Chemical Analysis and Aqueous Speciation Of

CHEMICAL ANALYSIS AND AQUEOUS SPECIATION OF

SURFACE WATERS AT THE HISTORIC LIGHTS CREEK

MINERAL DISTRICT, PLUMAS COUNTY, CALIFORNIA

A Thesis

Presented

to the Faculty of

California State University, Chico

In Partial Fulfillment

of the Requirements for the Degree

Master of Science

Environmental Science

Fall 2011 CHEMICAL ANALYSIS AND AQUEOUS SPECIATION OF

SURFACE WATERS AT THE HISTORIC LIGHTS CREEK

MINERAL DISTRICT, PLUMAS COUNTY, CALIFORNIA

A Thesis

Kara E. Scheitlin

Fall 2011

APPROVED BY THE DEAN OF GRADUATE STUDIES AND VICE PROVOST FOR RESEARCH:

______Eun K. Park, Ph.D.

APPROVED BY THE GRADUATE ADVISORY COMMITTEE:

______William M. Murphy, Ph.D., Chair

______David L. Brown, Ph.D.

______Stewart Oakley, Ph.D.

PUBLICATION RIGHTS

No portion of this thesis may be reprinted or reproduced in any manner unacceptable to the usual copyright restrictions without the written permission of the author.

iii

ACKNOWLEDGEMENTS

First, I would like to thank Dr. William Murphy, who is not only the best advisor and professor that I could ask for, but also a wonderful human being. I feel incredibly lucky to have had him guide me through this research and graduate program. I would also like to express my gratitude to Dr. David Brown, and Dr. Stewart Oakley for their time, effort, and mostly patience.

I would also like to express my appreciation and gratitude to my family, who

has supported me through everything. I feel thankful for you every day.

Also, thank you to Norman Lamb and Robert Wetzel, who enthusiastically

and patiently assisted with my research. My study would have been impossible without

them, and I sincerely appreciate the time and effort they both dedicated to my graduate

work.

I would like to thank Nevoro Inc. for partially funding this research and taking

an interest in the environmental aspects of their operations.

I would like to express my gratitude to the California State University, Chico

College of Natural Sciences for partially funding this research, and providing a fantastic

opportunity for education.

Lastly, I would like to thank my Dad, Ani, and her friends Panda and MoMo

for being great helpers during my field sampling for this research.

TABLE OF CONTENTS

PAGE

Publication Rights ...... iii

Acknowledgements ...... iv

List of Tables ...... vii

List of Figures ...... viii

List of Symbols and Nomenclature...... xi

Abstract ...... xv

CHAPTER

I. Introduction ...... 1

Statement of the Problem ...... 1 Purpose of the Study ...... 7 Definitions...... 7 Limitations of the Study...... 10

II. Literature Review ...... 12

General Principles and Observations ...... 12 Specific Principles and Observations...... 26 Existing Data ...... 34

III. Methodology ...... 40

Introduction ...... 40 Overall Site Description ...... 40 Field Activities and Procedures ...... 50 Laboratory Analyses ...... 64 EQ3NR Aqueous Speciation...... 68

CHAPTER PAGE

IV. Findings and Results ...... 74

Introduction ...... 74 Presentation of the Findings...... 74 Hypothesis...... 108 Comments on Overall Results ...... 108

V. Summary, Conclusions, and Recommendations...... 111

Introduction ...... 111 Research Questions and Hypothesis ...... 111 Conclusions Relevant to Research Questions ...... 112 Limitations of the Study Design and Procedures ...... 114 Future Research and Recommendations ...... 115

References Cited ...... 117

Appendices

A. Laboratory Results ...... 132 B. EQ3NR Output – MNWAT01F ...... 162 C. EQ3NR Output – MNWAT07F ...... 172

LIST OF TABLES

TABLE PAGE

1. Monitoring Locations within the Moonlight Project ...... 51

2. Monitoring Locations Outside of the Moonlight Project ...... 52

3. Activation Laboratories Trace Metals Code 6 Analysis Analyte Symbols ...... 65

4. Activation Laboratories Anion Code 6B and 6C Analyses ...... 66

5. Temperature Data, October 2008 through May 2009 (˚C) ...... 77

6. pH Data, October 2008 through May 2009 ...... 79

7. Electrical Conductivity Data, October 2008 through May 2009 (µS/cm) ...... 81

8. Dissolved Oxygen Data, October 2008 through May 2009 (Percent Saturated) ...... 83

9. Eh Data, April through May 2009 (mV) ...... 85

10. EPA Drinking Water MCL, SMCL, or TT Action Level for Analyzed Constituents ...... 87

11. Measured Major Anion Concentrations in MNWAT16 (Soda Creek) and MNWAT13 (Field Duplicate) ...... 88

vii

LIST OF FIGURES

FIGURE PAGE

1. Waste rock and ruins of the Superior Mill at the Superior Mine ...... 2

2. Mine tailings along the embankment of the lower Lights Creek within the Moonlight Project ...... 3

3. California State University, Chico geology students touring the No. 5 level of the Superior Mine in 2008 ...... 4

4. Water emerging from the Engels Mine No. 10 level (monitoring location MNWAT09) ...... 5

5. A portion of the facilities constructed to remediate AMD at Iron Mountain Mine in Shasta County, California ...... 16

6. Typical sources of contamination from mining ...... 18

7. Transport pathways for contaminants in a hypothetical tailings pile ...... 19

8. Hypothetical supergene enrichment crosssection ...... 22

9. The earliest known photo of Engels Lower Camp along Lights Creek, 1905...... 27

10. Smelter under construction in 1910 ...... 29

11. The first mill in the United States to use only the flotation process to concentrate its copper ore ...... 30

12. Superior Electric Railroad connecting the No. 10 Level of the Engels Mine with the Superior Mill ...... 31

13. Engelmine, Lower Camp, 1923 ...... 32

14. The 108 foot high steel headframe over the vertical three compartment Superior shaft was built in 1917 ...... 33

viii

FIGURE PAGE

15. The fourth level of Engels Mine in 1915 ...... 34

16. Lights Creek running through Lights Canyon and to the Indian Valley ...... 42

17. Bornite (in the No. 5 level of the Superior Mine) ...... 45

18. The flotation cells in the Engels Mill at Upper Camp ...... 48

19. Sampling location MNWAT04 (downstream side of bridge), Lights Creek at Moonlight Valley Road fish ladder...... 55

20. Orion® 5Star Portable meter being used to measure field parameters in waters emerging from the remediated Engels Mine adit, monitoring location MNWAT11 ...... 56

21. Waters emerging from the remediated Walker Mine adit, monitoring location MNWAT14 ...... 57

22. Temperature Data, October 2008 through May 2009 ...... 78

23. pH Data, October 2008 through May 2009 ...... 80

24. Electrical Conductivity Data, October 2008 through May 2009...... 82

25. Dissolved Oxygen Data, October 2008 through May 2009 ...... 84

26. Eh, April through May 2009 ...... 86

27. Measured elemental concentrations, 0 – 16 µg/L MNWAT 16 (Soda Creek) v. MNWAT13 (field duplicate) ...... 89

28. Measured elemental concentrations, 0 – 20,000 µg/L MN WAT16 (Soda Creek) v. MNWAT13 (field duplicate) ...... 90

29. Measured elemental concentrations, 0 – 45,000 µ g/L MN WAT16 (Soda Creek) v. MNWAT13 (field duplicate) ...... 91

30. Copper v. arsenic concentration in unfiltered water samples ...... 95

FIGURE PAGE

31. Copper v. arsenic concentration in filtered water samples ...... 96

32. Quantitatively diluted v. undiluted concentration of Code 6 metals in water samples, 0 40,000 µg/L ...... 97

33. Quantitatively diluted v. undiluted concentration of Code 6 metals in water samples, 0 200 µg/L ...... 98

34. Quantitatively diluted v. undiluted concentration of Code 6 metals in water samples, 0 25 µg/L ...... 99

35. Unfiltered v. Filtered Concentrations, October 2008 through May 2009, 0 – 2,000 µg/L ...... 100

36. Unfiltered v. Filtered Concentrations, October 2008 through May 2009, 0 – 45,000 µg/L ...... 101

37. Malachite (shown in the No. 5 Level of the Superior Mine) ...... 106

LIST OF SYMBOLS AND NOMENCLATURE

ABBREVIATION SYMBOL/NOMENCLATURE

i ...... chemical potential of gas i

...... standard chemical potential of gas i io ...... fugacity of the standard state of i

...... the fugacity of i °C ...... degrees Celcius

A ...... thermodynamic affinity

Ah ...... redox affinity

ai or [ i] ...... activity of product of reactant i

AMD ...... acid mine drainage

atm...... atmospheres (pressure unit)

b...... moles of product

Bureau ...... California State Mining Bureau

cal ...... calorie

CGS ...... California Geological Survey

d...... moles of H + ions

DO ...... dissolved oxygen

E0 ...... standard potential of a redox reaction, in volts

EC ...... electrical conductivity

ABBREVIATION SYMBOL/NOMENCLATURE

Eh ...... redox potential of aqueous solution, V

EIS...... Environmental Impact Statement

EPA ...... United States Environmental Protection Agency

F ...... Faraday constant, 23.06 kcal/V

IC...... ion chromatography

ICPMS ...... inductively coupled plasma – mass spectrometry

IEC ...... International Electrochemical Commission

IOCG ...... Ironoxide copper gold

ISO ...... International Organization for Standardization

K ...... degrees Kelvin, or elemental symbol for potassium

K ...... thermodynamic equilibrium constant

kg...... kilogram

km ...... kilometers

m ...... meters

MCL ...... maximum contaminant level

MDL ...... method detection limit

mi ...... molar concentration of a species i in a solution

mol ...... moles, 6.022x10 23 atoms or molecules

n...... number of electrons released / number of electrons in half reaction

N.A...... not applicable

N.D...... not determined

xii

ABBREVIATION SYMBOL/NOMENCLATURE

NELAC ...... National Environmental Laboratory Accreditation Conference

NIST ...... National Institute of Standards and Technology

no...... number

NPL ...... National Priorities List

ORP ...... oxidationreduction potential

oz ...... ounces

Q ...... the activity product of a reaction

QA ...... quality assurance

QC ...... quality control

R ...... the gas constant, 1.98726 cal/molK

RF ...... radio frequency

SCC ...... Standards Council of Canada

SHE ...... standard hydrogen electrode

SI ...... saturation index

SMCL ...... secondary maximum contaminant level

T ...... temperature

u...... moles of reactant

U ...... reactant

V ...... product

V ...... volts

w ...... moles of water

xiii

ABBREVIATION SYMBOL/NOMENCLATURE

zi ...... the electrical charge of a species i

γi ...... activity coefficient of a species i

0 G R ...... Gibbs free energy

xiv

ABSTRACT

CHEMICAL ANALYSIS AND AQUEOUS SPECIATION OF

SURFACE WATERS AT THE HISTORIC LIGHTS CREEK

MINERAL DISTRICT, PLUMAS COUNTY, CALIFORNIA

Master of Science in Environmental Science

California State University, Chico

Fall 2011

The Lights Creek Mineral District in Plumas County, California, is a site of historic mining for copper, gold, and silver. An area of the Lights Creek Mineral District called the Moonlight Project is a site of current exploration for copper in oxide dominated ores. Waste rock and mine tailings are deposited along the banks of Lights

Creek, and water drains into Lights Creek from abandoned adits within the Moonlight

Project.

