\ ' Cd Cd Ca Ba
/I Zn M' 1 S Cd Ba Mn Fe
_J \ Zj*\__/ y vS ^__ Cd _y\_-^ Ba Ba Mn Fe
LOO 2_00 3 00 4.OO 5.00 6.00 7.00
Point 5
o:\ea»x3^genesis\aenspc.apo
Pb
Pb
^n Zn As As P
8.00 9 00 10.00 11.00 12.00
Label A: 27mayO4 F-2C9 34B 1 OB Point S
A-77
-------
Point 6
g e n e s i s\g enspc.spc
Label A: Z7
ayO4 PZC9 34B 1 O5 Roint G
A
Ca
K
K Ba
Cd Cd
Cd Ca
Cd Cd
Pb
As
i.UU 2_00 3_00 -1 UU 5_00
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 348 1 O5 Point 7
c
A afl ' Cd Cd
A M , '. S cd Ca
^\_j \i VP cd___£i_
1.00 2.00 3.00 4.00
Ba Mn
Ba Mn
Ba Ba Fe Fe
5.00 1. III! 7.00
Point 8
Pb
Pb
~Z.n ^n As As P
8.00 9.00 10.00 11.00 12.00
c:\e d a:-c 3 2\g e n e s i s\g enspc.spc
Label A: Z7mayO4 PZC9 348 1 O5 Point 8
Pb
As
A-78
-------
Point 9
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 348 1 O5 Point 9
Pb
As
Point 10
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: Z7mayO4 PZC9 348 1 O5 Roint 1 O
Pb
As
LOO 2_00 3_00
Label A: 27mayO4 PZC9 34G 1 O5 Point 1 1
5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00
Point 11
cr:\c d ax 3 2\g e n e s i s\g enspc.spc
Ba Ti Ti
e.oo 7.00
9.00 10.00 11.00 12.1
A-79
-------
Point 12
c:\edax32\genesis\genspc.spc
Label A: 27mayO4 P2C9 3/18 1 05 Point 1 Z
Pb
As
A-80
-------
P2C9-372,114
BSE Image
>v
^. '
A-81
-------
EDS Scan Images by Point
Point 1
c:\e d ax 3 2\g e n e s i s\g e n s p c. spc
Label A: 27may04 P2C9 372 11 A Point 1
Pb
As
Point 2
e d ax:3 2\g e n e s i s\g enspc. spc
Label A: Z7mayO4 PZC9 37Z 111 Point Z
A-82
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 27mayO4 P2C9 372 11 A Point 3
8.00 9.00
11.00 12.00
Point 4
n e s i s\g enspc.spc
Label A: Z7mayO4 P2C9 372
Point 5
e s i s\g enspc.spc
Cd
Cd Cd ca
Cd Cd
Pb
As
As Pn
A-83
-------
Point 6
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: Z7mayO4 PZC9 372 114 Roint G
h
n [fje
Point 7
c:\e d ax3 2\g e n e s i s-\q cnspc.s-pc
I 11 A Roint 7
As Rb
1.00 2.00 3.00 4.00 5.00 6.00
e.oo 9.00 10.00 11.00 12.00
Label A: 27mayO1 P2C9 372 114 Point G
Point 8
e s i s\g enspc. spc
Cr
Cr
Pb Pb
Pb
Pb
Pb
A-84
-------
Point 9
Label A: Z7mayO4 PZC9 372 114 Roint <
I.UU Z.OO 3_00 -1.UU 5_00 L..IJU
Point 10
Label A: Z7mayO4 P2C9 37Z 114 Point 1 O
0.80 1.60 2.40 3.20 4.00 4.00 5.60 6.40 7.20 8.00
A-85
-------
P2C9 - 394, 083
BSE Image
A-86
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\e J a>: U 2\g e n e s i s\g enspc.spc
Label A: 27may04 P2C9 394 OO3 Point 1
Pb
As
1.00 2.00 3.00 4.00 S.OO 6.00 7.00 8.00 9.00 10.00 11.00
Point 2
g e n s p c. s p c
Label A: 27mayO4 P2C9 394 OB3 Point 2
JU
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
A-87
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 394 O83 Point 3
Pb
As
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc.spc
P2C9 39^1 O83 Roint A
Pb
As
Point 5
e s i s\g e n s p c. s p c
Label A: 27mayO1 R2C9 391 O83 Point 5
Cd B
Cd Co | B»
s__jEi___J LA
Pb
As
A-88
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 394 OB3 Point 6
J
Si
1
i1
Co
1 1 K
I ! K Ba Ti Ti
Cd Cd Ba Ba
Zn 1 1 S Cd Co Bo h
| Zn_^A\J lj= Cd Cd ^_ Bo
1
In FA Pb
_K|ln Fe Zn Zn As As
Point 7
c:\edaK32\genesis\genspc.spc
Label A: 27moy04 P2C9 394 083 Point 7
Ca
K
Cd Bo Ti Ti
Pb
As
Pb
Pb
A-89
-------
P2C9 - 428, 243
BSE Imaj
A-90
-------
Silicon
EDS Scan Images by Point
Point 1
n e s i s.\cj enspc. spc
Label A: 27mayO4 P2C9 428 243 Point 1
Pb
As
Point 2
c:\edax32\genesis\genspc.spc
Label A: 27may04 P2C9 428 243 Point 2
K Ba
Cd
Cd Ca
Pb
As
A-91
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 428 243 Point 3
0
1
Co
K
Cd K Ba Ti Ti
1 s Cd Ba
1 Ip Cd Ca Ba
V \^\ c&~^ Cd Ba Ba Fe Fe
Pb
Pb
Zn Zn As As Pb
Point 4
s i s\g e n s p c. spc
Label A: 27mayO1 P2C9 J
Z13 Point
Pb
As
Point 5
c:\e d a:-c 3 2\g e n e s i s\g enspc.spc
Label A: Z7mayO4 PZC9 1ZB
0
j
Ca
1 K
K Ba Ti Ti
Cd cd Ba Ba pb
i s Cd Ca Ba Pb
\F^____J____C^_^_^d___ Ba Fe Fe ~Z.n ~Z.n As As PI
1.00 2.00 3.00 4.0O 5.00 G.OO 7.00 0.00 9.00 10.00 11.00 12.00
A-92
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 27mayO4 P2C9 428 243 Point 6
Pb
^__^V___E5 ,___5G 55__>_-AS--,-, *8__E
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00
Point 7
Label A: Z7mayO4 PZC9 4Z8 Z^I3 Point 7
Ca
K
Pb
_Ziy As As P
1.00 2 00 3 00 4 00 5 00 6 00 7 00 8 00 9 00 10 00 11 00 12 00
Plot 4
A-93
-------
P4C7 - 333,151
BSE Image
»X -v^*4''*^
.w * .-""j
A-94
-------
EDS Scan Images by Point
Point 1
Label A: OBAprO^ P-flC? 333 T BT F'oiiil 1
s\g e n s p c. s p c-/-p e a kg e n , s p c
Label B: H KL
Point 2
Label A: QBAprfM P4C7 333 1 51 Point 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-f-p e a kg e n. s p c
Label B: H K
A-95
-------
Point 3
Label A: OSAprO.4 PJC7 333 I B I Point 3
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
Al
Ti
Ba
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00
Point 4
Label A: O5AprO4 P4C7 333 1 51 Roint A
\genspc. spc-/-peakgen.spc
Label B: H K
2_00 3.00 4.00 5.00 6.00 7_00 8.00 9.00 10.00 11.00
Point 5
Label A: O5AprO4 P-4C7 333 1 51 Roint 5
;:\e dax32\gen es i s\g e ns p c. sp c-/~p ea kg e n.s pc
Label B: H K
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.1
A-96
-------
Point 6
Label A: IH.AprlM P4C7 333 151 Point 6
x:32\genesis\genspc:-spc-/-pealcgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
Point 7
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. sp c
Label A: O5AprO4 P4C7 333 1 51 Point 7 Label B: H K
Pb
As
I mi 5.00 6_00 v mi
9.00 III llll I I till
Point 8
c:\e d ax: 3 2\g e n e s i s\g e n s p c. s p c-f-ft e a kg e n. s p c
Label B: H K
l.OO 2.00 3.00 -4.00 5.OO 6.00 7.00 8.00 9.00 10.00 11.00
A-97
-------
Point 9
Label A: OSAprO.4 PJC7 333 I B I Point 9
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8 00 9.00 10.00 11.00
Point 10
Label A: O5AprO4 P4C7 333 1 51 Roint 1 O
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
LOO 2 00 3_00 4.00 5.00 G 00 7 00 C 00 9_00 10.00 11.00
Point 11
Label A: O5AprO4 P-4C7 333 1 51 Roint 1 1
;:\e dax32\gen es i s\g e ns p c. sp c-/~p ea kg e n.s pc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
A-98
-------
Point 12
Label A: IH.AprlM P4C7 333 151 Point 1 2
>e32\genesis\genspc-spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
Point 13
Label A: D5AprO4 PJC7 333 1 51 Point 1 3
s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
100 200 3.00 1.00 5.00 6 00 700 000 900 10 00 11.00
A-99
-------
P4C7 - 403,199
BSE Image
A-100
-------
EDS Scan Images by Point
Point 1
Label A: O5AprO4 P-4C7 -4O3 1 99 Point 1
:\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Point 2
Label A: Ut-AprLM P4C7 403 1 99 Point 2
Label B: H K
l.BO 2.70 3.60
A-101
-------
Point 3
Label A: O5AprO4 R4C7 4O3 199 Roint 3
;:\eda;<3Z\genesis\genspc.spc-/-peakgen.spc
Label Rr H K
Point 4
Label A: O5AprO4 P4C7 4O3 1 99 Point A
n esi s\gens pc. spc-/-peakgen.spc
Label B: H K
Point 5
c:\edax32-\ge
Label A: OBAprO 1 P1C7 4O3 1 99 Point B
s\genspc.spc /pea kg
Label B. H K
A-102
-------
Point 6
Label A: O5AprO4 R4C7 4O3 199 Roint 6
;:\eda;<3Z\genesis\genspc.spc-/-peakgen.spc
Label Rr H K
6.30 7.20 S.IO 9.00
Point 7
Label A: O5AprO4 P4C7 JO3 1 99 Point 7
c:\edax32\genesis\genspc.spc / peakgen.spc
Label D: I I K
5.40 6.30
B.10 9.00
Point 8
Label A: O5AprO4 P4C7 4O3 1 99 Point S
:\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
a 10 9 00
A-103
-------
Point 9
Label A: O5AprO4 FMC7 4Q3 199 Point <
Label B: H K
i.ssij 2_70 3_60 4_50 5_40 6.30 7_20 8_10 9_00
Point 10
::\c-cla:-:JZ\qcncBis-\qc-nspc.s-pcjfpcal:c|c-n.-spc
Label B: H K
2.7O 3.GO 4.50 5 1(1 e.3D 7.20 ft I n 9.OD
Point 11
Label A: OSAprOI P4C7
-------
Point 12
Label A: IH.AprlM P4C7 4O3 199 Point 1 2 Label B: H K
A-105
-------
P4C7 - 456,153
BSE Image
A-106
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: M'.AprlM P4C7 456 153 Point 1
c:\edax32\genesis\genspc. spc^f peakgen.spc
Label B: l-l K.