Effects of historic mining on surface water quality within the Lights Creek

Mineral District were examined using field and laboratory analyses. Field data measurements included temperature, pH, redox potential, dissolved oxygen, and electrical conductivity. Commercial laboratory analyses provided data for major and trace element concentrations in filtered and unfiltered samples. Equilibrium aqueous speciation

xv models were generated to evaluate controls on water chemistry for samples taken within the Moonlight Project, and to develop a ‘signature’ of mineaffected waters.

Results demonstrate that measured pH and concentrations of dissolved metals within the Moonlight Project are typical of unaffected surface waters except for water emerging from adits. Although adit water has near neutral pH, dissolved oxygen is low and metal concentrations are elevated compared to background (upstream) samples and samples from Lights Creek.

Analyses and models for adit water are interpreted to indicate that the discharge interacts with sulfide minerals (which are observed in core samples). Reactions with aluminosilicates and oxygen of atmospheric origin appear to have led to supersaturation with respect to aluminum oxyhydroxides, and metastable aqueous manganese and selenium.

xvi

CHAPTER I

INTRODUCTION

Statement of the Problem

The Lights Creek Mineral District is located at the northern end of the Walker

Lane Mineral Belt in the Sierra Nevada physiographic province, in Plumas County,

California. The Lights Creek Mineral District is a site of historic mining for copper, gold, and silver, and a site of current exploration for copper in oxidedominated ore. The

Plumas County portion of the Walker Lane Mineral Belt extends 29 kilometers (km) in an approximately south 20° east direction from the Superior and Engels mines, which are part of the historic Moonlight Project (Lamb, 1995), to the historic Walker Mine (Smith,

1970a).

Waste rock and mine tailings occur along the banks of Lights Creek within the

Moonlight Project, and water drains into Lights Creek from abandoned adits at the site.

Mine tailings piles and waste rock debris are found in multiple locations at the Moonlight

Project Site including approximately 300 thousand tons of tailings at the ‘Upper Tailings pile’ at the Engels Mine, and approximately 2 million tons of tailings at the ‘midsand dam’ (Darcel, 2008). Photographs of waste rock surrounding the ruins of the historic

Superior Mill and tailings along the Lights Creek are shown in Figure 1 and Figure 2, respectively.

In addition to exploratory borings driven for exploration of ore at the

Moonlight Project site, channel samples of both of the major tailings areas within the 1 2

Moonlight Project have been collected to determine the feasibility of exploiting copper from the oxide copper remaining in the tailings (Darcel, 2008).

Figure 1. Waste rock and ruins of the Superior Mill at the Superior Mine.

Interpretations of the mineralization at the Moonlight Project site vary (e.g.,

Smith, 1970a; MacFarlane, 1981; Storey, 1978; and Stephens, 2011). However, the portion of the Lights Creek Mineral District within the Moonlight Project appears to be somewhat unique as far as the oxide dominated ores that characterize portions of the upper subsurface of the mined areas.

In contrast to the Moonlight Project’s Superior and Eng els Mines (shown in

Figure 3 and Figure 4 , respectively), th e proximal Walker Mine is known for extensive

3 acid mine drainage (AMD) resulting from historic mining in the sulfide dominated ores found in that portion of the Lights Creek Mineral District.

Figure 2. Mine tailings along the embankment of the lower Lights Creek within the Moonlight Project.

Remediation activities to prevent AMD release into surface waters flowing from the Walker Mine site began in the 1980s. Remedia tion methods used at the Walker

Mine include construction of a concrete adit seal, and canals to cap ture and redirect runoff to onsite ponds . As late as 2004, the Office of Mine Reclamation (OMR) prepared plans and reports for an investigation on a pit ba ckfilling and channel modification project for the Walker Mine s ite (OMR, 2010).

Much effort has been devoted to developing methods that can be used to determine the extent to which mining activities impact water quality at historic mine or

4 mine waste dis posal sites, especially with respect to metal and metalloid release from

AMD (Teaf et al., 2006 ).

Figure 3. California State University, Chico geology students touring the No. 5 level of the Superior Mine in 2008.

Approaches to estimate background (natural) environmental conditions at mining sites include mass balance with age determination of weathered material, mass balance on oxygen flux, statistical analyses, historical and anecdotal data, stable isotopes

(hydrogen, oxyge n, sulfur, and carbon), sediment sampling, remote analogs, proximal

5 analogs, and geochemical modeling (Alpers and Nordstrom, 2000). To examine the effects of historic mining within the Moonlight Project and Lights Creek Mineral District, surface water samp les were collected throughout the Moonlight Project site and at the

Walker Mine site.

Figure 4. Water emerging from the Engels Mine No. 10 level (monitoring location MNWAT09).

Sampling activities took place from November 20 08 to May 2009. Field data collected from November 2008 through May 2009 included temperature, pH, redox potential (Eh), dissolved oxygen (DO), and electrical conductivity (EC). Commercial laboratory analyses provided data for major and trace element conce ntrations in filtered and unfiltered samples.

While all of the approaches for estimating background environmental

conditions at mining sites presented by Alpers and Nordstrom (2000) have strengths and

limitations as they pertain to the Moonlight Project and greater Lights Creek Mineral

District, aqueous speciation modeling using the chemical analysis data was the principal

means of data interpretation in this research.

Analysis of analytical data and speciation model outputs provides an estimate

of the water quality degradation that may have previously, or continues to take place

within the Moonlight Project. Analysis also allows characterization of the evolving mine

water as it exits the subsurface environment and is exposed to atmospheric conditions.

This effectively provides a ‘signature’ of the chemical characteristics of the surface

water, transitioning groundwater (from the subsurface to oxidizing atmospheric

conditions), and the water quality within the Moonlight Project and greater Lights Creek

Mineral District. Alpers and Nordstrom’s (2000) proximal analog method of establishing background water quality was analyzed for feasibility as a secondary approach to

evaluate the Moonlight Project site. Samples from the Walker Mine site were collected to

determine if existing Walker Mine data could aid in characterization of background

conditions at the Moonlight Project site.

Much literature exists regarding AMD generation and effects on surface

waters at sulfidedominated sites (e.g., Walker Mine). In contrast, there is an absence of

literature that provides characterization of environmental effects of mining on surface

waters in mined areas that are oxide dominated (e.g., the Moonlight Project).

A description of surface water chemical conditions at locations within the

Lights Creek District are provided in this report. Data for trace and major element

concentrations and other water quality parameters is also analyzed herein.

Purpose of the Study

This research is a step in establishing the various controls on surface water

quality at the Moonlight Project, effectively developing a ‘signature’ of affected and

unaffected surface waters at this, and similar sites. These controls may include natural

systems such as mineral deposits (background chemical conditions), waterrock

interactions, and historical mining activities and products.

Another purpose of this research is to determine the extent to which historic

mining may affect surface waters in the Moonlight Project area. This objective was

achieved through evaluation of water quality hazards that may be indicators of possible

negative environmental impacts of the Moonlight Project.

Definitions

“Background environmental conditions,” as used herein, refers to the best available estimate of premining conditions at the Moonlight Project site. For the purposes of this study, the best available estimate for background environmental conditions for surface waters is taken to be upstream samples. For the land surface, the background (native) condition is considered to be areas that were not used for mining or the deposition of mining byproducts (e.g., waste rock and tailings)

“Bioaccumulation” is the “increase of concentrations of slowly oxidized or excreted substances in organisms” (Pfafflin et al., 2008, p. 19).

“Grade” is an empirical term describing the amount of a metal in an ore body, typically expressed as a percentage. A “cutoff grade” is the minimum percentage of a metal in a particular ore body that is economical to extract, based on technology, metallurgy, cutoff grade, economics, marketing, legal, environmental, social, and governmental issues.

“Heap leaching” describes a process used to extract metals from lowgrade ores by creating a pile (heap) of ore, which is soaked with a formulated chemical solution that dissolves and mobilizes target metals within the ore effectively leaching the valuable constituent from the ore (Burkhalter et al., 1999).

Laboratory “method detection limit” (MDL) is the smallest quantity of a constituent contained in a medium (e.g., copper in water) that can be detected using a specific laboratory method within a designated confidence limit. For example, if copper is present in aqueous solution at 0.1µg/L, but the MDL of the method being used to measure the copper concentration is 0.2µg/L, the copper concentration is below the

MDL, and would typically be expressed as “nondetect” (ND, or not present above the

MDL), or as “<0.2µg/L”.

A “maximum contaminant level” (MCL), is an enforceable standard defined as “the highest level of a contaminant that is allowed in drinking water” (EPA, 2009).

A “secondary maximum contaminant level” (SMCL) is a nonenforcable guideline that applies to “contaminants that may cause cosmetic effects (such as skin or tooth discoloration) or aesthetic effects (such as taste, odor, or color) in drinking water”

(EPA, 2009).

A “treatment technique” (TT) is a “required process intended to reduce the

level of a contaminant in drinking water” (EPA, 2009).

The “standard state” of a solute in solution is the defined state of a solute

demonstrating infinitely dilute solution behavior at the standard molality, concentration,

or pressure (Mills et al., 1993).

One “metric ton” is equal to 1,000 kg, or approximately 2,205 pounds. One

“ton” is equal to 2000 pounds.

“Ore” describes any host rock, mineral, or aggregate of minerals, containing

an economically valuable (and economically extractable) constituent, often metal.

Ore bodies are often classified within the two broad categories “mineral

resource,” or “mineral reserve” depending on the degree of economic and technical

evaluation of the ore that has occurred. Estimation of mineral reserves are dependent on

numerous factors, including technology, metallurgy, cutoff grade, economics, marketing,

legal, environmental, social, and governmental. Estimation of mineral resources is

generally carried out using geological data. Resources can become reserves, and reserves

can become resources (Vaughan and Felderhof, 2002).

The “vadose zone” or “unsaturated zone” is defined as one of two zones of

water occurring underground (the other is the groundwater aquifer zone). The vadose

zone occurs below the land surface and above the uppermost aquifer zone, and contains both water and air (Heath, 1983). Within the vadose zone, atmospheric oxygen leads to

oxidation of primary sulfides. The depth to which oxidation may occur is dependent on

the subsurface characteristics (e.g., porosity and chemical makeup).This oxidation causes

acid generation and dissolution of metals, which migrate vertically downward and

10 precipitate at depth below the groundwater table, resulting in enriched zones of metals.

This process is known as “supergene enrichment.”

“Waste rock” is a term used to identify any rocks, minerals, or complexes of

minerals, that are displaced during mining, but do not contain an economically valuable

grade of metal (or other constituent).

Water sample locations used in this study are distinguished using the format

“MNWATYYZ,” where “YY” is a variable representing the monitoring location

identification number (01 through 18. “Z” is a suffix that represents if the sample was

either quantitatively diluted (“X”), or field filtered (“F”). Where no suffix is used, the

sample is an undiluted, unfiltered sample.

Limitations of the Study

The field and laboratory analyses and aqueous speciation modeling conducted

for this study are useful tools for advancement of the objective of determining the effects

on surface water quality of mining activities in Moonlight Project or other mining sites

with similarly oxidebased ores. However, characterization of mine waste should be performed by “integrating results from a variety of characterization techniques over time,

rather than a single test or a onetime series of tests” (Maest et al., 2005, p. i). The degree

of confidence in models is “severely limited in part because the models are so complex…

[and]…should always be reevaluated over time at mines sites and compared to site

specific water quality information as it becomes available” (Maest et al., 2005, p. x).

The results of this study demonstrate that mining of ores such as those found

at the Moonlight Project appear to generate minimal AMD. However, further research

would be required to characterize the site to a level that would be sufficient to conclude

that future mining activities would have little to no acid generating potential. The extent,

depth, and location of the oxidedominated ore would need to be well described.

The multitude of other environmental factors that often affect mining sites must be examined. Such effects include, but are not limited to, ecological (e.g., animals, plants), hydrological (e.g., groundwater contamination), and aesthetic (e.g., waste rock and tailings piles), although these issues are not always mutually exclusive.

CHAPTER II

LITERATURE REVIEW

General Principles and Observations

Background

In 1848, James Marshall discovered gold at Sutter's Sawmill in Coloma,

California, on the South Fork of the American River. Since that time, extensive research and exploration for metal mining in California and the western United States has been conducted, and increasingly documented (CGSa, 2007). The gold rush that began as a result of Marshall’s discovery spurred the appointment of John B. Trask as the first

Honorary State Geologist for California in 1851. California began budgeting for a state geological survey in 1860, and in 1880 the California State Mining Bureau (Bureau) was formally established as a response to the increasing demand for information regarding the gold mining industry in the state. The Bureau’s primary stated goal at the time was “to encourage the development of the great mineral resources of California” (Socolow, 1988;

CGSa, 2007, electronic).

Since its inception in 1880, the Bureau has undergone several organizational and name changes, and currently exists as the California Geological Survey (CGS) under the State of California Department of Conservation. While the CGS still carries out many of the original functions of the Bureau, and is still charged with overseeing the mineral resources that exist in the state, its focus has expanded to implementing new technology to enhance the safety of the state (CGSb, 2007). 12 13

“Gold in greater or less quantity is found in almost all parts of California but

the principal deposits… are on the west slope of the Sierra Nevada” (Hittell, 1898, p.

548). Hittel (1898) further explains that, in the Sierra Nevada, gold tends to occur on the

west slope, silver tends to occur on the eastern slopes, and mercury is found in the

Coastal Range from Santa Barbara to Shasta.

Although copper was first discovered in California in 1840 near what is now

Los Angeles, the first important copper producer in the state was not discovered until

1860, when the Napoleon Mine was discovered in Copperopolis, Calaveras County

(Stevens and Weed, 1909). A copper boom began in California in 1862 and 1863, when production was approximately 2 million pounds statewide in 1864. However, the copper

industry in California was practically nonexistent after 1868, until Iron Mountain Mine

(in the Shasta District) became an important producer in 1896. The peak production of

copper in California occurred in 1901, when 34.9 million pounds of copper was produced. Of the 1901 yield, 30.9 million pounds of the 1901 yield was produced at Iron

Mountain Mine in Shasta County (Jared et al., 1908). As of the early 1900s, the three primary copper producing districts in California were Copperopolis, Plumas, and Shasta.

By 1920, the approximately twenty mines and prospects in the Plumas region were producing a most of the copper in the state, although the Walker and Engels mines were

the principal two of these producers during this period (Young, 1921).

Mining booms occurring in California have created economic incentives for

mining prospectors, and those whose business depends on exploitation of mineral

resources. This interest in mineral resources in California has also been beneficial to

researchers in the earth sciences area, who often receive funding to perform the research

required by prospectors.

Since the early days of mining in California, mineral extraction methods have

substantially evolved. The primary methods currently used for mining metals are

excavation, strip mining, open pit mining, and underground mining, depending on the

characteristics and physical structure and value of ore. Processing of rock is typically based on a predetermined cutoff metal grade deemed to be profitable. Rock containing

highergrade metal is processed to extract the ore, and rock with metal content below a predetermined cutoff grade is discarded as waste rock, especially in open pit and

underground mining operations. Each processing step generates a waste stream (Blowes

et al., 2003). For example “production of 1 metric ton of copper typically requires the

excavation and processing of 100 metric tons of rock” (Blowes et al., 2003, p. 151).

Production of copper worldwide in 2003 is estimated to be 1314 million

metric tons, with approximately onethird originating from Chile. The United States,

Australia, and Indonesia are also important producers (Blowes et al., 2003).

While vast amounts of private and public financial resources have been, and

continue to be, dedicated to fund geological and mineralogical research efforts in the

hopes of discovery of profitable mineral resources, much focus in the area of mining

research has necessarily shifted. The shift began with the 1883 case Woodruff v. North

Bloomfield Gravel Mining Company, in which the plaintiff alleged that the North

Bloomfield Gravel Mining Company dumped tailings from hydraulic mining operations

at the Malakoff Mine in North Bloomfield, California, into the Yuba River. The Malakoff

mine was the largest hydraulic mining operation in existence at the time, and Woodruff

alleged that the tailings and large volumes of water (all generated at the Malakoff Mining

operation and transported downstream), destroyed his farmlands. Historical records state

that the Malakoff mining operation “polluted streams, killed fish, damaged agricultural property, and caused repeated flooding in the towns of Marysville and Yuba City” (OAC,

2006, electronic). In 1883, Woodruff, who was an owner of impacted farmlands, took the

North Bloomfield Gravel Mining Company to Federal Court. Federal Judge Lorenzo

Sawyer handed down the 1884 verdict, known as the ‘Sawyer Decision,’ which

effectively banned hydraulic mining. The Sawyer Decision is considered to be the first

environmental law enacted in the United States (California State Parks, 2010).

As the understanding of the importance of environmental conservation and the

consequences of human and ecological health has grown, deleterious effects of historic

mining in California (and internationally) have become apparent. Environmental research

has led to widespread regulatory action, remediation, and billions of dollars spent by private industry and government to remediate contaminated mining sites (e.g., Walker

Mine and Iron Mountain Mine). Part of the remediation facilities at Iron Mountain Mine

are shown in Figure 5. This research has also led to increased efforts to create a balance between minimization of environmental impacts while continuing to provide essential

mineral resources. According to the EPA Abandoned Mine Land Team, in the United

States alone, the cost of remediation at historic mine sites designated on the National

Priorities List (NPL) is around 20 billion dollars (Maest et al., 2005).

Current federal regulations dictate that mining project administrators must

submit an Environmental Impact Statement (EIS) and other applicable documents prior to

commencement of mining operations.

Figure 5. A portion of the facilities constructed to remediate AMD at Iron Mountain Mine in Shasta County, California.

These docume nts must evaluate the proposed mining projects’ propensity for affecting surface and ground waters and the environment during and following mining operations . These assessments are made using a variety of field, laboratory, and modeling approaches, and are evaluated by regulators who examine if they are sufficient to

“guarantee that future environmental liability is adequately addressed” (Maest et al.,

2005).

Contamination at Mine Sites

Much research on the subject of the environmental effects of mining ha s been devoted to describing the consequences of mining and mine waste on surface water and groundwater. Mine sites are typi cally at higher elevations in drainage area s where bed rock tend to be closer to th e surface. Mining activities in the high elevation areas are

17 prone to affecting downstream surface water and ground water (Teaf et al., 2006). Many

studies have addressed soil and water pollution problems resulting from historic mining

activities in the western United States (e.g., Young and Clark, 1978; Graf et al., 1991;

Rhan et al., 1996; and Rösner, 1998). Such studies provide evidence of the wide ranging

and severe environmental and ecological effects of mining, primarily as a result of acid

generation and the resulting mobilization of heavy metals such as arsenic, cadmium, iron,

lead, copper, vanadium, and zinc in surface and ground water. The most common sources

of water contamination and AMD at mine sites are waste rock, tailings, ore stockpiles,

heap leach piles, dump leach piles, and the walls of open pits and underground workings

(e.g., adits, shafts, cuts). Heavy metal concentrations and pH are often the most important

indications of environmental degradation due to historic mines. A number of these

sources of water contamination at mine sites are depicted in Figure 6, and transport pathways for contamination in a typical tailings pile are depicted in Figure 7. These

sources of water contamination at mine sites can leach naturally occurring constituents

(e.g., metals and sulfate minerals), and can also leach constituents introduced during

mining processing (e.g., flotation or heap leaching chemicals).

The most severe environmental impact generally associated with mining and

mine waste disposal sites is AMD. AMD occurs as a result of the breakdown of sulfide

minerals (primarily FeS 2 [pyrite]) contained in waste rock piles, underground workings, pits, leach pads, tailings, or other mining waste or mined hard rocks when they are

exposed to water and air (Blowes et al., 2003). AMD can also occur in any situation that

sulfides are exposed to the atmosphere (e.g., during road construction or other civil

engineering projects, or during mining of coal containing sulfides).

Figure 6. Typical sources of contamination from mining. Adapted with permission from Maest, A.S., Kuipers, J.R., Travers, C.L., and Atkins, D.A., 2005, Predicting Water Quality at Hardrock Mines: Methods and Models, Uncertainties, and StateoftheArt: Boulder, Colorado and Butte, Montana, Kuipers & Associates, Buka Environmental, and Stratus Consulting, 77 p.

Blowes et al. (2003) describe pyrite as being the most important sulfide

mineral associated with copper ores. Equations showing oxidation of pyrite by

atmospheric oxygen and the release of ferrous iron and acid (1), oxidation of ferrous iron

to ferric iron (2), ferric iron oxyhydroxide precipitation and acid release (3) are shown below. The sum of equations (1) through (3) is shown in the overall complete reaction of pyrite oxidation and release of sulfuric acid (4) (Hadley and Snow, 1974; Nordstrom,

1982; Todd and Reddick, 1997; and Blowes et al., 2003):

2+ 2 + FeS 2 (s) + 3.5O 2 + H 2O → Fe + 2SO 4 + 2H ; (1)

2+ + 3+ Fe + 0.25O 2 + H ↔ Fe + 0.5H 2O; (2)

3+ + Fe + 3H 2O ↔ Fe(OH) 3 + 3H ; (3) and

2 + FeS 2 (s) + 3.75O 2(aq) + 3.5H 2O (aq) → 2SO 4 + Fe(OH) 3 (s) + 4H (aq) . (4)

Figure 7. Transport pathways for contaminants in a hypothetical tailings pile. Adapted with permission from Maest, A.S., Kuipers, J.R., Travers, C.L., and Atkins, D.A., 2005, Predicting Water Quality at Hardrock Mines: Methods and Models, Uncertainties, and StateoftheArt: Boulder, Colorado and Butte, Montana, Kuipers & Associates, Buka Environmental, and Stratus Consulting, 77 p.