1.00 2.00 3.00 -1.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
Point 2
c:\edax32\gene
Label A: OSAprOt P4C7 456 153 Point 2
sis\genspc.sftc f peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
A-107
-------
Point 3
Label A: O5AprO-4 P4C7 456 I 53 Point 3
c:\edax32\genesis\genspc.spc /peakgen.spc
Label R: I I K
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00
Point 4
Label A: OSAprCM
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
2_00 3.00 4.00 5.00 6.00 7_00 8.00 9.00 10.00 11.00
Point 5
c:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label A: O5AprO4 P-4C7 -456 1 53 Point 5 Label B: H K
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.1
A-108
-------
Point 6
Label A: OBAprOJ PJC7 J56 I 53 Point 6
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
Al Pb
Cd Ca Ba
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00
Point 7
Label A: OSAprCM
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
nt 7 Label B: H K
2_00 3.00 4.00 5.00 6.00 7_00 8.00 9.00 10.00 11.00
Point 8
Label A: O5AprO4 P-4C7 -456 1 53 Point 9
;:\e dax32\gen es i s\g e ns p c. sp c-/~p ea kg e n.s pc
Label B: H K
^
v^^^
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.1
A-109
-------
P4C7 - 485, 208
BSE Image
A-110
-------
EDS Scan Images by Point
Point 1
Label A: OSAprOI P4C7 485 208 Point 1
c:\edax32\genesis\genspe.spc-7-peakgen.spc
Label B: l-l K
Ti
Ba
Pb
As
1 30 2 30 3 30 1 30
6 30 7 30
9 30 10 30 11 30
Point 2
Label A: CH.AprlM P4C7 485 2O8 Point 2
;:\edax32\genesis\genspc.sp c-/-p eakgen.spc
Label B: l-l K
L30 2.30
5.30 6.30 7.30 0.30
9.30 10.30 11.30
A-lll
-------
Point 3
Label A: OBAprOJ PJC7 JBS 2OB Point 3
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
9.30 10.30
Point 4
Label A: 85Apr84 P4C7 485 ZOB Ro
s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
Point 5
Label A: O5AprO4 P-4C7 185 288 Roint 5
;:\e dax32\gen es i s\g e ns p c. sp c-/~p ea kg e n.s pc
Label B: H K
3.30 4.30 5.30 6.30 7.30
A-112
-------
Point 6
Label A: IH.AprlM P4C7 485 ZO8 Point 6
x:32\genesis\genspc:-spc-/-pealcgen.spc
Label B: H K
Pb
As
Point 7
Label A: O5AprO4 P4C7 485 2OO Point 7
s i s\g e n s p c. s p c-/-p e
Label B: H K
Pb
As
2.30 3.30
9_30 10.30 1L30
Point 8
c:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label A: O5AprO1 P-4C7 -4B5 ZOO Point S Label B: H K
A-113
-------
Point 9
Label A: OBAprOJ PJC7 JBS 2OB Point 9
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
Pb
As
Point 10
s i s\g e n s p c. s p c-/-p c a kg e
Label R. H K
i
Point 11
Label A: O5AprO4 F4C7 AB5 ZOB Point 1 1
:\edax32\genesis\genspc. spc-/-peakgen.spc
Label D: I I K
A' I
4.30 5.30 6.30
A-114
-------
Point 12
Label A: IH.AprlM P4C7 485 ZO8 Point 1 2
>e32\genesis\genspc-spc-/-peakgen.spc
Label B: H K
Pb
As
A-115
-------
P4C7 - 486, 202
BSE Image
A-116
-------
Silicon
Label A: Q5AprQ4 P4C7 186 2O2 Point 1
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc. spc-/-pea kge n.s pc
Label Is: 1-1 K
Pb
Pb
As
1.30 2.30 3.30 4.30 5.30 6.30 7.30 0.30 9.30 10.30 11.30
Point 2
Label A: O5AprO4 P-1C7 48G 2OZ Point 2
c:\edax32\genesis\genspc. spc-/-peakgen-spc
Label B: H K
Al Pb
Ti
Ba
Pb
As
1.30 2.30 3.30 4.30 '.rill 6.30 7.30 8.30 9.30 10.30 11.30
A-117
-------
Point 3
Label A: OSAprO.4 PJC7 JB6 2O2 Point 3
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label R: I I K
Point 4
c:\edax3Z\ge
Label A: 05Apr04 P4C7 486 202 Point A
i e s i s\g e n s p c. s p c-/-p eakgen.spc
Label B: H K
1 30 230
5 30 6 30
i 30 9 30
10 30 1130
Point 5
cr:\e d ax3 Z\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
nt 5 Label B: H K
A-118
-------
Point 6
Label A: O5AprO-4 P4C7 486 2O2 Point 6
c:\edax32\genesis\genspc.spc /peakgen.spc
Label R: I I K
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00
Point 7
c:\edax3Z\gc
s i s\g e n s p c. s p c-/-p e a kg e
Label R- H K
2_00 3_00 1 Illl S.llll 6.1
Mill 9_00 10.00 111
Point 8
Label A: O5AprO4 F4C7 ABB 2O2 Point 8
Label D: I I K
1
JLwtf
1.00
XI
1
Pb Ca Ba
2.00 3.00 4.00 5.00 G.OO 7.00 B.OO 9.00 10.00 11.00
A-119
-------
Point 9
Label A: O5Apr04 P4C7 486 202 Point 3
c:\edax32\genesis\genspc.spc f peakgen.cpc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
A-120
-------
P4C8 - 354, 306
BSE Image
A-121
-------
Label A: P4CB X-354 Y-3O6 Point 1
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc. spc
1.00 2.00 3.00 -4.00 5.00 (.1111 7.00 8.00 9.00 10.00 11.00
Point 2
c:\e d a>c3 2\g c n c s. i s\g enspc. spc
Label A: FMCO X-351 Y-3O6 Point 2
Pb
As
1-00 2 00 3 00 4 00 S 00 6 00 7 00 S 00 9 00 10 00 11 00
A-122
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: F>4C8 X-354 Y-3O6 Point 3
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
Point 4
Label A: P4CB X-354 Y-3O6 Point A
LOO 2_00 3_00
Label A: P1C8 X-351 Y-3OB Point 5
5_00 G 00 7.00 C 00 9_00 10.00 11. OO
Point 5
r:\"C d ax 3 2\g e n e s i s\g enspc.spc
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00 12.00
A-123
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: P4C8 X 354 Y 3O6 Point S
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 7
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P4C8 X-354 Y-306 Point 7
Pb Cd
^AvVWJ^A^V^Mvv-VA^^-^vvv
Pb
As
1 00 2 00 3 00 4 00 S.UU 6 00 7 00 0 00 y.UU 10.00 11 00 12 00
A-124
-------
P4C8-370,216
BSE Imaj
» *-«
t>-', *
A-125
-------
EDS Scan Images by Point
Point 1
n e s i s.\cj enspc. spc
Label A: P1C8 X-37O Y-21 6 Point 1
8.GO 10-00
Point 2
Label A: P4C8 X-37O V-216 Point 2
14.00 16.00
A-126
-------
Label A: P4C8 X 37O Y 21 6 Point 3
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
"-^W WV-AA-^
Fe
l^JX-^-Vw,
Label A: FMCB X-37O Y-216 Point A
Point 4
e d ax 3 2\g e n e s i s\g enspc.spc
Point 5
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: R1C8 X-37O Y-21B Point 5
A-127
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: P4C8 X-370 Y-Z1 B Point B
A-128
-------
P4C8 - 391, 328
BSE Image
A-129
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P1C8 X-391 Y-328 point 1
Al Pb
cd A
^-V.^VA/^HV
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 2
c:\eda>c32\genesis\genspc. spc
Label A: P4CB X 391 Y 328 point 2
Pb Cd
Pb
As
100 200 300 400 500 600 7.00 800 900 10.00 1100 1200
A-130
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: P4C8 X 391 Y 328 point 3
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 4
c:\edaK32\genesis\genspc.spc
Label A: P4C8 X-391 Y-328 point 3
100 200 300 4 00 500 fc.llll 700 800 9 00 1000 1100 1200
Point 5
c:\edax3Z\genesis\genspc.spc
Label A: P4C8 X-391 Y-328 point B
A-131
-------
P4C8 - 408, 221
BSE Imaj
A-132
-------
Silicon
EDS Scan Images by Point
Point 1
n e s i s.\cj e n s p c. spc
Label A: P4C8 X-4O8 Y-221 Point 1
.'^V^V*Wr'%/lU,V^VJ
i.oo 2.00 3-00 -1 an 5.00 s_oo 7 no B oo 9.00 io_oo 11.00 12.00
Point 2
r::\ii=? d ax3 2\g e n e s i f-\t~] enspc. spc
Label A: P4C8 X-^O8 Y-221 Point 2
I
\ F*b
Cd Ba
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
A-133
-------
Point 3
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: P4C8 X-4OS Y-2Z1 Point 3
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Label A: FMCB X-^OB Y-221 Point A
Point 4
e d ax 3 2\g e n e s i s\g enspc.spc
0
I -
JLJ
LAi Pb
Pb_^ C
-------
P4C8 - 424, 202
BSE Image
A-135
-------
EDS Scan Images by Point
Point 1
c:\e d .ti x J 2\g e n e s i s\g e n s p c. s p c-/-p c a kg e n. s p c
Label A: 2OaprO4 pP4C8 424 2O2 Point 1 Label B: H K
Pb
As
Point 2
c:\edax32\genesis\genspc. spc^f peakgen.spc
Label A: ZOaprOI pP1C8 4Z4 2O2 Point 2 Label B: H K
Ti
Ba
Pb
As
A-136
-------
Point 3
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
abel A: ZOaprOI pP4CB 424 2OZ Point 3 Label B: H K
Jfe-_w IP
C cl __
Mn I c
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.OO
Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
abel A: 2OaprO4 pP-ICG 424 2O2 Point 4 Label B: H K
Ca Ce
1_00 2_00 3.00 4.00 5 00 6 00 7.00 8 00 9_00 10.00
Point 5
Pb
As
Label A: 2OaprO4 pPICQ 12-4 2O2 Point 5
Label B: H K
1.00 2.00 3.00 4_00 5.00 G_00 7.00
Pb
As
9_00 10.00
A-137
-------
Point 6
c:\edax32\gene
Label A: 2OaprO4 pP4CG 424 2O2 Point G
s i s\g e n s p c.. s p c-/-p e a leg e n. s. p c
Label B: H K
1.00 2.00 --t mi A 00 5.00 6.00 7.00 0.00 9 00 10.00
Point 7
Label A: ZOaprO4 pP4CB 424 2O2 Point 7
\genspc. spc-/-peakgen.spc
Label B: H K
Point 8
Pb
As
LOO 2_00 3_OO 4.00 5_00 C_00 7.00 0.00 9.00 10.00
Label A: 2OaprO4 pP4C8 424 ZOZ Point 8
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
LOO 2_00 J_UU 1_UU 5_00 6_00 7_00 8_00 9_OO 1U.UU
A-138
-------
Point 9
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
abel A: ZOaprOI pPICB 424 2OZ Point 9 Label B: H K
Pb K
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.OO
Point 10
c:\edax32\genesis\genspc.spc /pea kgen.spc
abel A: 2OaprO -1 pP4CS 424 2O2 Point 1 O Label B: H K
1_00 2_00 3.00 4.00 5.00 6 00 7.00 0.00 9.00 10.00
pb
A-139
-------
P4C8 - 424, 217
BSE Image
A-140
-------
EDS Scan Images by Point
Point 1
Label A: 1 6junO4 P6C7 424 21 7 Point 1
Point 2
Label A: 1 BjunO.4 P6C7 424 21 7 Point 2
A-141
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 6junO4 P6C7 424 217 Point 3
Point 4
Label A: 1 GjunO4 P6C7 424 21 7 Point 4
Point 5
Label A: 1 GjunOI PGC7 424 21 7 Point 5
I I
"B Al | i
A/V I
i.eo 2.40
A-142
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: 1 6junO4 P6C7 424 217 Point 6
0 80 1.60 2.40 3.20 4.00 4.00 5 60 6.40 7.20 0.00
Point 7
c:\e d ax: 3 i_\y e n e s i s\g enspc.spc
Label A: 1 GjunO4 P6C7 424 21 7 Point 7
I i Pb
,; < A
1_60 2.40 3_2O 4.00
7_20 8_
Point 8
c:\e d a>c3 2Vg e n e s i s\g enspc.spc
Label A: 1 6junO4 PEC7 424 21 7 Point 1
L.GO 2.40 3_2O 4 00 1 SO 5.60
7.20 S.I
A-143
-------
Point 9
c:\edax:32\genesis\genspc:.spc
Label A: 1 lijunlM P6C7 424 21 7 Point 3
O.BO 1.60 2.40 3.20 4.00
80 5.60 6.40 7.20
Label A: 1 6junO4 PGC7 424 21 7 Point 1 O
Point 10
0.90 1 80 Z.70 3.60 4.50 5.40 6.30 7.20 8.10
A-144
-------
P4C8 - 470, 208
BSE Image
A-145
-------
EDS Scan Images by Point
Point 1
Label A: 2OaprO4 P1C8 17O ZOB Point 1
c:\edax32\genesis\genspc. spcVpea kgen.spc
Label B: H K
Pb
As
^ ... -S/.. \*+^ir***?^^
LOO 2 00 3.00 4.00 5.00 6 00 7.00 8.00 9.00 10.00
Point 2
Label A: 2QaprO4 P4C8 47O 2O8 Point 2
n e s i s\g e n s p c. s p c-/-p e a kg e n . s p c
Label B: H K
Si
Al p I
-VvvVW
Pb
As
1 00 2 00 3 00 A 00 5 00 6 1)0 7 00 8 00 9 00 10 00
A-146
-------
Point 3
c:\edax32\genesis\genspc.spc /peakgen.spc
abel A: 2OaprO>l R4C8 47O 2OO Point 3 Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 S.OO 9.00 10.00
Point 4
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: 2OaprO4 P4C8 1 /U 2O8 Point -4 Label B: H K
I nn 2.00 3.OD 4.00 5.00 6.00 7.00
9.0O 10.OO
Point 5
Label A: 2OaprO4 PJCS ^17O 2O8 Point 5
:\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00
A-147
-------
Point 6
Label A: ZOaprO4 F*4C8 47O ZO8 Point G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.OO 10.OO
Point 7
Label A: 2OaprO4 P4C8 47O 2O8 Point 7
c:\edax32\genesis\genspc.spc-f-peakgen.spc
Label B: H K
Pb
As
i.oo 2.00 3.00 i nn 5.00 e.oo 7.00
9.00 10.00
Point 8
Label A: ZOaprO4 PICS 17O 2O8 Point 1
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
LOO 2_00 J_UU 1_UU
e_00 7_00 8_00 y.UU 1U.UU
A-148
-------
Point 9
Label A: ZOaprO4 F*4C8 47O ZO8 Point 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.OO 10.OO
Point 10
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: ZOaprO4 P4CQ 47O 2OO Roint 1 O Label B: H K
Pb
As
1_00 2_00 J_UU
5_00 6.00 7.00 0.00 9.00 10.00
Point 11
Label A: ZOaprO4 P4C8 47O 2O8 Point 1 1
':\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
1_00 2_00 3_00 -4_00 5_00 6_00 7_00 H <
9_00 10.00
A-149
-------
Point 12
Label A: 20apr04 P4C8 470 2O8 Point 1 2
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
A-150
-------
P4C8 - 473, 203
BSE Image
A-151
-------
EDS Scan Images by Point
Point 1
c:\e d ax:3 2\g e n e s i s\g enspc.spc
Label A: 1 GjunO4 P4C8 473 2O3 Point 1
1.90 1.80 2.70 3.60 4.50 5.40 6.30 7.20
.10 9.1
Point 2
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 1 GjunO4 P4C8 473 203 Point
-ft'-:'f'f^tl^ftH--^iff^f.f-V.