The AMD reactions (1) through (4) can occur in either anoxic or oxic systems, although oxidants differ in each situation. The simplified process described in (1) through

(4) involve electrochemical, biological, and chemical reactions that can follow a variety of pathways (Blowes et al., 2003). The precipitation of ferric iron as ferric hydroxide (3) is the cause of the typical reddish brown color of sediments contaminated by AMD (Todd

and Reddick, 1997). Within (1), pyrite oxidation by atmospheric oxygen produces one

2+ 2 + mole of Fe , two moles of SO 4 , and two moles of H for every mole of pyrite oxidized.

Within (4), the overall reaction of pyrite oxidation releases 4 moles of H + for every mole of pyrite oxidized (Blowes et al., 2003).

The USDA (1993) estimates that on United States Forest Service lands, there are between 20,000 and 50,000 mines releasing acidic drainage (Blowes et al., 2003).

Costs for remediating mine wastes are estimated to total in the tens of billions of dollars

(Blowes et al., 2003; Feasby et al., 1991). AMD dissolves metals, metalloids, or other constituents present in surrounding hard rock, and may be washed eventually to drainages or water bodies through runoff or other sources of water proximal to the acid generating site. The effects of AMD on the surrounding ecosystem can be devastating, since AMD potentially has deleterious effects on fish, plants, wildlife, and water supplies. Since mine waste can remain in place for centuries after mining operations have ended, it can continue to affect the surrounding waterways indefinitely (Maest et al., 2005).

Underground mining permanently alters underground rock permeability, so it is unlikely that groundwater conditions adversely affected by AMD will recover to their previous condition in a human time scale (Teaf et. al. 2006).

The Iron Mountain Mine in Northern California is considered to be one of the most toxic waste sites in the United States, due to the extensive AMD originating at the site. Mining at Iron Mountain Mine began in 1860 and continued through 1963. Since

1940, mining adits and other workings, waste rock and mine tailings piles, and an open pit mine located within the 4,400 acre Iron Mountain Mine site have been known to release large amounts of acid and leached metals (mainly copper, zinc, and cadmium)

into the surrounding watershed (USDOJ, 2000). The AMD at Iron Mountain Mine has

resulted in severe environmental consequences including fish kills and contamination of

drinking water supplies (EPA, 2010). The EPA promulgated regulations that required

state of the art treatment systems to be implemented at the Iron Mountain Mine site,

which are likely to be required for water treatment in perpetuity. According to the United

States Department of Justice (2000), site cleanup costs at the Iron Mountain Mine site

could eventually approach one billion dollars.

Another example of a historic site with extensive AMD problems is the

Walker Mine (proximal to the Moonlight Project). AMD generated at Walker Mine led to extensive fish kills and ecosystem damage kilometers away from Walker Mine site.

Surface water and mine waste exposed to oxidizing conditions near the

Earth’s surface often do not reflect geological and hydrogeochemical conditions at depth.

Supergene enrichment of copper porphyry deposits occurs when primary sulfides are oxidized on exposure to near surface oxidizing conditions, which results in acid generation and dissolution of heavy metals. The acidic drainage and dissolved heavy metals are transported downward in recharge water and through permeable routes (e.g., fractures or porous regions) within the vadose zone. Dissolved metals are precipitated at depth as high grade secondary oxides, carbonates, or under deeper reducing conditions, as sulfides (Ingebritsen and Sanford, 2006). Figure 8 shows a hypothetical cross section at a site where supergene enrichment has occurred. It shows the typical vadose zone consisting of mostly oxidized material, and a zone below the water table containing unoxidized sulfide minerals.

Figure 8. Hypothetical supergene enrichment crosssection.

In addition to equations (1) through (4), generalized chemical equations showing oxidation and leaching of pyrite, the first step in the supergene enrichment process are (5) and (6) (Guilbert and Park, 2007, p. 802805):

2+ 2 + 2CuFeS 2 + 8.5O2 + 2H 2O → Fe 2O3 + 2Cu + 4SO 4 + 4H ; (5) and

2CuFeS 2 + 8Fe 2(SO 4)3 +8H 2O → CuSO 4 (aq) + 17FeSO 4 + 8H2SO 4. (6)

During the precipitation in the reducing zones at depth, copper from the copper sulfide minerals replaces the iron and precipitates (7) (Guilbert and Park, 2007, p. 815):

2+ 2 2+ + 2 5FeS 2 + 14Cu + 14SO 4 +12H2O → Cu 2S + 5Fe + 24H + 17SO 4 . (7)

The unoxidized sulfide material in the reducing environment that occurs below the water

table may be an environmental issue if it is unearthed in a mining operation, since

sulfides exposed to atmospheric conditions produce AMD. The possibility of supergene

enrichment at the site was discussed in personal communications with the Moonlight

Project Geologist at the time of this study (Rob Wetzel, a registered Professional

Geologist in the State of California). He indicated that cores taken throughout the

Moonlight Project have not demonstrated any of the signatures of supergene enrichment

(e.g., a zone of secondary enrichment). The apparent absence of supergene enrichment

could be a result of many factors, such as the steep terrain that characterize much of the

Moonlight Project, since it may minimize penetration of water into the subsurface during

runoff.

Predicting Water Quality at Mines

Mine drainage condition predictions can be complicated by many factors including dissolution of minerals in mine wastes, and secondary reactions among gases, solutes, and solids, and the biological species existing within waters. Surface areas of minerals that are prone to reactions are often difficult to quantify, and reaction rates of species in complex systems are not well defined. On a larger scale, mining and processing methods, geology, climate, hydrology, and waste management may

complicate predictions (Maest et al., 2005). There is uncertainty in all methods of predicting water quality at historic mine sites (Maest et al., 2005). Such uncertainty is a result of “inadequate or inaccurate conceptual models, hydrologic and geochemical characterization data, and input data to hydrogeochemical models” (Maest et al., 2005).

However, “geochemical characterization techniques can provide predictive information

on mine waste drainage quality that is beneficial to the environmentally sound

management of mine wastes” (Maest et al., 2005, p. ix).

Thermodynamic equilibrium modeling of aqueous chemicals has been

conducted at least since the 1930s, when Pourbaix conducted the first such activities

(Pourbaix, 1939). Modern geochemical speciation was first presented in the 1965 work

“Solutions, Minerals, and Equilibria” by Garrels and Christ.

The first reaction path modeling computer code was developed by Helgeson

(a student of Garrels) in the 1960s (Helgeson, 1968; Helgeson et al., 1970 and 1984;

Wolery, 1992a). A variety of programs that are used to model hydrogeochemical processes are currently available and can be used to evaluate aqueous speciation and

waterrockgas interactions. These programs function by calculating complex chemical processes based on laboratoryderived constants and calculations of thermodynamic and

kinetic potentials. Such programs include (but are not limited to) PHREEQC2 and

PHRQPITZ (Plummer et al., 1988, Wolery 1992b, Parkhurst and Appelo, 1999, Teaf et

al., 2006) and SOLMNEQ, WATEQ, REDEQL, MINEQL, PATHI, and EQ3/6 (Wolery,

1979).

Each of the aforementioned codes utilizes the thermodynamic framework

identified 80 or more years ago, and much of the improvement of such codes is in their

interfaces, databases, and outputs (Maest et al., 2005).

Each individual code typically has a slight advantage or disadvantage for

various applications, but much of the usefulness of a given program is dependent on the

modeler experience, the input parameters and data, and model output interpretation,

rather than the actual code (Maest et al., 2005). “The ability of today’s codes and

advanced computers to predict an outcome far exceeds the ability of hydrogeologists and

geochemists to represent the physical and chemical properties of the site” (Maest et al.,

2005).

The EQ3/6 software package (where the EQ3NR portion of the code is used for aqueous speciation modeling, and the EQ6 portion of the code uses the output of

EQ3NR to perform reaction path modeling) originated in the mid1970s, and was developed at Northwestern University. The original author, Thomas J. Wolery, brought the EQ3/6 package to Lawrence Livermore Laboratory in 1978 (Wolery, 1992b). It was originally described by Wolery (1979) in the report “Calculation of Chemical

Equilibrium Between Aqueous Solutions and Minerals, the EQ3/6 Software Package”, and has since been updated with several new versions and accompanying documentation

(e.g., Wolery 1983, 1992a, 1992b, 1992c, and 1992d; Wolery et al., 1990; and Helgeson and Murphy, 1984).

EQ3NR is a key aqueous speciation program used in nuclear waste

management due to the relatively wide array of constraints (e.g., equilibrium constants,

temperatures) available for use within the program (Alpers, 2009). For example, the

thermodynamic temperature range available within EQ3NR data files ranges from 0 –

300 ˚C (Wolery, 1992b, 1992c).

The EQ3NR code can be used to compute equilibrium speciation for many

aqueous solutions including natural groundwater, surface water, sea water, and

hydrothermal solutions. EQ3NR or similar programs are commonly used for many types

of research, and scholarly endeavors, as demonstrated by Biddau et al., 2002; Casa et al.,

2000; Helgeson and Murphy, 1984; Marini et al., 2003; Milu et al., 2002; Murphy et al.,

1996; Murphy, 1986; Murphy and Grambow, 2008; and Ramirez et al., 2005; among

others.

EQ3NR is written in the computer language FORTRAN 77, and was developed for use with UNIX based operating systems. EQ3NR is not considered a geochemical computer model, but rather a code used to evaluate geochemical models that are described in the contents of a supporting input data file. A number of data file templates are available, and are widely suited to a variety of applications. For example, the data file ‘mgso4.3i’ evaluates pure water with a trace of MgSO 4, whereas the data file

‘swmajp.3i’ evaluates sea water using Pitzer's equations for concentrated aqueous

solutions, whereas ‘quenchfl.3i’ evaluates quenched fluid from a hydrothermal

experiment. For this research, the EQ3NR input file ‘acidmwj.3i,’was used. The input file

was adapted from its original use for modeling acid mine water at Spring Creek,

California (Wolery, 1992d). A detailed discussion of the EQ3 code is provided in the

methodology section of this document.

Specific Principles and Observations

The Moonlight Project spans approximately 6,857 acres in Plumas County,

CA, and is a site of historic mining operations that occurred over the last 150 years. From

1914 through 1930, 160 million pounds of copper, 23 thousand ounces of gold, and 1.9 million ounces of silver were recovered from the Engels and Superior Mines (Storey,

1978).

In 1880 Henry A. Engels and his family settled on Lights Creek where the

Superior Mine is located. Figure 9 is the earliest known photo of Engels Lower Camp

along Lights Creek, taken in 1905. Engels is given credit for discovering the Engels mine

in the early 1880s, and for the next 18 years, Engels explored the area by driving five

adits. In 1901, Engels and his brother incorporated Engels Mining Company in 1901, and began construction of a 100 ton blast furnace to smelt mediumgrade copper ores from

the Engels Mine.

Figure 9. The earliest known photo of Engels Lower Camp along Lights Creek, 1905. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

Elmer Paxton of Alexander & Baldwin, a Hawaiian based owner of sugar plantations, and Frederick Klamp, the VicePresident of H. Hackfeld & Co. Ltd., a

Honolulu based German merchant banking firm and owner of sugar plantations, visited

the smelter site and Engels Mine in 1910. Frederick Klamp raised money from his friends

and associates in Hawaii to build the infrastructure for the smelter project (Lamb, 2011).

A photo taken during the visit by Paxton and Klamp is shown in Figure 10. However, the

smelter was a failure, and in 1914 it was replaced by the first mill in the United States to

solely utilize flotation for processing ore, as shown in Figure 11 (McCutcheon, 2008;

Lamb, personal communications). “The mill was designed to mill 150 tons per day and

was milling 400 tons per day when it was closed on November 1, 1919, in lieu of the

larger and more favorably located Superior Mill at Lower Camp. (Courtesy of Norm

Lamb)” (McCutcheon, 2008, p. 78).

“The Superior Mill at Lower Camp began operation on November 1, 1917.

The Engels Mill at Upper Camp closed on November 1, 1919” (McCutcheon, 2008, p.

79). The supply of ore from Engels Mine was delivered to the mill (which has since been destroyed) by an 8milelong rope tramway and the Superior Electric Railroad, as shown in Figure 12. (Young, 1921). The photograph in Figure 13 shows Engelmine, Lower

Camp, in 1923, including the Superior Mine, Superior Mill, machine shop, office and warehouse, Indian Valley Railroad depot, and a power house. The supply of ore from the

Superior Mine (which was adjacent to the Superior Mill) was hoisted directly upwards from the mine to the mill, as shown in Figure 14.

The fourth level of the Engels Mine is shown in Figure 15. The combined

operation supplied approximately 1 thousand tons of ore per day from the Engels and

Superior mines. From 19141930, approximately 4.7 million tons of ore from the Engels

and Superior Mines was mined and milled.

Figure 10. Smelter under construction in 1910. The persons in this photo taken during their visit to the smelter are from left to right, Louise Girard, Harriet Paxton, William Engels, Frederick Klamp, Elmer Paxton and Henry Engels, President of Engels Copper Mining Company. It is thought that Louise Girard, age 28, the sisterinlaw of Frederick Klamp, came on the trip to meet William Engels, age 52, then thought to be a very eligible bachelor. In 1914 Elmer Paxton became the General Manager and Treasurer of Engels Copper Mining Company with the building of the Engels flotation mill at Upper Camp. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

Frederick Klamp became President of the Engels Mining Company in 1922

after ousting Henry Engels in a proxy fight. During World War I and throughout the

1920s, Engels Copper Mining Company was a significant employer that was the primary basis of the local economy. Engels Mining Company closed the mine and mill in July,

1930, due to the low price of copper (McCutcheon, 2008).

Figure 11. The first mill in the United States to use only the flotation process to concentrate its copper ore was completed in 1914 at the Engels Mine in Upper Camp. It was built by Minerals Separation American Syndicate (1913) Ltd. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

From 1962 through 1971 Placer Development Ltd. (now Barrick Gold

Corporation) reinitiated exploration of the Lights Creek Stock. During this time, Placer

Development Ltd. spent approximately 43 million dollars (adjusted for inflation from

1965 to 2011, using the United States Bureau of Labor Statistics Consumer Price Index data [CSI, 2011]) exploring the Moonlight Project.Placer Development Ltd. drilled 199 holes for a total of 99,436 feet of core (Darcel, 2008).

Figure 12. Superior Electric Railroad connecting the No. 10 Level of the Engels Mine with the Superior Mill. The railroad ran 8,300 feet underground and 6,500 feet above ground crossing 1,180 feet of trestle. In this photo from 1924 it is carrying 100 tons of ore across the trestle over the Superior Mine Glory Hole to the Superior Mill. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

Placer Development Ltd. discontinued their exploration activities at the

Moonlight Project in 1971, and officially ceased exploration of the site in 1993, when the company changed their interest exclusively to gold exploration (McCutcheon, 2008).

Sheffield Resources Ltd. acquired the project in 2004. From 2005 to 2008,

Sheffield completed widespread exploration of the site using limited drilling, geophysics,

and geochemistry, initially to verify historically reported grades in the Moonlight Valley

deposit. Sheffield Resources Ltd. also sampled underground workings at the Superior

Mine, and explored the copper oxide near the surface at the Engels Mine (Darcel, 2008).

Figure 13. Engelmine, Lower Camp, 1923: (1) Superior Mine (2) Superior Mill (3) Machine Shop (4) Office and Warehouse (5) Indian Valley Railroad Depot (6) Power House. The Superior Mill at Lower Camp began operation on November 1, 1917. The Engels Mill at Upper Camp closed on November 1, 1919. The consolidated operation milled 1,000 tonsperday from the Engels and Superior mines until July 15, 1930 when the mines and mill were closed due to the low price of copper. Ore was delivered to the mill from the Engels Mine first by the No. 6 Level aerial tramway then by the Superior Electric Railroad. From the adjacent Superior Mine ore was hoisted directly from the mine to the mill. During their operation from 19141930 approximately 4,700,000 tons were mined from the Engels and Superior mines and milled producing 160,170,000 pounds of copper and substantial values in gold and silver. Engels Copper Mining Company was a substantial employer during World War I and the 1920’s, supported the local economy and paid dividends to its shareholders. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

Figure 14. The 108 foot high steel head frame over the vertical three compartment Superior shaft was built in 1917. Fiveton steel skips hoisted through this main shaft dumped directly into the coarse ore bin at the head o f the Superior Mill. Ore was also delivered by the two mile long No. 6 Level aerial tramway from the Engels Mine Crushing Plant to the tramway terminal and into a separate storage bin above the mill. Reprinted with permission from Norman Lamb and Engels M ining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

Figure 15. The fourth level of Engels Mine in 1915. Reprinted with permission from Norman Lamb and Engels Mining Company, and McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

In 2008, Nevoro Inc. acquired Sheffield Resources Ltd. through merger and drilled addition holes at the Engels Mine and Moonlight Valley. Specifically, Nevoro considered reopening the site as an openpit copper mine.

Nevoro merged with Starfield Resources Inc. in June 2009. Starfield

Resources began a core drilling program at the Moonlight Project site in 2009.

Existing Data

Historical data for water quality was provided for this research project by N.

Lamb and R. Wetzel. Much of the data were collected for regulatory compliance (e.g., under California Code of Regulations Title 22 and 23). Sampling was conducted from

2000 through 2005 on an approximately monthly basis (except in 2004) by L. Foote.

Sampling locations were designated by L. Foote as ‘station locations’, and roughly correspond to MNWAT07 (station 1), MNWAT01 (station 2), MNWAT03 (stations

3, 4, and 5, which are all nearby one another), and MNWAT04 (station 6) in this research. Water quality parameter data measured included total dissolved solids (TDS),

EC, pH, and temperature.

TDS values at station 1 ranged from approximately 30 to 70 mg/L, EC ranged from approximately 60 and 130 µS/cm, pH ranged from approximately 7.5 to 9.0, and temperature ranged from approximately 0 to 27 ˚C, although the typical temperatures were in the range of 4 to 23 ˚C. In comparison to the parameter values recorded for this study (discussed later in this report), the values recorded by L. Foote for EC were all lower, while the pH and temperature (for the respective months when this study was conducted) generally corresponded.

TDS values at station 2 ranged from approximately 30 to 80 mg/L, EC ranged from approximately 60 and 130 µS/cm, pH ranged from approximately 7.5 – 8.5, and temperature ranged from approximately 0 to 27 ˚C, although the typical temperatures were in the range of 4 to 23 ˚C. In comparison to the parameter values recorded for this study (discussed later in this report), the values recorded by L. Foote for EC were all

lower, while the pH and temperature (for the respective months when this study was

conducted) generally corresponded.

TDS values at stations 3 to 5 ranged from approximately 30 to 150 mg/L,

although the majority of the readings did not exceed approximately 80 mg/L. EC values

ranged from approximately 60 and 280 µS/cm, although the majority of the readings did

not exceed approximately 130 µS/cm. pH values ranged from approximately 6.7 – 8.5,

although all but one of the readings were above 7.0. Temperature values ranged from

approximately 0 to 27 ˚C, although the typical temperatures were in the range of 4 to 23

˚C. In comparison to the parameter values recorded for this study (discussed later in this

report), the values recorded by L. Foote for EC, pH and temperature (for the respective

months when this study was conducted) generally corresponded.

TDS values at station 6 ranged from approximately 30 to 90 mg/L, EC ranged

from approximately 60 and 170 µS/cm, pH ranged from approximately 7.0 – 8.5, and

temperature ranged from approximately 0 to 27 ˚C, although the typical temperatures

were in the range of 4 to 23 ˚C. In comparison to the parameter values recorded for this

study (discussed later in this report), the values recorded by L. Foote for EC, pH and

temperature (for the respective months when this study was conducted) generally

corresponded.

Additional, infrequent field measurements of monitoring parameters were

recorded from 2006 through the initiation of this project. Results demonstrated general

consistency in results in pH (typically ranging from 7.0 to 8.5), with the exception of the period following wildfire that burned through the Moonlight Project site on September

1315. Following the wildfire, pH values in surface waters at the Moonlight Project site

were temporarily elevated.

In addition to monitoring parameter data, a limited amount data for trace element concentrations in surface water at the Moonlight Project were obtained. Water samples were collected in November 1986 by L. Deem, and analyzed for aluminum, antimony, arsenic, barium, beryllium, cadmium, chromium III, chromium IV, cobalt, copper, iron lead, manganese, mercury, molybdenum, nickel, selenium, silver, thallium, vanadium, and zinc. The two samples collected were designated ‘Engels Mine no. 10 level’ (corresponding to MNWAT09 in this study), and ‘Lights CreekEngels’ (no description of this monitoring location was available for comparison). All metals in the

Engels Mine no. 10 level were present below the method detection limits (MDLs), with the exception of copper and iron, which were present at 0.2 and 0.1 mg/L, respectively.

All metals in the Lights Creek – Engels location were present below their respective

MDLs, with the exception of iron, which was present at 0.32 mg/L.

Analyses for copper, arsenic, zinc, and mercury was conducted by Sierra

Foothills Laboratory from 2006 through 2008 on samples collected by R. Wetzel and others. A sample was collected in 2006 at a location corresponding to sampling location

MNWAT08 (inside the Engels no. 10 portal) in this study. Results demonstrated that copper and arsenic were present at concentrations of 0.12 and 15 mg/L, respectively, while zinc and mercury were not present above their respective MDLs.

Samples were collected during eleven sampling events from 2006 through

2008 at a location corresponding to sampling location MNWAT01 in this study. Results demonstrated that copper was present at concentrations of 0.083 to 2.55 mg/L, arsenic

38 was present at concentrations of 819 µg/L, zinc concentrations ranged from below the

MDL to 13 µg/L, and mercury were not detected above its MDL.

One sample was collected in 2008 at a location corresponding to sampling location MNWAT02 in this study. Results demonstrated that copper, arsenic, and zinc were present at concentrations of 0.24 mg/L, 2.1 mg/L, and 96 µg/L, respectively.