^*J-^
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 6junO4 P4CS 473 2O3 Point 3
_J
0.90 1.00 2.70 3.60 4.50 5.40 £.30 7.20 8.10 9.00
Point 4
c:\e d ax: 3 i_\y e n e s i s\g enspc.spc
Label A: 1 GjunO4 P4CB 473 2O3 Roint
0_90 1_8O 2_70 3_60
6_30 7.20 8_10 9_OO
Point 5
c:\e d a>c3 2Vg e n e s i s\g enspc.spc
Label A: 1 6junO4 PICS 473 2O3 Point 5
0_9O 1.00 2_70 3.CO 4.50
G_3O 7.20 8_10 9.00
A-153
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: 1 6junO4 R4C8 473 2O3 Point 6
0.9O 1.80 2.7O 3.GO 4.5O ^ in 6_30 7.20 8.1O 9.1
Point 7
c:\e d a>c3 2\g e n e s i s\g enspc.spc
Label A: 1 BjunD4 R4C8 473 2D3 Roint 7
0.90 1.00 2.70 3.60 4.50 5.40 6.30 7.20 0.10 9.00
Point 8
c:\e d a>c3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 R4C8 473 2O3 Roint 1
Si
i.90 1.80 2_70 3.CO 4_50 5_40 G_3O 7_20 S.1.0 9.00
A-154
-------
Point 9
Label A: 1 6junO4 P4CS 473 ZO3 Point 9
0.90 1.80 2.70 3.60 4.50 5.40 6.30 7.20 8.10 9.00
Point 10
c:\e d ax: 3 i_\y e n e s i s\g enspc.spc
Label A: 1 GjunOI P4C8 473 2O3 Roint 1 O
I_7O 1.40 2.10 2.SO 3_SO 4_20
5_60 b_JU 7_OI
A-155
-------
P4C9-319,289
BSE Imaj
A-156
-------
EDS Scan Images by Point
Point 1
Label A: 2OaprO4 P4C9 319 289 Point 1
c:\edax32\genesis\genspc. spcV pea kgen.spc
Label B: H K
Pb Cd
Ti
Ba
Point 2
Pb
As
1.00 2.00 3.00 4.00 5.00 £.00 7.00 8.00 9.00 10.00
c:\edax32tge
Label A: 2OaprO4 P4C9 31 9 2B9 Point 2
s i s\g e n s p c. s pc f peakgen.spc
Label B: H K
Pb
As
1.00 2.00 3.00 4.00 5.00 I, nil 7.00 0.00 9.00 10.00
A-157
-------
Point 3
Label A: ZOaprO4 FMC3 31 9 ZB9 Point 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 4
Label A: ZOaprO4 P4C9 31 9 283 Point A
i:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Pb
As
Point 5
Label A: 20apr04 P4C9 31 9 289 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
Fe
ll
A-158
-------
Point 6
Label A: 28apr84 R4C9 31 9 289 Point G
Label B: H K
1_00 2_00 J UU
5_00 6 00
8_00 9_00 10.00
Point 7
Label A: 2OaprO4 P4C9 31 9 289 Point 7
:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Pb
As
LOO 2 00 3_OO -1.00 5_OO C.OO T.OO
i.OO 3.00
Point 8
Label A: 2OaprO4 P-4C9 31 9 289 Point a
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00
i.OO 9.00
A-159
-------
Point 9
Label A: 2OaprO4 P1C9 319 2S9 Point <
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
A-160
-------
P4C9 - 338, 318
BSE Image
A-161
-------
Silicon (Si
EDS Scan Images by Point
Point 1
c:\edax32\ge
Label A: ZOaprO4 P4C9 338 31 3 Point 1
e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
^JJJ1 V.^^
Point 2
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Label A: ZOaprO4 P4C9 338 31 3 Point 2
\genspc. spc-/-peakgen.spc
Label B: H K
1.00 2_OO 3.00 4.0O 5. DO 6.00 7.00 0.00 9.00
A-162
-------
Point 3
Label A: ZOaprO4 FMC9 338 31 3 Point 3
abel I !: I I K
Point 4
Label A: 2O«jprO1 P4C9 338 313 Point
c:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Point 5
Label A: 2OaprO4 P4C9 338 313 Point 5
c:\edax32\genesis\genspc. spr^f pea kgen.spc
Label B: H K
A-163
-------
Point 6
Label A: ZOaprO4 FMC3 33B 3T 3 Point 6
;:\eda;<32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
7.00 0.00
Point 7
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: ZOaprO4 P4C9 338 31 3 Roint 7 Label B: H K
Pb
As
Point 8
c:\edax32\ge
Label A: ZOaprO4 P4C9 33B 31 3 Point 8
s i s\g e ns p c. spc-/~P e
Label B: H K
A-164
-------
P4C9 - 443,152
BSE Image
A-165
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
Label A: 2OaprO4 P4C9 443 1 52 Point 1
:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 9.00 9.00 10.00
Point 2
c:\edax32\genesis\genspc. spc-/-pea kg en.spc
Label A: 2OaprO4 P4C9 443 1 52 Point 2 Label B: H K
1_00 2.00 3_OO -1.00 5_OO C 00 7 00 R 00 9.00 I.O.OO
A-166
-------
Point 3
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 -4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 4
Label A: ZOaprO4 P4C9 443 1 52 Roint A
:\edax32\genesis\genspc. spc / p ea kge n.s pc
Label B: H K
1_00 2_OO J_UU 4_00 'j_UU b.UU 7_00 8_00 9_00 10
Point 5
Label A: 20apr04 P4C9 443 1 52 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
1 00 2 00 3 00 4 00 5 00 f. 00 7 00 0 00 9 00 10 00
A-167
-------
Point 6
Label A: 2OaprO4 P1C9 4-43 152 Point G
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
1 00 2 00 3 00 -4 00 5 00 6.00 7.00 0.00 9.00 10 00
Point 7
Label A: ZOaprOI P-4C9 -413 1 5Z Point 7
e dax:3Z\gen esi s\g e ns pc. spc-/-p ea kge n.s pc
Label B: H K
1.00 2 00 3.OO 4_00 5.OO 6_00 7_00 B_00 9_00 10
Point 8
c:\eda>c3Z\genesis\genspc.spc-/-peakgen.spc
Label A: 2OaprO1 P-4C9 -413 1 52 Point 8 Label B: H K
1_00 2_OO J_UU 4_00 5_OO b U U Y.IIU ii.llll 9_00 III.UII
A-168
-------
P4C9 - 452, 298
BSE Image
A-169
-------
EDS Scan Images by Point
Point 1
Label A: 2OaprO4 P4C9 152 298 Point 1
c:\edax32\genesis\genspc. spcV pea kgen.spc
Label B: H K
c° /r »p R * - ce /
_$^J\> V^-jw^^J X-^^^i^^ca^^^Bta, ^Mji^y '
1.00 2 00 3.00 4 00 5 00 6.00
Point 2
Cu
^_JV_
7 oo a no
Pb
As
9.00 10.00
Label A: 2DaprO4 P4C9 452 298 Point 2
e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
3.00 4.00
5 00 6 00
9.00 10 00
A-170
-------
Point 3
Label A: ZOaprO4 FMC3 -HSZ 233 Point 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Fe
I
LA,
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.DO
Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
abel A: 2OaprO'l P4C9 452 298 Point 4 Label B: H K
Cd Ca Bo
Pb
As
1 00 2 00 3 00 1 00 5 00 6 00 7 00 8 00 9 00 10 00
Point 5
Label A: 2OaprO4 P-4C9 -452 298 Point 5
Label B: H K
1.00 2.00 3.00 4.00 5_00 6_00
'» ll«l Ill Illl
A-171
-------
Point 6
I A: 2OaprO4 R4C9 45Z 298 Roint 6
c:\edax3Z\genesis\genspc.spc /pea kgen.spc
Label B: H K
Point 7
c:\ed ax:3 2\g e ne sis\gen sp c. sp c/p e akg en. s pc
abcl A: 2Oapr84 R4C9 452 298 Point 7 Label B: H K
Point 8
Label A: ZOaprO-4 P4C9 452 298 Point 1
c:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
°
A Pb K Ti
___5^y \_ Na^.i!/ VE £d___Ca Ba Mn
FE Cu
Pb
As
A-172
-------
Point 9
c:\edax3Z\genesis\genspc.spc /pea kgen.spc
abel A: 2OaprO4 R4C9 452 298 Point 9 Label B: H K
Point 10
c:\ed a>e32\genesis\genspc.spc-/-pealegen-spc
Label A: ZOaprO4 P4C9 452 298 Point 1 O Label B: H K
1.00 2.00
Point 11
c:\ed ax:3 2\g e ne s is\ge n sp c. sp c-/-p e akg e n_ s pc
abel A: 2OaprCM P4C9 452 298 Point 1 1 Label B: H K
A-173
-------
Point 12
Label A: 2OaprO4 P4C9 452 298 Point 1 2
s\(j e n s p e. s p r.-/-p e a kg. e n. s p c
Label B: H K
A-174
-------
P4C9 - 459, 210
BSE Image
A-175
-------
Silicon (Si)
Label A: 2OaprO4 P4C9 459 21O Point 1
EDS Scan Images by Point
Point 1
c:\eda5-c3Z\genesis\genGpc. spc-/~peakge
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
Point 2
Label A: L'UoprCM P4C9 459 21 O Point 2
\genspc.sp c^/ p eakgen.spc
Label B: H K
Pb
I.iJU 2_00 3_00 4.110 S UU G 00 7_00
9_00 10.00
A-176
-------
Point 3
Label A: ZOaprO4 FMC9 4EB 21 II Point 3
abel I !: I I K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 4
Label A: i'll.nprlM PJC9 453 21 O Point 4
\genspc.sp c-/-p eakgen.spc
Label B: H K
1.00 2.00 3.00 -4.00 5.00 6.00 7.00 B.OO 9.00 10.00
Point 5
Label A: 2OaprO4 P-4C9 -459 21 O Point 5
Label B: H K
I mi 7 nil 3.00 1 mi 5.00 6_00 7.00 B.OO 9_00 10.00
A-177
-------
Point 6
Label A: 2OaprO4 P4C9 459 21 D Point B
c:\edax32\genesis\genspc.spc /peakgen.spc
Label B: H K
Pb
As
Point 7
Label A: 2OaprO4 P4C9 459 21 O Point 7
;:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Pb
As
5. DO G.OO
7.00 8.00
Point 8
Label A: 2OaprO4 P-4C9 -459 21 O Point a
n esi s.\gens pc. spc-/-peakgen.spc
Label B: H K
To
1.00 2.00 3.00 -4.00 5.00 e.OO 7.00 8.00
A-178
-------
Point 9
Label A: 2OaprO4 P1C9 459 21 O Point !
;:\edax:32\genesis\genspc:-spc-/-peak:gen.spc
Label B: H K
Rb
As
Point 10
Label A: ZOaprO4 P4C9 459 21 O Point 1 O
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Pb
As
Point 11
c:\edax32\genesis\genspc.spc / peakgen_spc
Label B: H K
A-179
-------
Point 12
Label A: 2OaprO4 P4C9 459 21 O Point 1 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
l.OU 2_00 3_
6.UU 7_00 8_00 y.UO
Point 13
Label A: 2OaprO1 P-4C9 -459 21 O Point 1 3
Label B: H K
A-180
-------
P4C9 - 487, 204
BSE Imaj
A-181
-------
Label A: 2OaprO4 P4C9 487 2O4 Point 1
EDS Scan Images by Point
Point 1
c:\eda5-c3Z\genesis\genGpc. spc-/~peakge
Label B: H K
0
(1 Pb
$ C SI * H C" Ce
LN^>^^ ^s£^^~^,^^
-
\ iJ \ AS
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 2
Label A: 2OaprO4 P4C9 487 204 Point 2
\Q e n s p c. s p c-/-p eakQen.spc
Label B: H K
1 00 2 00 3 00 4 00 5 00 I. 00 7 00 0 00 9 00 10 00
A-182
-------
Point 3
Label A: ZOaprO4 FMC3 -HB7 2O1 Point 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 4
Label A: 2OaprO4 P4C9 487 ZO4 Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Pb
As
1 00 2_00 3.00 ^.00 5.00 6 00 7_00 8 00 9.00 1O I
Point 5
Label A: 2OaprO4 P-4C9 -487 2O4 Point 5
Label B: H K
A-183
-------
Point 6
Label A: 2OaprO4 P1C9 4Q7 2Q4 Point G
;:\edax:32\genesis\genspc:-spc-/-peak:gen.spc
Label B: H K
I nil 2 00 3.00 A 00 5.00 6.00 7.00 0.00 9.00 10.00
Point 7
Label A: ZOaprO4 P4C9 AB7 2OA Point 7
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Point 8
Pb
As
1_00 2.00 3_OO 4_00 5_00 C 00 T.OO C 00 9 00
c:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Cd Ca Ba
PU
As
2_OO 3_OO 4_OO '. "ii 6_00 Y "in a: nil
A-184
-------
Point 9
Label A: 2OaprO4 P4C9 487 2O4 Point !
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
1_00 2_00 3_00 -4_00 5_00 b_UU
i_00 9_00 10.00
Plot 6
A-185
-------
P6C7 - 312, 242
BSE Image
Phosphorous(P)
A-186
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: 1 3aprO4 p6c7 312 242 Point 1
\genspc.spc-/ peakgen.spc
Label B: H K
Point 2
Pb
As
LOO 2_OO 3.00 -1.UU 5_00 6_OO 7_00 8_00 9_00 10.00 1LOO
Label A: 1 3aprO4 PGc7 31 2 242 Point 2
c:\e d ax.3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
LOO 2.00 3_00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
A-187
-------
Point 3
c:\ed ax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 4
Label A: 1 3aprO4 pBcT1 31 Z Z4Z Point A
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
K
Cd
Pb
As
Point 5
Label A: 1 3aprO4 p6c7 31 2 242 Point 5
s\g e n s p c. s p c-/-p e a kg e
Label B: H K
A-188
-------
Point 6
Label A: 1 3apr04 p6c7 31 2 242 Point 6
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
A-189
-------
P6C7 - 344, 248
BSE Image
A-190
-------
Silicon (Si)
^HF.^^K^^^^w«i- »inm_
EDS Scan Images by Point
Point 1
Label A: 1 3aprO4 p6c7 3^4 24B Point 1
:\edax32\genesis\genspc. spc / peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5 00 6.00 7.00 0-00 9.00 10.00 11-00
Point 2
18 Point Z
rt c s i s\g e n s p c. s p c / p c a kg e n. s p c
Label B: H K
Cd Ca
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00
A-191
-------
Point 3
c:\ed ax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 4
Label A: 1 3aprO4 pGc7 344 248 Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Pb
As
1 00 2_00 3 00
5 00 G.OO
Point 5
c:\edax32\genesis\genspc. spc-/-peakgen.spc
4B Point 5 Label B: H K
Pb
As
A-192
-------
Point 6
Label A: 1 3aprO4 pGc7 314 24G Point G
;:\edax:32\genesis\genspc:-spc-/-peak:gen.spc
Label B: H K
Pb
As
5.00 6 00
Point 7
48 Roint 7
s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
Pb
As
A-193
-------
P6C7 - 356, 231
BSE Imaj
1
>- -jfc-k-J?-.-<
Phosphorous(P)
A-194
-------
EDS Scan Images by Point
Point 1
Label A: 1 GjunO-4 P6C7 356 231 Point 1
LOO 2_OO 3_00 4.00 5_OO I, UK 7 00 8_OO 9_l
Point 2
D:\~Userdata on E PK1 A\U s e rl m a g e s\1 BjunO4 PBC7 356 231 Point Z.spc
Label A: 1 GjunO^f P6C7 356 231 Point 2
_>/
LOO 2_OO J 00 -I 00 5_OO 6_00 7.00 8_OO 9 00 10.00 11 00 12.00 U.i
A-195
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 BjunO4 P6C7 356 231 Point 3
LOO 2.OO 3.DO 4.OO 5.00 6. DO 7.OO 8.00 9.00 10. OO 11.00 12.00 13.OO
Point 4
c:\e d a>c3 2\g. e n e s i s\g enspc.spc
Label A: 1 BjunD4 PGC7 356 231 Point
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00
Point 5
c:\e d ax: 3 2\g e n e s i s\g enspc.spc
Label A: 1 GjunO4 P6C7 356 231 Point 5
O
X
Si
I
LOO 2_OO 3_00 'l.OO 5_00 6_00 7.00 0.00 9_00 10.00 11.00 12.00 13.1
A-196
-------
Point 6
Label A: 1 BjunO4 P6C7 356 231 Point 6
l.GD 2.40 3.20 A. DO 4_80 5.GO 6.40 7.20 0.00
Point 7
c:\e d a>c3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 PGC7 356 231 Point 7
0.80 1.60 2.40 3.20 4.00 4.80 5.60 6.40 7.20 0.00
Point 8
genesis\genspc. s p c
Label A: 1 GjunO4 P6C7 356 231 Point 8
0.80 1.60 2.40 3 20 4.00 4 80 5 60 6.40 7.20 0.00
A-197
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: 1 BjunO4 P6C7 356 231 Point 3
1.60 2.40 3.20 A. DO 4.8O 5.GO 6.40 7.20 0.00
Point 10
c:\e d a>c3 2\g. e n e s i s\g enspc.spc
Label A: 1 GjunO4 PGC7 35G 231 Point 1 D
0.80 1.60 2.40 3.20 4.00 4.80 5.60 £.48 7.28 8.08
Point 11
c:\e d ax: 3 2\g e n e s i s\g enspc.spc
Label A: 1 GjunO4 PGC7 35G 231 Point 1 1
0 80 LGO 2.-4O
3_2O 4_00
5_GO 6.-4O 7_2O 8_00
A-198
-------
Point 12
Label A: 1 llj.mlM P6C7 356 231 Poin! 1 2
1.60 2.40 3.20 4.00 4.80 5.60 6.40 7.20
A-199
-------
P6C7 - 358, 261
BSE Image
|V6 ( \ .
X
. * ->'v
.