Samples were collected during eight sampling events from 2006 through 2008 at a location corresponding to sampling location MNWAT03 in this study. Results demonstrated that copper was present at concentrations ranging from below its MDL to

0.0087 mg/L, zinc was present at concentrations ranging from below its MDL to 13 µg/L, while arsenic and mercury were not present above their respective MDLs.

Samples were collected during nine sampling events from 2006 through 2008 at a location corresponding to sampling location MNWAT5 in this study. Results demonstrated that copper was present at concentrations ranging from below the MDL to

0.0033 mg/L, and arsenic, zinc, and mercury were not detected above their respective

MDLs.

Samples were collected during eight sampling events from 2006 through 2008 at a location corresponding to sampling location MNWAT08 in this study. Results demonstrated that copper, arsenic, zinc, and mercury were not detected above their respective MDLs, with the exception of copper, which was present at 0.0017 mg/L on

August 21, 2007.

Samples were collected during nine sampling events from 2006 through 2008 at a location corresponding to sampling location MNWAT11 in this study. Results demonstrated that copper was present at concentrations of 0.07 to 0.103 mg/L, arsenic

39 was present at concentrations of 1033 µg/L, zinc concentrations ranged from below the

MDL to 20.8 µg/L, and mercury were not detected above its MDL.

The trace metal analysis results for samples collected by R. Wetzel and others generally corresponded with results of this study. Metals were generally elevated in waters emerging from adits, and were usually nondetect in the waters of Lights Creek, even directly downstream from the mine tailings that line the shores of the creek. pH values were all nearly neutral or slightly basic. Results for this study are discussed in detail later in this report.

Much literature exists concerning the geology of the Moonlight Project and greater Lights Creek District and Plumas Copper Belt regions. However, no research of environmental effects from historic mining at the Moonlight Project was located in the literature, aside from the previously discussed data collected by J. Deem, R. Wetzel, and others. As such, this is the first known study of the Moonlight Project area with a specific focus on developing a ‘signature’ of the surface waters using chemical analysis and aqueous speciation models.

CHAPTER III

METHODOLOGY

Introduction

This section provides an introduction and background of the Moonlight

Project within the historic Lights Creek Mining District, including a description of the overall site, geography, geology, and hydrology of the site. In addition, field and laboratory procedures and methods, as well as a description of the computer code used within this research for chemical speciation (EQ3NR) are presented herein.

Site Description

Overall Site Description

The Moonlight Project is located in Plumas County, California, approximately

140 km northwest of Reno, Nevada, and approximately 32 km north of Taylorsville,

California.

The climate at the Moonlight Project in and around the Indian Valley is mild during the summer, when average temperatures are in the 60s (degrees Fahrenheit).

Temperatures are cold during the winter, when temperatures tend to be in the 30s

(CDECa, 2010), although temperatures vary between the locations sampled for this research project due to elevation differences. The warmest month of the year is typically

July, and the coldest month of the year is December.

40 41

The annual average precipitation since January 1989 at Greenville, California

(located approximately 15 km west of Superior and Engels Mines) is 39.4 inches

(CDECb, 2010). Most of the area monitored for this research has varying levels snowfall throughout the winter months, depending on elevation.

During the previously mentioned wildfire that swept through the Moonlight

Project on September 1315, 2007, a total of 64,997 acres were burned (JimnezHoltz,

2007). The fire had measureable effects on water quality (elevated pH in surface waters

were reported in affected areas), as reflected by field monitoring parameter measurements

conducted by others. According to N. Lamb and R. Wetzel (personal communications,

October 2008 through May 2009), after the wildfire, research project personnel observed

elevated pH in affected areas. However, pH readings returned to their normal range by

the initiation of this study.

Site Geography and Geology

The Moonlight Project exhibits geography with high relief and incised stream

valleys. Lights Creek runs approximately southwest through Lights Canyon, which opens

up to the broad alluvial Indian Valley (Goerge et al., 2007), which is shown in Figure 16.

The Plumas Copper Belt constitutes the second most productive copper region

in California, and is known for a large number of high grade copper mines, most of which

have been inactive since the late 1930s. Large amounts of copper occur throughout the

Moonlight Project, with lesser amounts of gold and silver. The primary copper

mineralization in the Moonlight Project area occurs at the Superior and Engels Mines,

and Moonlight Valley (differentiated from the Moonlight Project).

Figure 16. Lights Creek running through Lights Canyon and to the Indian Valley.

The Superior mine is located “within the southern boundary of the Lights

Creek Stock, and the Engels mine is in a gabbroic just east of the stock” (Storey, 1978, p.

52). The granitic plutons associ ated with the Superior and Engels mines are located in

Sections 3,4,5,6,7,9,10,17,18, Township 27 north, Range 11 east (Smith, 1970 a). The diorite at Walker Mine is located in “underground intrusive relation in (main haulage adit ), Walker Mine” (Smith, 19 70a, p. 10).

Copper ore is often contained in large, low grade porphyry copper deposits

(typically hundreds of millions of metric ton s) that are contained in felsic granitoid intrusion host rocks, with significant but lesser amounts being found in massive sulfide, skarn, or other deposit types ( Blowes et al., 2003 ). The low sulfide, oxide dominated ore at the Moonlight Project is uncharacteristic of typical copper containing deposits . Various geologic interpretations of the Plumas Copper Belt a re presented in the literature , as are accounts of the mineralization throughout the Moonlight Project. The ore processed in

the early 1900s at the Engels and Superior mines is described as “copper sulphide

associated with magnetite and gangue” (von Bernewitz, 1916). The idea that significant

sulfide mineralization exists at the site is reinforced by accounts that the original ore processing smelter built at the site was a failure, and the flotation process was successful

(von Bernewitz, 1916; McCutcheon, 2008), as discussed later in this section.

According to Smith (1970a), the Plumas Copper Belt is the “most significant zone of copperiron sulfide, mineralized rock that is wholly within or closely associated with granitic intrusions [within California].” Smith (1970a) describes the Plumas Copper

Belt as being associated with eight granitic plutons, (quartz monzonite of Lights Creek, granite at China Gulch, quartz diorite at Engels Mine, quartz monzonite at LuckyS mine, diorite near Genesee, granodiorite of Little Grizzly Creek, diorite at Walker Mine, and

Mesozoic granitic rock, undifferentiated).

According to Smith (1970a), the bodies at the Moonlight Project include quartz diorite and gabbro at Engels Mine, the quartz monzonite of Lights Creek, and undifferentiated granitic rock. The quartz diorite ore body at Engels mine consists of

“disseminated chalcopyrite and bornite within sheared tonalite and diorite... [and] ore minerals in sheetlike forms, roughly parallel to the strike of the ore body” (Smith, 1970a, p. 13). Turner and Rogers (1914) and Graton and McLaughlin (1914) concluded that the copper ore at the Engels mine is “either of late magmatic or of hydrothermal origin”

(Smith, 1970a, p. 13).

MacBoyle (1918, p. 58) determined that the ore body at the Superior Mine was mostly covered by six feet of soil, but in exposed areas it shows “a leached rock stained by malachite, limonite, and chrysocolla… Below this, a zone of sulfide

enrichment… yielded considerable chalcocite carrying 16 to 20 percent copper.”

MacBoyle estimated that this zone was 25 feet thick and dipped gently southwest. “This

ore gives place to bornite, at depths of 100 to 130 feet…” (MacBoyle, 1918, p. 58).

MacBoyle’s account is in contrast to other accounts described herein. A photograph of bornite (Cu 5FeS 4) taken within the Superior Mine no. 5 level is shown in Figure 17.

Smith (1970a) indicates that the Superior Deposit is the largest ore body in the

Lights Creek Pluton, with primary sulfide minerals being chalcopyrite and subordinate bornite occurring in vein systems that are “associated with magnetite and minor portions

of pyrite. Tourmaline and epidote are pervasive minerals in the Lights Creek pluton”

(Smith, 1970a).

Other accounts of the Lights Creek District geology differ. According to

Hitzman et al. (1992), Oreskes et al. (1994), Barton and Johnson (1996), Williams et al.

(2005), the features of the Lights Creek Stock are “similar to the class of ores known as

ironoxidecoppergold (IOCG) deposits” (Stephens, 2011, abstract).

MacFarlane (1981) agrees with Storey (1978), who postulates that “the

mineral alteration assemblages and zonation [at the site] differ significantly from

literature descriptions of classic porphyry systems” (Stephens, 2011, p. 5). Classic copper porphyry deposits are characterized by

…granitoid porphyry intrusions, abundant veinlets of mm and cm width, disseminated low grades of Cu and/or Mo and/or Au and/or Ag sulfide mineralization with distal pyriterich zones, pervasive wallrock alteration to potassium silicate (biotiteK feldspar, sericitic (muscovite), propylitic (epidote chlorite), and local advance argillic (pyrophyllite) assemblages. (Stephens, 2011, p. 5)

Figure 17. Bornite in the No. 5 level of the Superior Mine. Bornite occurs at the Moonlight Project site.

Graton and McLaughlin (1914) and Anderson (1931) conclude that the copper

deposits at Superior and Engels Mines are a series of large easterndipping veins, which

are uncharacteristic of porphyry deposits. Stephens (2011, abstract) indicates that the

mineralization in the Lights Creek District “likely included components of both porphyrytype magmatichydrothermal and IOCGlike nonmagmatic sedimentary brine

fluids.” Stephens (2011) and Putman (1972) state that the Lights Creek District has some

level of hydrothermal alteration with minor amounts of sulfide present.

According to Smith (1970a, p. 13), at the Walker Mine, five ore bodies occurred in quartz veins “within a northwest striking shear zone that cuts basic schistose and hornfelsic rock near a contact with intrusive quartz diorite.” Although the primary

ore mineral at the Walker mine is chalcopyrite, the ore also contains minor amounts of

tetrahedrite and chalcocite (Smith, 1970a). In contrast, Averill (1937) determined that

the copper at Walker Mine is present principally as a massive ore body, but also within

fractures and veins within the host rock.

In a 2008 analysis of Sheffield Resources Ltd., a MineralSTOX ® analyst stated that the “Moonlight [Project] contains large sulfide copper deposits (“the

Moonlight deposit” and “the Superior deposit”), and highly prospective oxide copper targets that are now Sheffield’s development priority…” (Darcel, 2008, p. 2).

Although the Moonlight Project mineralization type is a subject of ongoing research and debate, there is little question that it differs from that found at the nearby

Walker Mine. Based on geological findings, the Walker Mine and Moonlight Project mines are not appropriate proximal analogs.

Copper mineralization varies throughout the area within the Moonlight

Project. Placer Development Ltd. exploration “encountered 2.86 percent Cu oxide mineralization from 18.6 to 37.5 m … with no core recovery to 18.6 m … on the Main

Zone in diamond drill hole E2 at Engels Mine” (Darcel, 2008, p. 5). Sheffield took samples of limited surface exposure samples at the primary zone of mineralization at the

Engels Mine, which averaged 1.66 percent copper over a combined width of approximately 36.6 m.

Smelting was the first method of copper extraction attempted at the Moonlight

Project, starting in 1901. As compared to ‘wet’ methods, which use chemicals to dissociate gangue minerals from a valuable target metal, smelting is a ‘dry’ method of metal extraction from ore. Smelting is based on the principle that sulfiderich immiscible

liquid in a solution sinks, since it is denser than gangue or silicate oxides. Therefore, if

the entire bulk of gangue and ore are liquefied through heating, it allows the separation of

the layers and extraction of the valuable metals. Additionally, the heating can convert the

oxide metals to pure metals (Peters, 1911).

Where the metal occurs throughout ore in minute amounts, a purifying or heat generating fluid is applied to the overall mixture. The appropriate fluid would dissolve the valuable metal(s), and have a higher specific gravity relative to the other components of the liquid so it sinks with the metal within the mixture (Peters, 1911). While a smelter was constructed at the Moonlight Project in 1901, it was a failure.

Likely reasons for this failure are the composition of the ore, which may consist of substances that do not melt at a temperature that can be easily reached in a smelter. Under these conditions, additional costs of fluxing material can make smelting economically prohibitive (Peters, 1911).

A flotation mill was constructed at the Moonlight Site in 1914 (see Figure 18).

Flotation is a ‘wet’ process initially introduced for processing sulfide ores by Froment,

Potter, and Delprat in 1902, although the concept was first introduced for use in bulk oil processing by Haynes in 1960 (Gaudin, 1957).

Although many varieties of the technology exist for many purposes, flotation generally operates under the principle that sulfide ores are typically hydrophobic (and are wetted by oil) and the gangue particles are generally hydrophilic (wetted by water). In flotation, oil (e.g., pine oil) is mixed with water in a cell. The ore to be processed is crushed and dropped into a cell, where the mixture is agitated.

Figure 18. The flotation cells in the Engels Mill at Upper Camp. Flotation was the most important development of the 20 th century for the mining industry. It opened new mineral resources and averted an industrial crisis with the exhaustion of highgrade mineral deposits. Shown are Will Gruss and Charles Scott Haley. Reprinted with permission from McCutcheon, R., 2008, Indian Valley: Charleston, South Carolina, Arcadia Publishing, 78 p.

The gangue is wetted by the water, and after agitation, settles to the bottom of the cell, while the sulfide minerals, wetted by the oil, float out of the mixture. The frothed mixture of oil and sulfide minerals is sent to a settling tank, where the pure sulfide ore is allowed to settle out and be removed for further processing such as filtering, heating, and drying. More specifically, a 1916 description of the flotation process used at the historic

Moonlight Project is as follows:

The ore [from the Superior and Engels mines] containing copper sulphide associated with magnetite and gangue is crushed by gyratorybreaker, rolls and 7 by 10ft. tube mill until only 5 per cent. remains on 100mesh. It is then fed to a 12cell Minerals Separation machine which makes finished concentrates froth from the first three cells and middlings froth from the rest, which is returned to the first cell for retreatment. The concentrates are settled in a settling tank and then go to Oliver filter reducing moisture to 10 or 12 per cent. The filter cake is finally dried down to 5 or 6 per cent. in an old drag classifier heated by fire. Oil used is 0.4 lb. per ton of ore, half of which is added in the tube mill. Feed averages 3.8 per cent. copper and the concentrates 40 per cent. The extraction is 84 per cent. and the capacity 200 tons per 24 hr. (von Bernewitz, 1916, p. 792)

Flotation proved to be successful for the Moonlight Project site, as discussed later in this report. By the conclusion of mining at the Engels and Superior mines, the majority of copper extracted had been exploited using flotation.

General Site Surface Hydrology and Aquatic Life

Lights Creek is a perennial tributary that drains approximately 122 square km

to Indian Creek, which flows to the North Fork of the Feather River. Clarkin (2006)

states that bankfull flow in Lights Creek is estimated at 380 cubic feet per second, while

100year peak flow is estimated at 5,750 cubic feet per second. Vegetation along the

Lights Creek includes willow, cottonwood, alder, pine trees, and shrubs. Among other

species, Lights Creek provides habitat for nonthreatened native brown and rainbow

trout, as well as nongame fish species (Clarkin, 2006).

The streams in the Lights Creek drainage and the greater Plumas County eventually reach a confluence with the Feather River, which flows to the Sacramento

River to the Sacramento Delta. The Sacramento Delta drains into Suisun Bay, which drains into San Francisco Bay.

Field Activities and Procedures

A description of field activities and procedures, including a description of

monitoring locations, sampling procedures, field parameter data collection, and field

instrumentation, is presented in the following sections.

Monitoring Location Descriptions

Surface water sampling locations were selected based on locations of mine adit entrances and tailings from the historic Moonlight Project, and in consultation with the Moonlight Project Geologist at the time of the research, Robert Wetzel (a California

State Board certified Registered Professional Geologist). Details of sampling locations within the Moonlight Project and outside of the Moonlight Project are presented in Table

1 and Table 2, respectively.

Selected samples were field filtered, and were designated as the location site

ID followed by “F”. In addition, selected samples were quantitatively diluted to 1:1 (parts sample water:parts deionized water), and were designated as the location site ID followed by “X”.

Sampling Procedures

Surface water sampling was conducted in accordance with the United States

Geological Survey (USGS) National Field Manual for the Collection of Water Quality

Data (USGS, variously dated).

Prior to each sampling event, any notable weather or other conditions were recorded, all instruments were decontaminated using deionized water, and all instruments were calibrated at a minimum of daily intervals using standard solutions and techniques recommended by the manufacturer.

TABLE 1. MONITORING LOCATIONS WITHIN THE MOONLIGHT PROJECT UTM NAD 27 coordinates* Site northing easting identification Location Body of water (m) (m) MNWAT01 Superior Mine #2 level Adit entrance 4452549 689441 MNWAT02 Blue Copper Mine Adit entrance 4452453 688338 MNWAT03 Lower Lights Creek downstream Lights Creek 4451378 688607 of tailings piles (upstream of bridge) MNWAT04 Lights Creek at Moonlight Lights Creek 4449188 688182 Valley Road fish ladder MNWAT05 Moonlight Creek Junction at Moonlight Creek 4453557 685175 Moonlight Valley Road MNWAT06 Superior Ravine at Diamond Superior Ravine 4452765 689785 Mountain Road MNWAT07 China Gulch at Diamond China Gulch 4453373 690131 Mountain Road MNWAT08 Trout Bridge on Lights Creek 4 Lights Creek 4456485 691241 km upstream of Superior Mine MNWAT09 Engels Mine # 10 Level Adit entrance 4453383 690703 MNWAT10 Engels Mine drill pond Upper China Gulch 4454406 692255 MNWAT11 50ft downstream of Engels Mine Downstream from 4434041 671217 † #10 level adit Note: The identification number MNWAT13 was used as a field duplicate sample identifier for quality assurance purposes. * Zone 10T. † GPS data were converted to latitude and longitude.

All instruments were decontaminated using deionized water at each sampling location. A GPS reading was recorded at each monitoring location, and field chemistry measurements of surface water monitoring parameters were taken in a triplerinsed polyethylene sample bottle and documented after parameter readings stabilized.

A direct grab method of sampling was utilized, and labels denoting the research project, time, date, and sampling location were placed on each sampling bottle.

Sample bottles were rinsed once with deionized water and rinsed twice with sample water before a sample was collected.

TABLE 2. MONITORING LOCATIONS OUTSIDE OF THE MOONLIGHT PROJECT UTM NAD 27 coordinates* Site northing easting identification Location Body of water (m) (m) MNWAT12 Feather River at Paxton Road Feather River 4453699 690582 † Bridge MNWAT14 Adit entrance 4426709 699409 † MNWAT15 Culvert on Walker Mine Road Dolly Creek 4426244 698925 † (downstream end) MNWAT16 Highway 70 at Soda Creek Soda Creek 4434087 670633 † (upstream side of Hwy 70 Bridge) MNWAT17 Walker Mine tailings upstream Little Grizzly 4425704 714018 † location Creek MNWAT18 Walker Mine tailings downstream Little Grizzly 4425424 697480 † location (upstream of bridge) Creek Note: The identification number MNWAT13 was used as a field duplicate sample identifier for quality assurance purposes. * Zone 10T. † GPS data were converted to latitude and longitude.

The sample containers were fully submerged in the surface water (at a depth

of approximately 10 cm, where possible) and filled slowly to collect a representative

sample and to avoid disturbance of sediments.

Quality assurance and quality control (QA/QC) techniques that were used in

this research include chainofcustody control of samples, decontamination of field

equipment at each sampling location, field duplicate samples, field calibration of all probes according to manufacturer specifications, laboratory methods (Activation

Laboratories), method blanks (for Code 6 analyses), and laboratory duplicate samples

(for all analyses). A National Research Council of Canada (NRCC) standard SLRS4 was run every 25 samples for Code 6 analyses. A National Institute of Standards and

Technology (NIST) water standard 1640 was run at the beginning and the end of each batch as control materials for Code 6 analyses.

Field duplicate samples at monitoring location MNWAT16 were obtained

on three occasions, and were submitted as MNWAT13. Select samples were filtered to

remove colloidal solids using standard 0.45 micron glass fiber filters and a hand vacuum pump. A minimum of three sample volumes were pumped through the filter and

discarded before collecting a final filtered sample for analysis. Designated samples were

diluted quantitatively with distilled water to obtain accurate data for analytes present in

laboratory results in concentrations that were previously over maximum detection limits.

After each sampling event, samples were refrigerated at approximately 4° C

until being submitted under chainofcustody documentation to Activation Laboratories

(a professional analytical service located in Ontario, Canada).

Activation Laboratories is accredited by the Standards Council of Canada

(SCC), which requires onsite assessment of laboratories by SCC auditors, as well as proficiency testing. The QA/QC for Activation Laboratories is accredited to international

standards for environmental laboratory analysis through the International Organization

for Standardization /International Electrotechnical Commission (ISO/IEC) 17025, which

specifies the requirements for accreditation to carry out laboratory tests or instrument

calibrations. Sampling location MNWAT04 is shown in Figure 19, MNWAT11 is

shown in Figure 20, and Figure 21 shows MNWAT14.

Activation Laboratories is also accredited by the National Environmental

Laboratory Accreditation Conference (NELAC) program and Health Canada (Activation

Laboratories, 2011).

Field Instrumentation

At the initiation of this research project, water field parameter measurements were collected using a waterproof Hanna® HI 991300 pH/EC/total dissolved solids/temperature meter. Beginning on October 13, 2008, water field parameter measurements were taken with an Orion® 5Star Portable meter. Two GPS units were utilized during research project: an External Antenna Garmin GPSMAP® 60 CSx, and a

Brunton MultiNavigator™.

Field Parameter Data Collection and Analysis

Initial sample sites were selected, and measurements of field parameters including temperature, pH, EC, oxidation reduction potential (Eh or ORP or redox), and

DO were taken during the study period.