^
It
i
;i
Iron (Fe)
'&&&
Manganese (Mnj
A-200
-------
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc. spc-/ pea kgen.spc
Label A: 1 3APR.O4 P6c7 3S8 261 Point 1 Label B: H K
2 00 3 00 1.00 5 00 6.00 7 00 8 00 9.00 10 00
Point 2
Label A: 1 3APRO4 P6e7 358 261 Point 2
Xf]enspc.sp c-/-p e akgen.spc
Label B: H K
2_00 3_00
5_00 6_00 7.00 0.00 9.00 10.00
A-201
-------
Point 3
Label A: 1 3APRO4 P6c7 358 261 Point 3
c:\edax32\genesis\genspc.spc /peakgen.spc
Label B: H K
Point 4
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APFIOJ P6c7 358 261 Point A Label B: H K
7.00 0_00
Point 5
c:\edax32\genesis\genspc.spc-X-peakgen.spc
Label A: 1 3APR.O4 P6c7 358 261 Point 5 Label B: H K
A-202
-------
Point 6
Label A: 1 3APRO4 P6c7 358 261 Point G
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Pb
As
1.00 7 llll 3.00 A 00 5 00 6.00 7.00 0.00 9.00 10.00
Point 7
c:\edax3Z\genesis\genspc. spc-/-pea kge n.s pc
Label B: H K
1.00 2_OO 3_00 4_00 5_OO G_00 7_00 8_OO 9.00 10.00
Point 8
c:\cdax3Z\genesis\genspc. spc-/-peakgen.s pc
Dint 8 Label B: H K
i nn 2-Od 3_oo
nn B_OO
nn io_oo
A-203
-------
P6C7-371,216
BSE Image
J4'
-------
EDS Scan Images by Point
Point 1
Label A: 1 GaprO4 p6c7 371 21 6 Roint 1
e n e s i s\g e n s p e. s p c-f-p e a kg e n - s p c
Label B: H K
1.00 2.00 3.00
1 00 5_00 6 00
9_00 10.00 11.00
Point 2
Label A: 1 6aprO4 p6c7 371 21 6 Point 2
c:\edax32\genesis\t|enspc.sp r,-/-p eakgen.spc
Label B: H K
d
1 1
..JXS^l ^
Pb
K
Cd Ca
Ti
Ba
Mi.
Fe
Pb
As
1.011 2.00 -J.OU -1.00 'b 00
fo 00 7_00
00 9_00 10.00 11.00
A-205
-------
Point 3
Label B: H K
l.UU 2_00 J.UU l.UU S_00 6.00 7.00
Point 4
Label A: 1 GaprOI pGc7 371 21 6 Point A
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00
Point 5
Label A: 1 6aprO4 pGc7 371 21 E Point 5
Label B: H K
Pb
As
A-206
-------
Point 6
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
oint G Label B: H K
c
CJ
1
Na/v/
1
K
1 A
1 WJ? ^\^J »n - To"
Point 7
Label A: 1 GaprO4 p6c7 371 Z1 B Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
1 20 2_20
Point 8
Label A: 1 6aprO4 pGc7 371 21 E Point G
Label B: H K
Pb
As
A-207
-------
Point 9
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
oint a Label B: H K
1.20 2.20 3.20 4.20 5.20 6.20 7.20
: .30 9.2O 1O.20
Point 10
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
1 20 2_20 3_20 4 20 5 20 6_20 7_20 8 20 9 20 10.20
Point 11
Label A: 1 GaprOI pGc7 371 21 6 Point 1 1
;:\eda>c3Z\genesis\genspc.spc-/-peakgen.spc
Label B: H K
_C^I_ C_^_ _ __J3a_
1 20 2_20 3_20 4 20 5 20 6_20 7_2O 8 20 9 20 10.20
A-208
-------
Point 12
Label A: 1 6apr04 P6c7 371 216 Point 1 2
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 13
Label A: 1 BaprOI p6c7 371 21 E Point 1 3
c:\edax32\genesis\genspc.sp c^f p e a kg e n. s p c
Label B: H K
Pb
As
A-209
-------
<(*'-
A-210
-------
EDS Scan Images by Point
Point 1
LabelA:11junO4 P6C7 378 276 Point 1
0.80 1.60 2.40 3.20 4.00 4.80 5.60 6.40 7.20 8.1
Point 2
3 2\cj e n e s i s\{) e n s p c. s p c
Label A: 1 I j.11,111 PBC7 378 276 Point 2
Si
A
I Pb
1.60 2_40 3.20 4_00 4_80 5.60 6_40 7.20
A-211
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 1 junO4 P6C7 378 276 Point 3
II nil 1.60 2.40 3.20 4.00 4.00 5.GO 6.40 7.20 0.00
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 1 1 junOI P6C7 378 276 Point 4
1.80 1.6O 2.-10 3_ZO
Label A: 1 1 junO4 P6C7 378 276 Point 5
4_8O 5_6O
7.20 8_l
Point 5
n e s i s\g enspc.spc
0.00 1.60 2.40 3.20 4.00 4 00 5.60 6.40 7.20 8.00
A-212
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: 1 1 junO4 P6C7 378 276 Point 6
5.GO 6.10 7.20
Point 7
c:\edax32\genesis\genspc.spc
LabelA:11junO4 P6C7 378 276 Roint 7
0.80 1 60
Label A: 1 1 junO4 P6C7 378 276 Point 1
Point 8
c:\e d a>c3 2Vg e n e s i s\g enspc.spc
LGO 2.40
A-213
-------
Point 9
Label A: 1 1 junO4 P6C7 378 276 Point 3
II 11II 1.60 2.40 3.20 4.00 4.00 s Ml 6.40 7.20 0.00
Point 10
g e n e s i s\g enspc. spc
Label A: 1 1 junOd P6C7 37B 276 Point 1 D
Al ,'
A/.
070 140 2 10 2 80 350 4 20 490 5 60 6 30 7 00 7.7
A-214
-------
P6C7 - 398, 208
BSE Image
A-215
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
! Point 1 Label H: l-l K
2.00 3.00
5.0O 6.00 7.00 B.OO 9.00 in nil
Point 2
Label A: 1 3APRO4 P6c7 398 2O8 Point 2
c:\edax32\genesis\genspc. spc-/-peakgen.spc:
Label B: H K
5.00 6.00 7.00 0.00 9.00 10.00
A-216
-------
Point 3
Label A: T 3AF>Fia4 F-BcT 398 ZOB Point 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 4
Label A: 1 3APRO4 PBc7 398 2O8 Point
c:\edax32\genesis\genspc.spc-f-peakgen.spc
Label B: H K
Pb
As
1.00 2.00
Point 5
Label A: 1 3ARROJ RBc7 398 ZO8 Point 5
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
A-217
-------
Point 6
Label A: 1 3APRO4 P6c7 398 2GQ Point G
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Point 7
c:\edax32\ge
Label A: 1 3APRO-4 P6c7 398 ZO8 Point 7
s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
Point 8
Label A: 1 3APRO-4 P6c7 39S 2O8 Point t
s\g e n s p c. s p c-/-p e a kg e
Label B: H K
A-218
-------
Point 9
Label A: T 3AF*ROJ| F*6c7 333 ZOB Point a
abel I !: I I K
Point 10
Label A: 1 3APRO4 P6c7 398 2O8 Point 1 O
c:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
1.00 200 3 00 400 5.00 600 7.00 0.00 900 1000 1100
A-219
-------
P6C7 - 402, 315
BSE Image
'--' : .<>
' V-
\ cu . i^-**'-
^iK t«A-^
^ '^vi
^
A-220
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
Label A: 1 GjunO4 PGC7 4O2 31 5 Point 1
0_90 i.JtU 2_7O 3_60
6_30 7.20 8_1O 9_00
Point 2
c:\e d as<:3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 RGC7 4O2 31 5 Point 2
i i
0.90 I 110 2.70 3.60 4.50
A
6.30 7.20 0.10 9.00
A-221
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 6junO4 P6C7 4OZ 315 Point 3
0.90 1.00 2.70 3. GO 4.50 5.40 6.30 7.20 0.10 9.00
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 PGC7 4O2 31 5 Point 4
.9tt 1_80 Z_7O 3_60 4_5O
C.30 7_20 8.10 9_l
Point 5
n e s i s\g enspc.spc
Label A: 1 GjunO4 P6C7 4OZ 31 5 Point 5
0.90 1.00 2.70 3.60 4.50 5.40 6.30 7.20 0.10 9.00
A-222
-------
Point 6
O.90 1.8O 2.70 3.6O 4.50 5.40 6.30 7.2O 8.10 9.0O
Point 7
c:\e d a>c3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 RGC7 4O2 31 5 Roint 7
0.90 1.88 2.70 3.GO 4.50 5.40 G.30 7.20 8.10 9.01
Label A: 1 6junO4 P6C7 4O2 31 5 Roint 1
Point 8
0.90 L8O 2_70 3_6O 4_5O 5_40 6.30 7.20 8_10 9_0(
A-223
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: 1 BjunO4 P6C7 4O2 31 5 Point 3
2.7O 3.GO 4.50 5.40
e.3O 7.20
Point 10
s\g enspc.spc
Label A: 1 GjunO4 PGC7 4O2 31 5 Point 1 O
A-224
-------
P6C7 - 434, 278
BSE Imaj
A-225
-------
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 11 junOI P6C7 131 278 Point 1
A
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 It
Point 2
e d ax3 2\g e n e s i s\g enspc.spc
LabelA:11junO4 PGC7 431 278 Point 2
1 00 2_00 3_00 4 00 5_00 G 00 7_00 0_00 9 00 10.00 11.00
A-226
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: 1 1 junOI PGC7 434 27S Point 3
2_DD 3.00 1 00
0_00 9_OO 10.00 11.00
Point 4
LabelA:11junO4 PEC7 434 278 Roint
Mg P
1.00 2.00 3.00 4.00 5.00 6.00 7 00 8.00 9.00 10.00 11.00
Label A: 1 1 junO4 PGC7 434 278 Roint 5
Point 5
l.OO 2.OO
5.00 e.oo
9.00 1O.I
A-227
-------
Label A: 1 1 junO4 P6C7 434 278 Point 6
Point 6
0.70 1.40
2.10 2.80 3.50 4.20 4.90 5.60 6.30 7.00
LabelA:11junO4 P6C7 434 278 Point 7
Si
I
Point 7
2_10 2_80
5_60 6_30 7_00 7.7
Label A: 1 1 junO4 PEC7 434 278 Point 1
Point 8
0.70 1.40 2.10 2_80
4.90 5_60 6_30 7.00
A-228
-------
Point 9
c:\eda:x:32\genesis\genspc:.spc
Label A: 1 1 j.mlM PGC7 -13-1 278 Point 3
1.40 2.10 2.80 3.50 4.20 4.90 5.60 6.30 7.00 7.7
Point 10
c:\edax32\genesis\genspc.spc
Label A: I I j.mill PEC7 434 278 Point 1 O
Si
A
0.70 1.40 2.10 2.80 3.50 4.20 4.90 5. CO 6.30 7.00
A-229
-------
P6C7 - 465, 249
BSE Imaj
r *
A-230
-------
Silicon
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspe.spc
Label A: 1 GjunO4 P6C7 165 249 Point 1
^>Vw^-^V^V^^^^^
0.00 1 60 2.40 3 20 4.00 4.80 5.60 6_40 7.20 8 00
Point 2
Label A: 1 6junO4 R6C7 465 219 Point 2
s*t
I
0.80 1.60 2.40 3.20 4.00 4.00 3.60 G.40 7.20 8.00
A-231
-------
Point 3
Label A: 1 6junO4 P6C7 465 249 Point 3
Point 4
Label A: 1 GjunO4 P6C7 465 249 Point 4
Point 5
Label A: 1 GjunOI PGC7 465 249 Roint 5
A-232
-------
Point 6
Label A: 1 BjunO4 P6C7 465 Z49 Point 6
1.60 2.40 3.2O 4.DO 4.80 5.60 6.40 7.20
Point 7
;:\e d ax3 Z\g e n e s i s\g enspc.spc
Label A: 1 GjunO4 PGC7 465 249 Point 7
l.GO 2.4O 3.2O -4.00 4.80 5.GO 6.4O 7.2O
Point 8
Label A: 1 6iunO4 PGC7 ^165 2^19 Point 1
0.80 1.60 2.40 3.20 4.00 4.00 5.60 6.40
7.20 0.00
A-233
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: 1 GjunO4 PGC7 465 249 Roint 9
Si
e
_xJ
)
\^__A?
ft '.
i ' *
ii | p ft
; ''-A^?^___y V-, __^L^V^____
0.00 1.60 2.40 3.20 4.00 4. BO 5.60 6.40 7.20 8.00
Point 10
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 1 6junO4 PGC7 165 219 Roint 1 O
o oo i_eo
7.20 0_00
Label A: 1 GjunO4 RGC7 465 249 Roint 1 1
Point 11
0.80 1.60 2.40 3.20 4.00 4.80 5.60 £.40 7.20
A-234
-------
Label A: 1 GjunOI PGC7 465 249 Point 1 2
Point 12
c:\edax32\genesis\genspc.spc
A-235
-------
P6C7-498,110
BSE Image
A-236
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
Label A: lljunt)4 P6C7 498 1 1 O Point 1
Si p
V J \
2.10 2_80 3_50 4.20 4.90 5.60 6.30 7.00 7.70
Point 2
LabelA:11junO4 RGC7 498 1 1 D Roint Z
0.70 1 40 2.10 2_80 3.5O 4.29 4.9O 5.6O 6.30 7 00 7.7
A-237
-------
Point 3
c:\edax32\genesis\genspc.spc
abel A: 1 1 junO4 P6C7 498 1 1 O Point 3
D.7O 1.4O 2.1O 2.BO 3.5O 4.2O 4.9O 5.GO G.3O
Point 4
Label A: 1 1 junO4 P6C7 498 1 1 D Point 4
0.70 1.10 2.10 2.80 3.50 4.20 4.90 5. GO G.30 7.00
Point 5
Label A: 1 1 junO-4 P6C7 498 1 1 O Point 5
A
Si
A-238
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: lljunO4 P6C7 498 1 1 O Point 6
0.70 1.40 2.10 2.80 3.50 4.20 4.90 5.60 6.30 7.00 7.7
Point 7
c:\e d ax: 3 i_\y e n e s i s\g enspc.spc
Label A: 11junO4 P6C7 498 1 1 O Point 9
jWls^wv'A
2_10 2_80 3_5O
S_60 6_30 7_OO 7.7
Point 8
LabelA:lljunO4 P6C7 498 1 1 O Point !
v
Fe
A
2_1D 2_8D 3_50 A.20 4.9tt 5_60 6_30 7_00 7_7
A-239
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: lljunOI PGC7 498 110 Point 9
-1 XII -1.90
Point 10
e s i s\g enspc. spc
LabelA:lljunO4 PGC7 498 1 1 D Point 1 D
A-240
-------
P6C8 - 345, 256
BSE Image
Manganese (Mn)
K*
A-241
-------
EDS Scan Images by Point
Point 1
c:\e d ox3 2\g e n e s i s\g enspc. spc
Label A: 3OMarO4 PGC8 345 Z56 Point 1
F»b
As
l.nn 2.00 3.OO
5_OO 6.0O 7.00 6.OO 9.OO 10.00 11. OO 12. OO
Point 2
s i s\g enspc. spc
Label A: 3OMarO4 P6C8 315 256 Point
A-242
-------
Point 3
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6CB 345 256 Roint 3
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGCO 345 25B Point A
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 5
c:\e d a:-c 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 RGCO 345 256 Point 5
1.00 2.00 3.00 4.00 5.00 G.OO 7.00
Pb
As
'I »l< 10.00 11.00 12.00
A-243
-------
Point 6
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6CB 345 256 Roint 6
Pb
As
Point 7
l.OO 2.00 3.00 4.00 5.00 6. DO 7.00 0.00 9.OO 10.00 11.00 12.00
Point 8
e d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: 3OMarO4 PGC8 345 256 Point 8
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
A-244
-------
Point 9
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 345 256 Point 9
PbM
|P K
K K
CdL
PbL
AsK
1-00 2.00 3.00 4.00 5.00 6.00 7.00 B.OO 9.00 10.00 11.00 12.00
Point 10
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGCB 345 256 Point 1 D
LOO 2.00 3.00 4.00 5.00 6.00 7.00 S.OO 9.00 10.00 11.00 12 00
Point 11
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGC8 345 Z5G Point 1 1
2.00 3.00 4.00 5.00 6.00 7.00
PbL
AsK
9.00 10.00 11.00 12.00
A-245
-------
Point 12
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 RGC8 345 256 Roint 12
J
Point 13
c:\edax32\genesis\genspc.spc
Label A: 30Mar04 P6CB 345 256 Paint 1 3
100 200 3 00 400 500 600 700 0 00 900 1000 1100 1200
A-246
-------
P6C8-361,147
BSE Image
A-247
-------
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6CB 361 1 47 Point 1
1.00 2.00 3.00 4.00 5.00 f> III! 7.00 0.00 9.00 10.00 11.00 12.00
Point 2
cl\e d a>:3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 361 1 47 Point
JV
1 00 200 3 00 400 500 GOO 700 0 00 9 00 1000 1100 1200
A-248
-------
Point 3
Label A: 3OMarD4 PGC8 361 1 47 Point 3
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 4
s i s\g enspc.spc
Label A: 3OMarO4 P6C8 3E1 1 47 Point A
I ON 2_00 3_
5_00 6_OO 7.00 0.00 9.OO 10.00 11.00 12.00
Point 5
tr:\"C d ax 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGC8 361 1 47 Point 5
n
-^-vv^^vW W
1.00 2.00 3.00 4.00 5.00 6.1
Pb
As
00 9.00 10.00 11.00 12.00
A-249
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: 3OMarO4 PBC8 361 1 47 Point 6
I Pb K
\P Cd
1 00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 7
c:\e d ax 3 2\g e n e s i s\g enspc..spic
Label A: 3OMarO4 P6CB 3B1 1 A~f Point ~f
Pb
As
1 00 2.00 3.00 4.00 5.00 6.00 7.00 S.OO 9.00 10.00 11.00 12 00
Point 8
c:\e d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: 3OMarO4 PGC8 361 1 47 Point t
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
A-250
-------
Point 9
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 361 1 47 Point 9
Fe
4IL/Y_
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.1
Point 10
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 RGCB 3G1 1 47 Point 1 D
All i
LOO 2 00 3.00 4.00 S.OO li.OO T.OO 0_00 9 00 10 00 11.00 12 00 13.00 14.00
Point 11
cr:\c d ax 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGC8 361 1 47 Point 1 1
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00 12.00 13.00 14.00
A-251
-------
Point 12
c:\c d a::-c3 i^\q c n c s i s\fl c n s p c. s p c
Label A: 30MorO4 PEC8 361 147 Point 1 2
1.00 2.00 3.00 1.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00 13.00 14.00
A-252
-------
P6C8 - 399, 228
BSE Imaj
A-253
-------
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: JuMarU'1 P6C8 399 228 Point 1
I (HI 2_00 3_00
5_00 6_00 7_00 IJ.UU 9.OO 111 UU
Label A: JUMarO-1 P6CB 399 228 Point 2
Point 2
i no 2_00
LOO 5_00 6.00 7 00 8 00 3.00 10.00
A-254
-------
Point 3
Label A: 3OMarO4 P6CB 399 2Z8 Roint 3
^^^^^
l.UU 2_00 3_00 -1.UU 5_00 6_00 7_00 0 00 9_00 10.00
Point 4
Pr MII Fe
i i«< 2.00 3.00 i nn 5.00 e.oo 7.00 e.oo 9.00 10.00 11.00
Point 5
Label A: JUMurUJ P6C8 399 228 Point B
1 00 2 00 3 00 4 00 5 00 6 00 7 00 tt 00 900 10 00 11 00
A-255
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 399 228 Point 6
Pr Mn Fe
1.00 2.00 3.00 4.00 5.00 6.00 7 00 Ji 00 9.00 10.00 11.00
Point 7
c:\e d ax: 3 2\g e n e s i s\g e n s p c. spc
1_OO 2_00 :t IMI
Label A: :tl]MjirlM P6C8 399 228 Point 8
9_00 10
Point 8
c:\edax32\genesis\genspc.spc
IN u 2 no 3 no 4 no 5 on e on -t.ua u.ua -j.ua in uu 11 on
A-256
-------
Point 9
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 399 228 Point 9
Point 10
c:\e d ax 3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 RGCB 399 22S Point 1 D
LOO 2_00 3_00
Label A: 3OMarO4 PGC8 399 228 Point 1 1
5.00 G 00 7 00
Point 11
r:\c d ax 3 2\g e n e s i s\g enspc.spc
1.00 2.00
A-257
-------
Point 12
Label A: 30MorO4 PBC8 399 228 Point 12
1.00 2.00 3.00 -1 III! 5.00 6.00 7.00 a 00 9.00 10.00 11.00
A-258
-------
P6C8 - 400, 208
BSE Imaj
A-259
-------
Silicon (Si)
^^^^^m^^m^m-ff .
EDS Scan Images by Point
Point 1
c:\e d a ~-T 3 Z\ tj e n e s i s\g e n s p c. s p c
Label A: 3O Mar OA P6C8 X=4QQ Y=2O8 Point 1
Pb
As
1.00 2_00 3 00 A 00 5 00 6 00 7 00 8.1IU 9_00 10.00 11.i
Point 2
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGC8 4OO 2O8 Point
Pb
1 Oil 2_00 3_00 -1.0(1 'J 00 li 00 7.00 S.UU 9_00 10 00 11.1
A-260
-------
Point 3
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 R6C8 4OO 2O8 Roint 3
Point 4
Label A: 3OMarO4 RGCQ 4OO 2OG Roint A
1.00 2.OO
Label A: JUMurUJ PBC8 lOO 2O8 Point
4.00 5.00 G.OO 7.0O
9.00 10.OO
Point 5
l.DO 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
A-261
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 4OO 2O8 Point 6
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.1
Point 7
e d ax3 2\p c n e s i s\g e n s p c. spc
Al |
Pb
As
LOO 2.00 3.00 4.00 5.00 ft III! 7_OO
MM Ml Ml IMI
Label A: 3OMarO4 PBC8 4OO 2OO Point
Point 8
c:\e d ax3 2\g e n e s i s\g enspc.spc
LOO 2.00 3.00 -1_00 5_00 b_00 7_00 8_00 9_00 10.00
A-262
-------
Point 9
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 4OO 2OQ Roint
K
\fwwM^AJ^ \r*tjit~w,jjVs^-
l.UU 2_00 J.iJU -1.UU 5_00 6_00
i.iJU 9_00 10.00
Point 10
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 -4OO 2O8 Point 1 O
1.00 2.00 3.00 4.00 5.00 6.00 7.00 B.OO 9.00 10.00
A-263
-------
P6C8 - 454, 290
BSE Image
A-264
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\e d fi-.-' 2\g e n e s i s\9 e n s p c. s p c
Label A: 30h1ar04 F-GCB J5^l 2SO Point T
Al i , I Pb
A
Point 2
c:\e d ax 3 2\g e n e s i s\g e n s p c. spc
Label A: 3OMarO1 Pf.CO 454 29O Point
i.oo 2_no ji.oo -i oo s_oo e_oo 7.00 e on y.oo 10 oo 11.00 12.00
A-265
-------
Point 3
Label A: 3OMarO4 P6C8 454 29Q Point 3
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00
9.00 10.00 11.00 12.00
Point 4
c:\e d ax 3 2\g e n e s i s\g enspc..spic
Label A: 3OMarO4 PGCB 454 29O Point A
Pb
As
LOO 2_OO 3_00
5.00 G 00 7.00 8.00 9.00 10.00 11.00 12.OO
Point 5
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: 3OMarO4 PGC8 454 Z9O Point 5
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
A-266
-------
Point 6
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: 3OMarO4 P6C8 454 29O Roint
Pb
As
Point 7
l.OO 2.00 3.00 4.00 5.00 6. DO 7.00 0.00 9.OO 10.00 11.00 12.00
Point 8
Label A: JUMurUJ PBC8 4E4 29O Point G
Pb
^ As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
A-267
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: 30Mar04 PBC8 454 290 Point 9
L/wv *'
Fe
A-268
-------
P6C9 - 395,183
, & »
. >V\
--^? f^ik rs
BSE Image
Iron
Manganese (Mn)
^ m m
Lead (Pb)
A-269
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc.spc-/ peakgen.spe
Label A: 1 3APRB4 P6C9 395 1 83 Point 1 Label B: H K
hJ
i rJ
-I
Si K
Al 11
NaA/^
'-^v^-^-^ ^
1 00 2 00
Ba
!\
\ \ \
\ - 1 A
^*j&^~^^ ^ v^Xv^j^yv,_.^__.
3 00 4 00 5 00 e 00 7 00
Point 2
I
o on 9 no 10 oo
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APR04 P6C9 395 183 Point 2 Label B: H K
Si
K
Cd Ca
3 00 1 UU
Pb
As
5 00 6 00
7 00 8 00
9 00 10 00
A-270
-------
Point 3
Label A: 1 3ARRO4 RGC9 395 1 S3 Point 3
Label B: H K
Point 4
c:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APRO-4 P6C9 395 1 S3 Point A Label B: H K
0
Al
_JJ VJS2-J\HJ
Fe
i», Ca M
V /v K /I Pb
V \^^v^,!^f^^^^^^^J^Ss^^^^^^^^^Jti}Si^J V.^.^-x.^ As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 5
Label A: 1 3APRO-4 P6C9 395 1 S3 Point 5
n esi s\g e ns pc. spc-/-peakgen.spc
Label B: H K
Rb
As
5.00 e_oo
A-271
-------
Point 6
9S 1 83 Point B
erie sis\gen spc.spc / pe akgen . sp c
Label B: H K
Point 7
Label A: 1 3A.PR.0.4 P6C9 39B 1 S3 Point ~f
e da>c3ir*\gen esi s\g e ns pc. spc-/-p ea kge n.s pc
Label B. H I'
5_00 6_00
Point 8
Label A: 1 3APF«.O^ PBC9 39B T B3 Point 1
s\genspe.spe-/-peakg
Label B: H K
1 KII 2.00 3_00
A-272
-------
P6C9 -452,188
BSE Image
Iron (Fe)
Manganese (Mn)
Lead (Pb)
A-273
-------
Silicon
EDS Scan Images by Point
Point 1
c:\e d arc3 2\g c n c- s i s\g e n s p c. s p c-/-p e a kg e n. s p c
abel A: 1 3APROJ P6C9 45Z 1 88 Point 1 Label B: H K
Pb K
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.1
00 9.00 10.00
Point 2
c:\edax32\genesis\genspc.sp c^f p e akgen.spc
Label A: 1 3APR04 P6C9 452 188 Point 2 Label B: H K
Si
, I Pb K Pb
c_/ \___Na _AL' _\p_, ^ £i___c«i__ ,-!?*_-_», -_Mc,__J;? __*£_
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
A-274
-------
Point 3
c:\ed ax32\genesis\ge
Label A: 1 3ARP.O4 RGC9 4B2 1 88 Roint 3
spc-spc-/-pealege
el B: H K
Point 4
Label A: 1 3APRB4 P6C9 452 1 88 Point 4
n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
Pb
As
Point 5
Label A: 1 3APROJ R6C9 452 1 1
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
A-275
-------
Point 6
c:\ed ax32\genesis\genspc-spc-/-peak:gen.spc
abel A: 1 3ARRO4 RBC9 452 1 88 Roint 6 Label B: H K
LA/
A Al ".
y i A i
i nn 2.00 a_oo -4.00 5_oo G.oo 7 nn it nn i nn in nn
Point 1
c:\e dax:3Z\gen esi s\gens pc. spc-/-pea kge n.s pc
Label A: 1 3APRO4 P6C9 452 1 88 Point 7 Label B: H K
I '. P
Cd Ca Ba
Pb
As
J.llll .: IIU
1 IIU 5_00 (, IIU
9_00 MJ.UII
Point 8
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label A: 1 3APRO4 PBC9 452 1 88 Point 8 Label B: H K
| ' Pb
LOO 2_00 3_00 -1.00 5_00 C.OO 7.00 8_00 5.00 10.00
Cd C
Pb
As
A-276
-------
P6C9 - 482, 224
BSE Image
Iron (Fe)
Manganese (Mn)
Phosphorous(P)
Lead (Pb)
A-277
-------
Silicon (Si)
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc.spc-jT-peakgen_spc
Label A: 1 3APRQ4 P6C9 482 224 Point 1 Label B: H K
Pb
As
1.00 2.00
4.00 5.00 6.00
00 9.00 10.00
Point 2
Label A: 1 3APR04 P6C9 482 224 Point 2
\genspc. spc-/-peakgen.spc
Label B: H K
1 00 2 00
4 00 5.00 6 00 7 00 8.00 9 00 10 00
A-278
-------
Point 3
Label A: 1 3APRO4 R6C9 4BZ ZZ4 Point 3
;:\edax3Z\genesis\genspc-spc-/-peak:g.en.spc
Label B: H K
I nn 2.00 3.00 -4.00 5_00 G.OO 7_00 B_OO 9_00 10.0O
Point 4
c:\e dax:3Z\gen esi s\gens pc. spc-/-pea kge n.s pc
Label A: 1 3APRO4 P6C9 182 221 Point A Label B: H K
Pb
As
LOO 2.00 3.00 4.00 5_00 (, IIU 7_l
9_00 IU.UII
Point 5
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label A: 1 3APROJ PBC9 4BZ 2Z4 Point 5 Label B: H K
LOO 2 00 3_00 -1.00 5_00 6_00 7 00
9.00 10.00
A-279
-------
Point 6
Label A: 1 3APRO4 R6C9 4BZ ZZ4 Point B
;:\edax3Z\genesis\genspc-spc-/-peak:g.e
Label B: H K
Point 7
c:\e dax:3Z\ge
Label A: 1 3APRO4 P6C9 182 221 Point 7
esi s\gens pc. spc-/-pea kge n.s pc
Label B: H K
Rb
As
Point 8
Label A: 1 3APROJ PBC9 4BZ 2Z4 Point 1
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
A-280
-------
P6C9-331,212
BSE Image
Iron
Manganese (Mn)
A-281
-------
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APROA P6C9 331 212 Point 1 Label B: H K
100 200 3 00 400 500 600 700 000 9 00 1000 1100
Point 2
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APRO4 P6C9 331 212 Point 2 Label B: H K
:; c
;; f.
iJv
Si
Al
Wv^
, ^b *-
i AS ^ ' [ 1 i^, pb
X^^M^-^^VJv-Jv^^^v-v^--^^v^wv^^ V.-^ ^.^A^V.-^W^-^-^-^V.-^-^^^^^^^ ^^^,ir^Ss -^
2_00 3_00 -1 HO 5_00 6
-------
Point 3
c:\ed axS 2\gene sis\gen spc.s pc/pe akgen. sp c
Label A: 1 3ARRO4 RGC9 331 21 2 Roint 3 Label B: H K
1 00 2 00 3 00 4 00 5 00 6 OO 7 OO 0 00
Point 4
c:\edax32\genesls\genspc.spc / peakgen.spc
Label A: 1 3ARROJ R6C9 331 21 2 Roint 4 Label B: H K
JJ^VV"-"VV ^V^"/V,
Pb
As
LOO y. UU 3_00
-------
Point 6
e:\ed ax:3Z\genesis\genspe-spe-/-peakgen.spc
nt G Label B: H K
Pb
As
I 00 2.00 3.0O 4.00 5.00 6.OO 7.OO 8.00 9.DO
Point 7
c:\edax3Z\genesis\genspc. spc-/-p ea kge n.s pc
Label A: 1 3ARRO^I R6C9 331 21 2 Roint 7 Label B: H K
5_00 G.UU 7_OO 8_00 9_00 10.00
Point 8
Label A: 1 3APROJ PBC9 331 2T Z Roint B
s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H 1C
6.0O 7.OO 8.00 9.OO
A-284
-------
P6C9-357,180
BSE Image
Iron (Fe)
Phosphorous(P)
A-285
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: 1 3APFtO4 P6C9 357 1 8O Point 1
\genspc.spc-/ peakgen.spc
Label B: H K
F"b
As
LOO 2_00
Label A: 1 3APRO-*! F*6C9 357 1 BO Point Z
_OO y.uu
Point 2
Label B: H K
2.OO 3.0O 1 "ii mi 6.OO /"' 8.00 9.0O 1O.OO
A-286
-------
Point 3
Label A: 1 3ARRO4 P6C9 357 1 8O Roint 3
c:\ed ax32\genesis\genspc-spc-/-pealege
Label B: H K
Point 4
Label A: 1 3APR04 P6C9 357 1 BO PC
c:\edax32\genesis\genspc. spc-/-peakgen.spc
nt 4 Label LI: I I K
A-287
-------
Point 5
Label A: 1 3ARRO4 RGC9 357 1 SO Roint 5
:\edax3Z\genesis\g en spc.s pc-/-pe akg en.spc
Label B: H K
00 9.DO 10.00
Point 6
Label A: 1 3ARR.O4 P6C9 357 1 BO Point I
;:\edax32\genesis\genspc.spc X peakgen.spc
Label B: H K
Pb
As
Point 7
Label A: 1 3ARR.O4 P6C9 357 1 BO Point 7
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
A-288
-------
Point 8
Label A: 1 3ARRO4 RGC9 357 1 BO Point 1
Label B: H K
Pb
As
2 00 3 00 4 00 5 00
9_00 10.00
Point 9
Label A: 13APR04 P6C9 357 180 Points
Label B: H K
Pb
As
2 00 3 00 4 00 VUU G 00 7 00
9 00 10 00
A-289
-------
Point 10
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label A: 1 3APRQ4 P6C9 357 1 SO Point 1 0 Label B: H K
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
Plots
A-290
-------
P8C7-312,164
BSE Imaj
Iron
\ ;
Manganese (Mn)
A-291
-------
EDS Scan Images by Point
Point 1
D:\~Userdata on EPMA\Userlmages\O1 junOI PGC7 312 164 Roint 1 .spc
Label A: O1 junO4 P8C7 312 164 Point 1
A
J \
5.00 6.00
9_00 10_00 11.00
Point 2
Label A: O1 junO4 PBC7 312 1 64 Point Z
9_OO 10.00
A-292
-------
Point 3
Label A: OljunO4 P8C7 312 164 Point 3
0.90 1.00 2.70 3.GO 4.50 5.40 £.30 7.20 0.10 9.00
Point 4
Label A: O1 junO4 P8C7 312 164 Roint
2_1O 2_80 3_5O 4.20 4.90 5_60 6.30 7.00
Point 5
Label A: O1 junO4 PBC7
2_1O 2_80 3_5O 4.20 4_9O 5.60 6_30
A-293
-------
Point 6
Label A: O1junO4 R8C7 312 164 Point 6
I.SO 1.6O ? -in 3.20
m 7.20
Point 7
i.eo 2.40
A. SO 5.60
7.2O 0.00
Point 8
Label A: O1 iunO4 PBC7 312 1 B'l Point 1
Mg §J^^-^_»_JlE
0.8D 1.60 Z.40 3.20 4.00 4.00 5.60 6.40 7.20 8.00
A-294
-------
Point 9
Label A: O1junO4 P8C7 312 164 Point !
I
D.BO 1.6O 2.4O 3.2O 4.OO
Point 10
Label A: O1junO4 P8C7 312 164 Point 1 O
A-295
-------
P8C7 - 325, 345
BSE Imaj
A-296
-------
EDS Scan Images by Point
Point 1
Label A: P8C7 X-3ZS Y-Z^IS Point T
Cd Ca
2.00 3.00 -4.00 5.00 6.00 7.OO
Point 2
c:\e d ax 3 2\g c n c s i s\g e n s p c. s p c
Label A: RBC7 X-3Z5 Y-245 Point
1.00 2.00 3.00 4.00 5.00 r. nil 7.00 0.00 9.00
A-297
-------
Point 3
c:\ed.-»;.[ ~.'\fj e n e s i r,\rj enspc.spc
Label A: PBC7 X-3Z5 Y-Z^I5 Point 3
LOO 2_00 3_00 4_00 5_00 6 OO 7.OO 8_00 9 00
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: PBC7 X-325 Y-245 Point A
1 00 2 00 3 00 1 00 5 00 6 00 7 00 0 00 9 00
Point 5
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: PBC7 X-325 Y-245 Point 5
2 00 3.00 4_00 5_00 G_00 7_00 G.OO 9_00
A-298
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: P8C7 X-325 Y-245 Point 6
2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
Point 7
c:\edaK32\genesis\genspc.spc
Label A: P8C7 X-325 Y-245 Point 7
i no 2 on 3 oo 4 no 5 on & no 7 no n on
A-299
-------
P8C7 - 380, 269
BSE Imaj
A-300
-------
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P8C7 X-38O Y-269 Point 2
2_10 2_80 3_50 4_20 4_90 S.ftU 6_30 7_00
Point 2
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P8C7 X-3OO Y-269 Point 2
0.70 1-40 Z.10 2-80 3.50 -4.20 4-90 5-60 6,30 7.00
A-301
-------
Point 3
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: PBC7 X-3OO Y-269 Roint 3
I.iJU 2.00 3_OO 4_00 S_00 6 00 7_00 8 00 9.00
Point 4
:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: PBC71 X-3BO Y-2B9 Point
I
c* I C"
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
Point 5
c:\e d a:-c 3 2\g e n e s i s\g enspc.spc
Label A: PBC71 X-3BO Y-Z69 Point 5
Mn /
v^J"J^Jf*SSfv'*-s*S/f^fJ^fJ
2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
A-302
-------
Point 6
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: PBC7 X-3OO Y-269 Roint B
J.UU 4_OO S_00 6_00
Point 7
c:\e d ax3 2\g e n e s i sAq enspc.spc
s_oo 9_ao
Label A: PBC71 X-3BO Y-2B9 Point
5.00 G.OO 7.OO 0.00
Point 8
i s\g e n s p c. s p c
Label A: PBC7 X-3BO Y-269 Point S
1.00 2.00
5.00 6.00
7.00 8.00
A-303
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: P8C7 X-380 Y-Z69 Point 9
Al ,' '[ P
A-304
-------
P8C7 - 398, 323
BSE Imaj
V
,-
I
A-305
-------
EDS Scan Images by Point
Point 1
Label A: O I j.ir.ll/l PGC7 398 323 Point 1
1.00 2.00 3.00 4.00 5.00 £.00 7.00 8.00 9.00 10.00
Point 2
Label A: O1junO4 F*8C7 398 323 F*oint 2
i on 2.00 vt (ID >4_oa s_oo
7_oa 8_oo
A-306
-------
Point 3
c:\edax32\genesis\genspc.spc
Label A: OljunO4 P8C7 398 323 Point 3
o
A
1.00 2.00 3.00 4.00 b 00 6 00 7.00 0.00 9.00 10.00
O
A
Si
j
Point 4
1_OO 2_00 3_
Label A: OljunO-4 P8C7 398 323 Point 5
5_OO 6_
7_00 8_OO 9_00 1U.I
Point 5
5_00 6_00 7_00
9_00 10.00
A-307
-------
Point 6
Label A: OljunO4 P8C7 398 323 Point S
1.00 2.00 3.00 4.00 5.00 6 00 7.00 8.00 9.00 10.00
Point 7
1_OO 2_00
3_OO 4_00 5_OO 6 00
8_00 IP UU
Point 8
Label A: O1junO4 P8C7 398 323 Point 1
0_8O 1_6O
A-308
-------
Point 9
Label A: OljunO4 P8C7 398 323 Point 9
Label A: II I j.n.lM P8C7 398 323 Point 1 O
Point 10
i no 2 oo
5 oo cmi
I 00 9 00 10 00 11.00 12.00
A-309
-------
P8C7 - 456,196
BSE Image
A-310
-------
EDS Scan Images by Point
Point 1
Label A: O1junO4 PBC7 456 196 Point 1
l.UU 2_00 3_00 4.00 5.00 6_00 7_00 8.00 9_00 10.00 11.00 12.1
Point 2
Label A: O1 junO4 PBC7 456 196 Roint 2
l.OO 2.00 3.OO 4.00
7.00 8 DO 9.OO 10 00 11.00 12.00
A-311
-------
Point 3
Label A: OljunO4 P8C7 456 196 Point 3
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
Point 4
c:\e d ax: 3 i_\y e n e s i s\g enspc.spc
Label A: O1 junO4 P8C7 456 196 Point
_J\J
1_OO 2.00 3_
S_00 6_00 7_00
9.OO 1U.UO II.UU
Point 5
c:\e d a>c3 2Vg e n e s i s\g enspc.spc
Label A: D1junD4 P8C7 456 196 Point 5
Si
LOO 2.00 3_OO -1 00 5_00 6.00 7.00
y.oo jo.no 11.00
A-312
-------
Point 6
c:\edax32\genesis\genspc.spc
Label A: O1junO4 P8C7 456 196 Point 6
2.00 3.OO A. 00 5. DO 6. DO 7.00 8.DO 9.00 10.OO 11.1
Point 7
Label A: O1junO4 P8C7 456 196 Roint 7
A
Si
1.00 2.00 3.00 4.00 5 00 6.00 7.00 8.00 9.00 10.00 11.00
Point 8
c:\e d a>c3 2Vg e n e s i s\g enspc.spc
Label A: D1junD4 PBC7 456 196 Roint 1
LOO 2.00 3_OO 4 00 5_00 6_00 7_00
9 00 10.00 11.00
A-313
-------
Point 9
c:\edax32\genesis\genspc.spc
Label A: OljunO4 P8C7 456 196 Point 9
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00
Label A: O1 junOI P8C7 456 1 96 Point 1 O
Point 10
l.OO 2 00 3.00 4.00 5.00 6.00 7.00
9_OO 10.00 11.00
A-314
-------
P8C7 - 490, 265
BSE Image
"
A-315
-------
EDS Scan Images by Point
Point 1
cr:\e d ax 3 2\g e n e s i s\g e n s p c. s p c
Label A: P8C7 X--49O Y-265 Point 1
I
1.00 2 Illl H Illl 4.DO S Illl I l"l 7.00 8.00 9.00
Point 2
:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P8C71 X-^I9O Y-26B Point
I 00 2 00 3 00 A 00 5 00 6 00 7 OO 8 00 9 00
A-316
-------
Point 3
c:\ed -»---! Z\g e n e s i s\g enspc.spc
Label A: RBC7 X-49O Y-265 Roint 3
s_oo 6_ao ?_
s_oo 9_ao
Point 4
c:\e d ax3 2\g e n e s i s\g enspc.spc
Label A: P8C7 X--49O Y-265 Point -
2.00 3.00 4.00 5.00 6.00 7.00
Point 5
s\g enspc.spc
Label A: PBC7 X-J9O Y-2B5 Roint 5
A-317
-------
Point 6
c:\ed ax3 2\g e n e s i s\g enspc.spc
Label A: P8C7 X-490 Y-ZG5 Point 6
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00
A-318
-------
P8C8 - 302, 323
BSE Imaj
A-319
-------
EDS Scan Images by Point
Point 1
Label A: 1 6aprO4 p8c8 3O2 323 Point 1
c:\e d sj.x 'J 2\g e n e s i s\g e n s p c. s p c~/-p e a kg e n. s p c
Label B: H K
Pb
As
Point 2
Label A: 1 EaprOI p8c8 3O2 323 Point 2
Xf]enspc.sp c-/-p e akgen.spc
Label B: H K
Cd Co
Pb
As
A-320
-------
Point 3
Label A: T GaprO4 pBeB 3OZ 323 Roint 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
I I
Pb
As
Point 4
Label A: 1 GaprO4 p8c8 3OZ 323 Point A
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
2 10 3 10
5 10 6 10 7 10 B 10
9 10 10 10
Point 5
Label A: 1 6aprO4 pGcG 3O2 323 Point 5
Label B: H K
2.10 3_10
4.10 5.10
9.10 10.10
A-321
-------
Point 6
Label A: 1 GaprO4 pBeB 3O2 323 Roint
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.10 2.10 3.10 4.10 5.1O G.10 7.10 8.10 9.1O 10.10
Point 7
Label A: 1 GaprOI P8c8 3O2 323 Point 7
:\e da>c3ir*\gen esi s\g e us pc. spc-/-p ea kge n.s pc
Label R : H K
Pb K
Cd Ca Ba
i la 2 in 3 in
5 10 e 10 7 10
10 in 10
Point 8
: 323 Point 1
n esi s\gens pc. spc-/-peakgen.spc
Label B: H K
I I H 2_10 : I " 4_10 5.10 t. lit 7.10 8_10 9_10 10.10
A-322
-------
Point 9
Label A: 1 GaprO4 pOcO 3Q2 323 Roint 9
;:\edax32\genesis\genspc-spc-/-peak:ge
Label B: H K
Point 10
! Roint 1 O
c:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Pb
As
A-323
-------
Point 11
l A: 1 GaprOI pHcH 3O2 323 Po
c:\edax32\genesis\genspc.spc^V peakgen.spc
Label B: H K
Point 12
Label A: 1 GaprO4 P8c8 3O2 323 Point 1
e dax32\gen esi s\gens pc. spc-/-p ea kgen.s pc
Label B: H K
A-324
-------
P8C8 - 328, 276
BSE Image
?*;'.'" ;|i-
Or *! N-
»?r
<-'
T
I
<^
/
* ^
A
Iron (Fe)
Manganese (Mn)
A-325
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: 1 6aprO4 p8c8 328 276 Point 1
c:\e d sj.x 'J 2\g e n e s i s\g e n s p c. s p c~/-p e a kg e n. s p c
Label B: H K
9.10 10.10
Point 2
Label A: 1 GaprO4 p8c8 328 276 Roint 2
n e s i s\g e n s p c. s p c-/-p e a kg e n - s p c
Label B: H K
A-326
-------
Point 3
Label A: 1 GaprO4 pBeB 3ZB Z7G Roint
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Mn Fe
Pb
As
Point 4
Label A: 1 GaprO4 p8c8 328 276 Roint A
i:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
2.10 J.IU
Point 5
Label A: 1 6aprO4 P8c8 328 276 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
A-327
-------
Point 6
Label A: 1 GaprO4 pBeB 3ZB Z7G Roint G
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 7
Label A: 1 GaprO4 pOcO 328 27G Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Pb K
/y L^J v v^yv
1.10 2.10
C
-------
Point 9
Label A: 1 GaprO4 pScS 328 ZZG Point 9
abel I !: I I K
Si
I
i ;
1.10 2.10 3.10 1.10 5.1O 6.10 7.10 8.10 9.1O 10.10
Point 10
Label A: 1 GaprO4 P8c8 302 323 Point 1 0
n e s i s\g e n s p c. s p c^-/-p e a kg e n. s p c
Label B: H K
1.10 2.10 3.10 4.10 5.10 G.10
9.10 10.10
Point 11
Label A: 1 GaprOI pGcG 328 276 Point 1 1
Label B: H K
Pb
As
1.10 2.10 3_10 4.10 5.10 6_10 V Ml
A-329
-------
Point 12
Label A: 1 GaprO4 pHcH 32B 276 Po
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
A-330
-------
P8C8 - 333, 340
BSE Image
A-331
-------
Silicon
EDS Scan Images by Point
Point 1
Label A: 1 6aprO4 p8c8 333 34O Point 1
:\edax32\genesis\genspc.sp c f p eakgen.spc
Label B: H K
Point 2
9 10 10.10
n esi s\gens pc. spc-/-peakgen.spc
Label B: H K
9.10 10.10
A-332
-------
Point 3
Label A: 1 GaprO4 pBeB 333 34O Roint 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 4
Label A: 1 GaprO4 PBc8 333 34O Point A
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
1 10 2 10 3 10 1 10 5 10 6 10 7 10 B 10 9 10 10 10
Point 5
4O Point 5
Label B: H K
A-333
-------
Point 6
Label A: 1 GaprO4 pBeB 333 34O Roint
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.10 2.10
SK^
Pb
As
Point 7
Label A: 1 GaprO4 p8c8 333 34D Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
1 10 2.10
Point 8
4O Point G
Label B: H K
1.10 2.10
A-334
-------
Point 9
Label A: 1 GaprO4 pBeB 333 34O Roint 9
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
_2!J
-------
P8C8 - 354, 225
BSE Imaj
*
V.
A-336
-------
EDS Scan Images by Point
Point 1
Label A: 1 BaprOI P8c8 354 225 Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
1_20 2.20 3.20
4.20 5_20 6.20
9.20 10.20
Point 2
Label A: I GaprCM pOcO 354 225 Roint 2
::\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Cd Ca Ba
Pb
As
9.20 10.20
A-337
-------
Point 3
Label A: 1 GaprO4 pBeB 3E4 ZZ5 Roint 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 4
Label A: 1 GaprO4 PBc8 354 225 Point A
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
5 20 6 20 7 20
Point 5
Label A: 1 GaprOI pGcG 351 225 Point 5
Label B: H K
A-338
-------
Point 6
Label A: 1 GaprO4 pBeB 3E4 ZZ5 Roint G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 7
Label A: 1 GaprO4 p8c8 354 225 Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Point 8
Label A: 1 GaprOI pGcG 351 225 Point G
s\genspc.spc-/-peakge
Label B: H K
A-339
-------
Point 9
Label A: 1 GaprO4 pGcO 354 225 Point 9
c:\edax32\genesis\genspc.spc /peakgen.spc
Label B: H K
Point 10
Label A: 1 GaprO4 P8c8 354 225 Point 1 O
::\e dax32\gen esi s\gens pc. spc-/-pea kgen.s pc
Label B: H K
2_10 3_1O
9_10 10.10
Point 11
Label A: 1 GaprO4 p8c8 354 22B Point 1 1
:\edax32\genesis\genspc.spc-X-peakgen.spc
Label B: H K
9.10 10.10
A-340
-------
Point 12
Label A: 1 6apr04 pBc8 354 225 Point 1 2
c:\ed ax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
A-341
-------
P8C8-361,241
BSE Image
A-342
-------
EDS Scan Images by Point
Point 1
c:\edax32\genesis\genspc. spc-/ pea kgen.spc
Label A: O9APRO4 r-BCB 361 241 Point 1 Label B: H K
1.10 2.10 3.10 4.10 5-10 6-10 7.10 8.10 9.10 10-10 11-10
Point 2
c:\edax32\genesisXgenspc.sp c-/-p e akgen.spc
Label A: O9APRO4 P8C8 361 241 Point 2 Label B: H K
1_10 2_10 3_10 4.10 5.10
_10 9_10 10.10 11.10
A-343
-------
Point 3
I F-BCB 361
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 4
Label A: O9APFIOJ PBCB 361 241 Point
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Pb
Point 5
Label A: D9APRO4 P8CB 3G1 2*11 Point 5
s\genspc.spc-/-peakge
Label B: H K
A-344
-------
Point 6
Label A: DBAF-RDI F-BCB 361
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
atjrV v^^-^y^
1.10
V^L^^-^^^^^^S? v-^L,_ -^_JJ--...-..^_.^^^JJ^^
2.10 3.10 4.10 5.10 610
Point 7
Pb
. >^_ ____ ^^ _ Ao
7.10 0.10 9.10 10. 1O 11.10
Label A: O9APFIOJ PBCB 361 241 Roint 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
1 1 Pb K
CJ \_ Na__A!/ \£_ Cdt Ca Ti Mn F«=
1.10 2.10 3.10 4 10 5 10 6 10 7.10
Point 8
Pb
As
0 10 9 10 10 10 11 10
Label A: O9APRO4 PGCG 3G1 211 Point G
Label B: H K
A-345
-------
Point 9
Label A: O9APRO1 P8C8 361 211 Point 9
;:\edax:32\genesis\genspc:-spc-/-peak:gen.spc
Label B: H K
Point 10
c:\edax3Z\ge
Label A: O9APRO1 PBCO 361 211 Point 1 O
esis\genspc. spc-/-pea kge n.s pc
Label B: H K
Pb
As
Point 11
Label A: D9APRD4 P8CO 3G1 211 Point 11
c:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Pb
As
A-346
-------
Point 12
Label A: O9APRO4 PSCB 361 241 Point 1 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
1
1
Co Fe
A-347
-------
P8C8 - 395, 203
BSE Imaj
Vtf\: r *
.vj-»
Iron (Fe)
'f-^\^^
i>vT ^
A-348
-------
Silicon (S
EDS Scan Images by Point
Point 1
Label A: 1 GaprOI p8c8 335 283 Point 1
e d ax: 3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
6.20 7.20 8.20 9.20
Point 2
Label A: 1 GaprO4 p8c8 395 283 Point 2
e d ax:3 l-"\g e n e s i s\g e n s p c. spc-/-peakgen.spc
Label B: H K
6_20 7_20
9_20 10.20
A-349
-------
Point 3
Label A: 1 GaprO4 pBeB 39S ZO3 Roint
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Si
1.20 2.20 3.20 4.20 5.20 6.20 7.20 8.20 9.2O 1O.20
Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label A: 1 GaprO4 pOcO 395 2O3 Point 4 Label B: H K
JV I
Pb
As
1 20 2_20 3_20 4 20 5 20 6 20 7_20 8 20 9 20 10.20
Point 5
Label A: 1 6aprO4 pGcG 395 2O3 Point 5
Label B: H K
1.20 2.20 3_20 -4.20 5.20 6_20 7_20 8.20 9_20 10.20
A-350
-------
Point 6
Label A: 1 GaprGI pQcQ 395 2O3 Point G
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Point 7
Label A: 1 GaprOI pGcG 335 2O3 Point 7
c:\edax3Z\genesis\genspc. spc-/-pea kge n.s pc
Label B: H K
5_20 6.20 7.20
Point 8
Label A: 1 GaprOI pGcG 395 2O3 Point G
Label B: H K
A-351
-------
Point 9
Label A: 1 GaprO4 pBeB 39S ZO3 Roint 9
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1
-
1 ' 1 "-e
Lwv si^sL^i ^/L^ , =
1.20 2.20 3.20 4.20 5.20 G.20 7.20 8.20 9.20 1O.20
Point 10
Label A: 1 GaprO4 p8c8 395 2O3 Roint 1 O
Label B: H K
Point 11
Label A: 1 6aprO4 P8c8 395 203 Point 1 1
c:\edax32\genesis\genspc. spc t pea kge n.s pc
Label B: H K
1 20 2 20
4 20 5 20 6 20 7 20 8 20
A-352
-------
Point 12
Label A: 1 GaprO4 pBeB 395 ZO3 Roint 1 2
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
*UIV-jinjr ViJLJW-^
1.20 2.20 3.20 4.20 5.20 6.20 7.20 8.20 9.2O 1O.20
Point 13
c:\e da>c3ir*\gen esi s\g e us pc. spc-/-p ea kge n.s pc
Label A: I BoprO'l P8c8 395 2:03 Point 13 LabelB:HKL
1.2O 2_2O 3_2O 4_2O 5_2O G_2O 7_2O B_2O 9_2O 1O_2O
Point 14
c:\edax32\gen esis\genspc.spc-/-peakgen.spc
Label A: 1 GaprQ4 pGcG 395 2O3 Point 1 A Label B: H K
1.20 2.20 3.20 4.20 5.20 6.20 7.20 8.20 9.20 10.20
A-353
-------
P8C8 - 399, 204
BSE Image
A-354
-------
EDS Scan Images by Point
Point 1
Label A: O9APR.O.4 PBCB 399-ZO4 Point 1
:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00
8.00 9.00
Point 2
c:\edax32\genesis\genspc. spc-/-pea kg en.spc
Label A: O9APRO4 P8CG 399-2O4 Point 2 Label B: H K
5 00 6 00
Pb
As
9 00 10 00
A-355
-------
Point 3
Label A: a9AF>Fl[]4 F-BCB 399-ZO4 Roint 3
Label B: H K
Point 4
Label A: O9ARR.O4 RBC8 399-2O4 Roint A
:\edax32\genesis\genspc. spc / p ea kge n.s pc
Label B: H K
Point 5
Label A: 09APR04 P8C8 399-201 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
A-356
-------
Point 6
Label A: a9AF>Fl[]4 F-BCB 399-ZO4 Roint G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 1O.OO 11.00 12.00
Point 7
Label A: O9ARR.O4 RBC8 399-ZO4 Roint 7
i:\edax32\genesis\genspc.spc / p ea kge n.s pc
Label B: H K
Pb
As
1 00 2_00 J.
S_00 6_00 7_00 8_00 9_00 10.00 11_00 12_00
Point 8
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label A: 09APR04 P8C8 399-204 Point 8 Label B: H K
I Pb
ww ^~*\vW-,,
100 200 300 400 500 £00 700 000 9 00 1000 1100 1200
A-357
-------
Point 9
Label A: O9APRO4 P8C8 399-2O4 Point 9
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
0
R
n
Pb
AS
I III! 2.110 3 00 4 00 5.110 6.011 7.110 8 00 9.00 10.00 11.00 12 00
Point 10
c:\edax32\genesis\genspc. spc-/-pea kge n.s pc
Label A: O9APRO-4 PBCO 399-2O1 Point 1 O Label B: H K
A-358
-------
P8C8 - 413, 208
BSE Image
rO^fcX^-SL
A-359
-------
Phosphorus(P
EDS Scan Images by Point
Point 1
c:\edax32\gen esis\genspc.spc-/-peakgen.spc
Label A: O9APRO^I PBC8 41 3 ZOB Roint 1 Label B: H K
1.00 2.00 3.00 4.00 5.00 C.OO 7.00 8.00 9.00 10_00 11.00 12.00
Point 2
Label A: D9APRDJ PBCO 41 3 ZDB Point
\genspc.sp c-/-p eakgen.spc
Label B: H K
ion 2 on
4_00 5_00 G_00 7_00
Pb
As
y.uu io_oo n_oo I2_oo
A-360
-------
Point 3
Label A: a9AF>Fl[]4 F-BCB -dl 3 ZOB Roint 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 4
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: O9ARR.O4 RBC8 41 3 2OB Roint A Label B: H K
Pb
As
Point 5
Label A: 09APR04 P8C8 41 3 208 Point 5
c:\edax32\genesis\genspc.spc /pea kge n.s pc
Label B: H K
A-361
-------
Point 6
Label A: O9APRO4 R8CB 41 3 SOB Point G
Label B: H K
Pb K
Cd Ca
Pb
As
I.UU 2_00 J_UU 4_00 5_00 6_00 7_00 8_00 9_00 1O_00 11.00 12.00
Point 7
Label A: Q9APRO4 P8CS 41 3 2O8 Point 7
n esi s\g e ns pc. spc-/-peakgen.spc
Label B: H K
r'-^^-v-^-.-^^AA-VVArt^Y*-^
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00 11.00 12.00
Point 8
c:\eda>c3Z\genesis\genspc.spc-/-peakgen.spc
Label A: O9APRO4 PGCG 41 3 2O8 Point G Label B: H K
:k
Pb K
.Co Ti
Pb
As
100 200 300 400 500 600 700 SOO 9 00 1000 1100 1200
A-362
-------
Point 9
Label A: a9AF>Fl[]4 F-BCB -dl 3 ZOB Roint 9
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1
o
A'
-^
1
K
1 pb l''1
M P A cA <=. TI
WV V^A*^P \J"-.,^^,,^^i\^^^.^_^.
n" A P"
f~J\~J V_^_*-^^_ -^^_^ _^^ , ,>= _^^
i nn 2.00 3.00 4.00
s.oo e.oo
OO 11.00 12.00
Point 10
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: O9ARRO4 RBC8 41 3 2OB Roint 1 O Label B: H K
Pb
As
1 00 2_00 J.UU
10.00 11_00 12_00
Point 11
c:\edax32\genesis\genspc.spc /pea kge n.s pc
Label A: 09APR04 P8C8 41 3 208 Point 11 Label B: H K
Pb
As
A-363
-------
Point 12
Label A: O9APRO4 PSCB 41 3 2O8 Point 1 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
l.UO 2.00 3_00 4_00 5_00 6_00 7_00 8_00 9_00
A-364
-------
P8C8 - 429, 346
BSE Image
A-365
-------
Silicon
EDS Scan Images by Point
Point 1
s\g e n s p c. s p e-/-p e a kg e n. s p c
Label B: H K
1.10 2.10 3.1O 4.10 5.10 6.1O 7.10
9.10 10.10
Point 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-f-p e a kg e n. s p c
I Point 2 Label B: H K
Vrf1 \^-*^-^\,w^,fV-^vf**w***^^
2_10 3_1O
5_10 6_10 7_10
III Hi. Ill
A-366
-------
Point 3
Label A: 1 GaprO4 pQcQ 429 34G Point 3
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Pb
As
Point 4
Label A: 1 6aprO4 pBcS 429 346 Point 4
e dax:3Z\gen esi s\g e ns pc. spc-/-p ea kge n.s pc
Label B: H K
I in z_10
5.10 G_10
Point 5
Label A: 1 6aprO4 pGcG 429 346 Point 5
Label B: H K
1.10 2.10 3_10 4.10 5.10
6_10 V III
A-367
-------
Point 6
Label A: 1 GaprO4 pBeB 429 34G Roint G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Si
1.10 2.10
5.1O 6.10
9.1O 10.10
Point 7
Label A: 1 GaprO4 p8c8 429 346 Roint 7
Label B: H K
Pb
As
2.10 J.iU 4_10 5_10
9_10 10_10
Point 8
Label A: 1 EaprOI pOcO 429 346 Point 8
c:\edax32\genesis\genspc.spc-y-peakgen.Bpc
Label B: H K
1 pb
2 10 3.10 4.10 5.10 6.10 7.10
9 10 10 10
A-368
-------
Point 9
Label A: 1 GaprO4 pBeB 429 34G Roint 9
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
1.10 2.10 3.10 4.10 5.1O G.10 7.10
9.1O 10.10
Point 10
c:\edax32\genesis\genspc.spc / p ea kge n.s pc
Label A: 1 GaprO4 p8c8 429 346 Roint 1 O Label B: H K
2.10 J.iU 4_10 5_10
9_10 10.10
Point 11
Label A: 1 6aprO4 P8c8 429 346 Point 1 1
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
1 10 2 10 3 10 4 10 1.10 6 10 7 10 0 10 9 10 10 10
A-369
-------
Point 12
Label A: 1 GaprO4 pScS -429 34G Point 1
Ag e n s p c. s p c-/-p e a leg e
Label I !: I I K
A-370
-------
P8C8 - 442, 252
BSE Image
A-371
-------
EDS Scan Images by Point
Point 1
s\g e n s p e. a: p c-f-ft e a kg e n . s p e:
Label B: H K
I.OO 2_OO 3.0O -4_OO 5.OO 6_OO 7.OO
9_OO 10. OO 11. ISO 12 OQ
Point 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-f-p e a kg e n. s p c
Label A: O9APFIO4 P8C8 442 252 Point 2 Label B: H K
LOO 2.00
A-372
-------
Point 3
Label A: O9APRO4 P8C8 442 252 Point 3
Label B: H K
Pb
As
1.00 2.00 3 00 4.00 5.00 6.00 7 nil 0 00 9.00 10.00 11.00 12.00
Point 4
Label A: O9APRO4 PBC8 442 252 Point 4
s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
_10 2_10 310
5_10 6_10 710 C. 10 9.10 10.10 11.10
Point 5
c:\edax32\genesis\genspc.spc / peakgen.spc
: Point 5 Label B: H K
1.10 2.10 3.10 4.10 5.10 6.10 7.10 8.10 9.10 10.10 11.10
A-373
-------
Point 6
Label A: O9APRO4 P8C8 442 252 Point G
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
1-1-J L -_
Pb
As
Point 7
c:\edax32\ge
Label A: Q9APRO4 PBCO 142 252 Roint 7
s i s\g e n s p c. s p c-/-p e
Label B: H K
Point 8
Label A: O9APRO4 P8CO 142 252 Point B
Label B: H K
A-374
-------
Point 9
Label A: a9AF>Fl[]4 F-BCB /H1Z ZSZ Roint 9
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 10
Label A: O9ARR.O4 RBC8 442 252 Roint 1 O
c:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
A-375
-------
P8C8 - 472, 213
BSE Image
If
A-376
-------
Silicon (Si
^^^^^^^^^^^mr^»
EDS Scan Images by Point
Point 1
1 3 Roint 1
s\g e n s p e. a: p c-f-ft e a kg e n . s p e:
Label B: H K
1.00 .2.GO 3.HO 1.QO 5.00 6_OO 7 OO
9_OO IO.OI) 11.00 12.0O
Point 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-f-p e a kg e n. s p c
Label A: O9APFIO4 P8C8 472 21 3 Point 2 Label B: H K
Pb
As
LOO 2_OO 3_OO 4_OO
A-377
-------
Point 3
Label A: a9AF>Fl[]4 F-BCB 47Z 21 3 Roint 3
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Pb K
Pb
As
i nn 2.00 3.00 4.00 s.oo e.oo 7.00 e.oo 9.00 10.00 11.00 12.00
Point 4
c:\edax32\genesis\genspc. spc-/-pea kge n.s pc
Label A: O9ARR.O4 RBC8 472 21 3 Roint A Label B: H K
Pb
As
1 00 2_00 J.UU
5.00 6_00 7_00 8_00 9_00 10.00 11_00 12_00
Point 5
c:\edax32\genesis\genspc. spc^/ pea kge n.s pc
Label A: 09APR04 PSC8 472 21 3 Point 5 Label B: H K
\**VJ* V^A-Xj^^WHV^^
Pb
As
1JIII 2 00 3 00 4 00 5 00 6 00 7 00 0 00 9 00 10 00 11 00 12 00
A-378
-------
Point 6
Label A: O9APP.O4 PBCB 472 21 3 Point B
c:\edax32\genesis\genspc.spc /peakgen.spc
Label B: H K
Pb
As
Point 7
Label A: O9APRO4 PBCB 472 21 3 Point 7
;:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
F-b
As
Point 8
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label A: O9APRO4 PBCB 472 21 3 Point B Label B: H K
Pb
As
00 9_00
A-379
-------
Point 9
Label A: O9APR84 P8C8 472 21 3 Point 9
;:\edax:32\genesis\genspc:-spc-/-peak:gen.spc
Label B: H K
1 mi 2 00 3_00 1 nil 5.00 6.00 7.00 8 00 9.00 in nil 11 00 12 00
Point 10
c:\edax:32\genesis\genspc:. spc-/-peakgen.spc
abel A: O9APRO4 P8C8 472 21 3 Roint 1 O Label B: H K
'^''^^^^^l-^^^
I.111! 2.00 3_00 4_00 5_00 G_00 7 00 0.00 9.00 10.00 11.00 12.1
Point 11
c:\edax32\genesis\genspc.spc-X-peakgen.spc
! 21 3 Point 1 1 Label B: H K
) I Pb K
CJ\ Ga _,._*!/ VE__ .jCd^
A-380
-------
Point 12
Label A: O9APRO4 PSCB 472 21 3 Po
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
Pb
As
A-381
-------
P8C9 - 413,154
BSE Image
S^+ W1 *t» -
*i\
m&
*^-PV^H . J* . .* .?.*.*. 'M'.!
I
Iron (Fe)
A-382
-------
Silicon
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
nt 1 Label H: l-l K
e.oo 9.00 10.00
Point 2
e:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label A: 1 3APR.O4 PBC9 41 3 154 Point 2 Label B: H K
0 I !
A i '
i i \ 'I Pb K Ti
L-£j V__Jla-^^ Vp Cd Ba MnFe
LOO 2_OO 3_OO 4_OO S_00 6 OO 7 CIO
Rb
As
8_OO 9_00 (0 00
A-383
-------
Point 3
Label A: 1 3AF-RO4
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 4
Label A: 1 3ARR.O4 RBC9 41 3 154 Roint 4
c:\edax32\genesis\genspc.spc / p ea kge n.s pc
Label B: H K
Point 5
Label A: 1 3APR04 P8C9 41 3 1 54 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
A-384
-------
Point 6
Label A: 1 3AF-RO4
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 7
Label A: 1 3ARR.O4 RBC9 41 3 154 Roint 7
c:\edax32\genesis\genspc.spc / p ea kge n.s pc
Label B: H K
Pb
As
Point 8
Label A: 1 3APR04 P8C9 41 3 1 54 Point 8
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
I '
A-385
-------
Point 9
Label A: 1 3AF-RO4
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Pb
As
1.00 2.00 3.00 -4.00 5.00 6.00 7.00
9.00 10.00
Point 10
c:\edax32\genesis\genspc.spc / peakgen.spc
Label A: 1 3ARR.O4 RBC9 41 3 154 Roint 1 O Label B: H K
1_00 2_OO 3_00 4_00 5_00 6.00 7.1
,.00 9.00 10.00
A-386
-------
P8C9 - 448, 239
BSE Image
ml^i^
L *?***»* -r "M^ -
t»
Lead (Pb)
A-387
-------
Silicon (Si)
m.
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label A: 1 3APRO4 P8C9 44G 239 Point 1 Label B: H K
Pb
As
2 00 3.00
0.00 9.00 10.00
Point 2
Label A: I 3APRO^I P8C9 4^18 239 Point
::\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
Pb
As
LOO 2.0O 3.00 4_OO
9_00 10 00
A-388
-------
Point 3
Label A: T 3AF-FUHI PBC9
239 Roint 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 4
Label A: 1 3ARR.O4 RBC9 44B 239 Roint
i:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Pb
As
Point 5
Label A: 1 3APR04 PSC9 448 239 Point 5
c:\edax32\genesis\genspc. spr^f pea kge n.s pc
Label B: H K
Cd Ca
Pb
As
A-389
-------
Point 6
Label A: T 3AF-FUHI F-BC9 A4& 239 Roint G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
j^X/vyv^^c/ c, JL
1.00 2.00 3.00 -4.00 5.00 6.00 7.00
9.00 10.00
Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
abel A: 1 3APFIOJ PBC9 448 233 Roint 7 Label B: H K
i no 2 on 3 no i on 5 no t, on 7 no a on 9 no in on
Point 8
c:\edax3Z\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APRO-4 P8C9 44B 239 Point O Label B: H K
Pb
As
1.00 2_00 3.00 4_00 5.00 G_00
00 n till 10.00
A-390
-------
Point 9
Label A: T 3AF*ROJ| PBCS 44& 233 Roint
abel I !: I I K
Mil Fe
1.00 2.00 3.00 -4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 10
c:\edax32\genesis\genspc.spc /pea kgen.spc
I Roint 1O Label B: H K
1.00 2.0O 3.00 A. DO 5.00 6. DO 7.1
:.OO 9.00 10.DO
A-391
-------
P8C9 - 451, 293
BSE Image
v M. - '*?il * >5
^/^ -.:;.,,-^f^ j>X
'.'. t'lt:^' * As iV^^O^/. >»
V-->^.^
A-392
-------
EDS Scan Images by Point
Point 1
Label A: 13APRO4 P8C9 451 293 Point 1
e d ax:3 2\g e n e s i s\g e n s p c. spc-/-peakgen_spc
Label O: H K
Pb
As
1.00 2.00
3.00 4.00
9.00 10.DO
Point 2
Label A: 1 SAPRO^I PBC9 151 293 Point 2
-:\e d o>e3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
LOO 2_00
A-393
-------
Point 3
Label A: T 3AF-FUHI F-BC9 -dBI 293 Roint 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 4
Label A: 1 3APR.O4 PBC9 451 293 Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
LOO 2.00 3_00
Point 5
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APRO-4 P8C9 151 293 Point 5 Label B: H K
A-394
-------
Point 6
Label A: T 3AF-FUHI F-BC9 -dBI 293 Roint G
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Pb
As
Point 7
Label A: 1 3APP.O4 P8C9 451 293 Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Pb
As
Point 8
Label A: 1 3APRO-4 P8C9 151 293 Point B
Label B: H K
Pb
As
A-395
-------
Point 9
Label A: T 3AF-FUHI PBC9 -dBI 293 Roint 9
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
Point 10
Label A: 1 3APR01 P8C9 4B1 293 Point 1 O
esl s\ger»spc. spc / peakgen.s pc
Label B: H K
ii^J
Point 11
Label A: 1 3APRO-1 P8C9 451 293 Point 1 1
c:\edax32\genesis\genspc.sp c / p eakgen.spc
Label B: H K
A-396
-------
P8C9 - 456, 227
BSE Image
A-397
-------
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
abel A: 1 3APRO1 P8C9 456 227 Point 1 Label B: H K
Pb
I Al | I K
V^/v<^v WvSL.
J' I Fr?
\^j^-/
Pb
As
1.00 2.00 3.00 4.00 5.00 6.00
8.00 9.00 10.00
Point 2
e:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label A: 1 3APRO4 P8C9 456 227 Point 2 Label B: H K
LOO Z 00 3.00 4.00 5_00 6.00
C 00 9_00 (0 00
A-398
-------
Point 3
Label A: 1 3APRO4 P8C9 456 227 Point 3
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Point 4
c:\e dax:3Z\gen esi s\gens pc. spc-/-pea kge n.s pc
Label A: 1 3APRO4 P8C9 156 227 Point A Label B: H K
Point 5
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label A: 1 3APRO-4 P8C9 156 227 Point 5 Label B: H K
Pb
As
A-399
-------
Point 6
Label A: T 3AF-FUHI F-BC9 -dBG ZZ7 Roint G
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
Point 7
Label A: 1 3ARR.O4 RBC9 456 ZZ7 Roint 7
i:\edax32\genesis\genspc.spc / peakgen.spc
Label B: H K
Pb
As
Point 8
Label A: 1 3APR04 PSC9 456 227 Point 8
c:\edax32\genesis\genspc. spc t pea kge n.s pc
Label B: H K
A-400
-------
Point 9
Label A: 1 3APRO4 P8C9 456 227 Point 9
;:\edax:32\genesis\genspc.spc-/-peab:gen.spc
Label B: H K
Point 10
Label A: 1 3APRO4 P8C9 456 227 Point 1 O
c:\edax32\genesis\genspc. spr^f pea kgen.spc
Label B: H K
Pb
Point 11
Label A: 1 3APRO-4 POC9 156 227 Point 1 1
c:\e dax32\gen es i s\g e ns p c. spc-/~P ea kg e n.s pc
Label B: H K
A-401
-------
Point 12
Label A: 1 3APRO4 PSC9 456 227 Point 1 2
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label B: H K
A-402
-------
P8C9 - 484, 269
BSE Image
V*
&-v:*ws
Iron (Fe)
i3&.^*U
'lite
Phosphorous(P)
*
A-403
-------
Silicon (S
EDS Scan Images by Point
Point 1
c:\e d ax3 2\g e n e s i s\g e n s p c. s p c-/-p e a kg e n. s p c
Label A: 1 3ARRO4 RGC9 484 2G9 Point 1 Label B: H K
LOO 2 00
3.00 4_00
8.00 9.00 10_00
Point 2
Label A: I 3APRO4 P8C9 4G4 269 Point 2
:\edax:32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
LOO 2 00
3.00 4.0O
i*.oo 10.00
A-404
-------
Point 3
Label A: T 3AF-RO1 F-BC9 18 1 269 Roint 3
;:\edax32\genesis\genspc.spc-/-peakge
Label B: H K
1.00 2.00 3.00 -4.00
Point 4
Label A: 1 3APR.O4 PBC9 481 269 Point 4
c:\edax32\genesis\genspc.spc /pea kgen.spc
Label B: H K
Si
Pb
As
1 00 2_00 3.00 4.00 5.00 6_00
Point 5
Label A: 1 3APRO-4 P8C9 181 269 Point 5
Label B: H K
A-405
-------
Point 6
Label A: T 3AF-RO1 F-BC9 18 4 269 Roint G
;:\edax32\genesis\genspc.spc-/-peakgen.spc
Label B: H K
"SSu^A-'^sEv
Cd Ca Ba
1.00 2.00 3.00 -4.00 5.00 6.00 7.00
9.00 10.00
Point 7
c:\edax32\genesis\genspc.spc /pea kgen.spc
abel A: 1 3APR.O4 P8C9 4B4 269 Roint 7 Label B: H K
Si
Pb
As
1.00 2.00 3.00 ^.00 5.00 6_00 7.00 8_00 9.00 10.00
Point 8
Label A: 1 3APRO-4 PGC9 481 269 Point Q
Label B: H K
1.00 2_00 3.00 1_00 5.00 6.00 7.1
i_00 9_00 10.00
A-406
-------
Point 9
Label A: 1 3APRO4 P8C9 ASH 269 Point 9
Label R: I I K
cj
1
Al 1 t Pb K Ti " pb
^,v Na^ ,V^J \P_^^___ Cd Ca Ela K?L_y V___^^__ As
1.00 2.00 3.00 4.00 5.00 6.00 7.00 0.00 9.00 10.00
Point 10
Label A: 1 3APR04 P8C9 484 2G9 Point 1 0
c:\edax32\genesis\genspc. spc-/-peakgen.spc
Label B: H K
A-407
------- |