Temperature . Water quality data typically include temperature measurements, which are essential for determination of many other water quality parameters (e.g., DO,

EC, and pH). Temperature measurements were recorded in units of ˚C using the Orion®

5Star Portable meter with an Orion 013010MD combined temperature and conductivity cell.

pH . The number of protons or hydrogen ions present in an aqueous solution is the pH. More specifically, pH is defined as (9):

+ pH= log H . (8)

An aqueous solution of water undergoes dissociation to distinct ionic species as follows in equation (9):

+ H2O ↔ H + OH . (9)

Figure 19. Sampling location MN WAT04 (downstream side of bridge), Lights Creek at Moonlight Valley Road fish ladde r.

Figure 20 . Orion® 5 Star Portable meter being used to measure field parameters in waters emerging from the remediated Engel s Mine adit, monitoring location MN WAT11.

Figure 21. Waters emerging fr om the remediated Walker Mine adit , monitoring location MNWAT14.

The activity of a dissolved species i (ai or [ i]) is used in calculations for chemical reactions of aqueous and solid solutions. For aqueous solutions, ai is defined as the product of the molal concentration of a species in a solution ( mi, or molality) and an

activity coefficient, ( ) of a species. The reference state for the a is a hypothetical 1 i molal solution with , because, as the dilution of an aqueous solution approaches = 1 infinity, approaches unity (10):

ai=γimi. (10)

+ Assuming at 25˚C the activity of H 2O ( or [H 2O]) is unity, and the activity of H and

+ 7 OH in the dissociation of pure water at 25˚C are both aH+ = [H ] = aOH = [OH ] = 10 .

Since neutral solutions of pure water have equal amounts of H + and OH ions present, the

equilibrium constant and pH calculation for the dissociation of water at 25˚C are shown

in equations (11) and (12), respectively:

+ H [OH ] 14 Keq = = = 10 (11) [H2O] [1] ; and

7 pH= log 10 = 7. (12)

If an excess of H + ions are present, the aquous solution is acidic (pH < 7), and if an excess of OH ions are present, the solution is basic (pH > 7). Often, pH is not

automatically adjusted for temperature with a field meter. Therefore, when water

temperatures vary from 25˚C (as they did for the entirety of this field research) the true

neutral pH will vary from instrument readings, and must be adjusted accordingly.

Measurements of pH were collected for this research using the Orion® 5Star Portable

meter equipped with an Orion® 9107BN pH probe through March 2009, at which time

an Orion® 9107BNMD Triode Low Maintenance pH electrode with a temperature

adapter was used with the same meter. All unadjusted measurements were adjusted for

the temperature dependence of pH.

Electrical Conductivity . EC issometimes referred to as conductance or specific electrical conductance of a solution is “the sum of the conductivities of all the conducting constituents” (McCleskey, 2011, p. 317). EC measurements can be used to estimate many other properties of an aqueous solution under various assumptions, including total dissolved solids (McCleskey, 2011; Gustafson and Behrman, 1939; Lystrom et al., 1978;

Day and Nightingale, 1984; Singh and Kalra, 1975) salinity (McCleskey, 2011; Lewis,

1980; Brown et al., 1989;Wilson, 1981) concentration of major solutes (McCleskey,

2011; McNeil and Cox, 2000; Pollak, 1954), and ionic strength (McCleskey, 2011; Lind,

1970; Pintro and Inoue, 1999; Polemio et al., 1980; Ponnamperuma et al., 1966). EC is a function of the dissolved substances such as ions and other dissolved particulates in water

(although total dissolved species are not linearly related to EC). EC measurements were taken using units of microsiemens per centimeter (µS/cm) at 25 ˚C with the Orion® 5

Star Portable meter equipped with an Orion 013010MD combined temperature and conductivity cell electrode.

Dissolved Oxygen . DO is the molecular oxygen (oxygen gas) dissolved in water as a result of the activity of atmospheric air, rock, and aquatic plants. The DO in water is a function of several variables including temperature, plant presence, ion presence, and atmospheric pressure, and is a useful tool for monitoring natural or

humancaused changes induced in water bodies. Many reactions in aqueous solutions

occur based on the amount of oxygen present in water, which dictates if the aqueous

environment is anaerobic or aerobic. Survival of many aquatic plants and animals

depends on the amount of DO in the water that they inhabit. As such, DO concentration

serves as one indicator of the relative ‘health’ of many surface aquatic ecosystems.

Measurements for DO were collected with the Orion® 5Star Portable meter

equipped with an Orion 083010MD DO electrode attachment (with temperature

adjustment), and were reported as percents of total oxygen saturation at the measured

water temperature.

Oxidation Reduction Potential . In many chemical reactions that occur in the environment, the valence states of elements that can exist at different valence states change through gains or losses of electrons. The gain of an electron is termed ‘oxidation’ and the loss of an electron is termed ‘reduction.’ The ORP, or redox potential, of a solution describes the propensity of elements with varying valence states in an aqueous solution to undergo oxidation or reduction, measured on the thermodynamic scale of redox potentials using a standard hydrogen electrode (SHE). The ORP of low temperature systems is typically variable, as there is often disequilibrium between chemical species under lowtemperature conditions. Several measures of ORP exist, including dissolved O 2 and Eh. Redox potential measurements for this research used Eh,

since, in contrast to pH (which describes the number of protons present in an aqueous

solution), the Eh of an aqueous solution describes the number of electrons present in a

solution (Fetter, 1999). Many oxidationreduction reactions are catalyzed by

microorganisms. The following halfreaction (13) shows the reduction of manganese:

Mn 3+ + e → Mn 2+ , (13) and the following halfreaction (14) is an example of oxidation of manganese:

Mn 2+ → Mn 3+ + e . (14)

For oxidation or reduction to occur in a chemical reaction, one element must be reduced, and one must be oxidized. For example, the complete equation for the oxidation of Mn 2+ to pyrolusite (MnO 2) may be expressed as (15):

2+ + Mn + H 2O + 0.5O 2 (aq) ↔ MnO 2 + 2H . (15)

The halfreactions for the above reaction are shown in (16) and (17):

2+ Mn ↔ MnO 2 + 4e ; (16)

and

+ O2 +4H + 4e ↔ 2H 2O. (17)

According to Robinson (1975) and Fetter (1999), the equation for a solution of H 2O and

H+ ions equation (18) is:

+ vV + dH + ne ↔ uU + wH2O, (18)

where V is the reactant, U is the product, n is the number of electrons released, v is the moles of reactant, w is the moles of water, u is the moles of product, and d is the moles of

hydrogen ions.

The Nernst equation (19) corresponding to the above equation (18) for a

+ solution of H 2O and H ions is (Fetter, 1999):

u w 0 RT [U] [H2O] Eh = E 2.303 log m (19) nF [V]v[H+] ,

where E0 is the standard potential of redox reaction in volts, R is the gas constant

(0.00199 Kcal/(mol·K)), T is the temperature in Kelvins, F is the Faraday constant (23.06

Kcal/V), n is the number of electrons transferred in the overall redox reaction, and [ i ] is

the activity of product or reactant i.

Eh measurements may also be taken using field equipment. Since Eh is

affected by temperature (see [21]), an Eh probe must either have a temperature

adjustment or data must be adjusted for temperature. Eh measurements were taken using

the Orion® 5Star Portable meter equipped with an Orion 91080BNMD Triode Refillable

oxygen reduction potential (ORP) temperature dependence adjusted electrode, and are

reported in units of millivolts (mV).

EhpH Relationship . At 1 atmosphere (atm) of pressure and 25˚C, the Nernst equation (19) can be simplified to relate the Eh and pH (20):

0.0592 [U]u d Eh = E0 log 0.0592 pH. (20) n [V]v n

The standard potential of a reaction (Eo) can be determined using the free energy (i.e.

0 Gibbs free energy, ∆G R ) in the equation (21):

0 0 -∆G R (21) E = nF . Gibbs free energy is the difference between the free energies of the products in a reaction and the free energies of the reactants in a reaction. Reaction (22) may be used to calculate the Gibbs free energy (23):

pP + qQ + sS ↔ gG + hH + jJ; (22)

0 0 0 0 0 0 0 ∆GR=g∆Gg+h∆Gh+j∆Gj p∆Gp+q∆Gq+s∆Gs . (23)

where p, q, and s are moles of reactants P, Q, and S (respectively), and g, h, and j are moles of products G, H, and J (respectively). Laboratory measured free energy values are available in standard reference sources. The equilibrium constant, Keq , is related to Gibbs free energy (24):

0 ∆GR= RT ln Keq . (24)

Potential and pH relations of species existing in a closed system are often expressed in potentialpH diagrams (typically in EhpH or pepH forms).

PotentialpH diagrams (often called ‘Pourbaix Diagrams’) were introduced by

M. J. N. Pourbaix in his 1939 doctoral dissertation (first published in 1949) entitled

“Thermodynamics of Dilute Aqueous Solutions with Applications to Electrochemistry

and Corrosion.”

In the foreword of Pourbaix’s dissertation, J. N. Agar states that Pourbaix

“developed a graphical method, based on generalized thermodynamical equations, for the

solution of many different kinds of scientific problems, [particularly] the discussion of

the passage between the metallic and combined states” (Pourbaix, 1939).

Since elements can exist in several valence states or as various compounds

within such a system, free energies of the various interactions that may be occurring in a

system may be calculated. Such calculations are performed using the Gibbs free energy

of the individual constituents in the system to derive the free energy of a chemical

reaction, and to calculate a standard potential . The Nernst equation can be used to

calculate the Eh of a solution (in volts), as a function of the pH of a solution. The

resulting equations provide boundaries between predominant valence states of an element

at equilibrium in a system, which can be used to create an EhpH diagram.

The complex interactions that control the amounts of one or more chemical

constituents can be graphically portrayed using an EhpH diagram. EhpH diagrams are based on the standard state assumption (25˚C, 1 atm pressure).

The thermodynamic equations used to prepare EhpH diagrams for the

standard state include the previously discussed equations (20), (21), and (24) (Hem,

1963). For a nonstandard state situation, equation (19) should be used in place of

equation (24).

Laboratory Analyses

Elemental Analysis

All surface water samples were analyzed by Activation Laboratories for trace

elements using inductively coupled plasma mass spectrometry (ICPMS). The laboratory

elemental analysis at Activation Laboratories is termed the “Code 6 Hydrogeochemistry

Analysis.” The constituents included in the Code 6 Analysis are presented in Table 3.

Major Ion Analysis

To determine the dominant water characteristics of the water samples

2 collected, major ion analyses were conducted for chloride (Cl ) , sulfate (SO 4 ) ,

2 bicarbonate (HCO 3 ), carbonate (CO 3 ), and total alkalinity.

The laboratory analyses for major ions at Activation Laboratories are the

“Code 6B” and the “Code 6CAlkalinity.” The constituents that are included in the Code

6B and Code 6CAlkalinity Analyses are presented in Table 4. Laboratory results are attached as Appendix A, and results are discussed in subsequent sections of this report.

Inductively Coupled Plasma Mass Spectrometry

The Code 6 Analysis is conducted using ICPMS. ICPMS is a highly sensitive analytical technique that provides multielement and isotopic analyses for samples in solution. The ICPMS at Activation Laboratories uses a quadrupole mass filter

MS, and is capable of determining the concentrations of more than 70 elements at high sensitivity limits in a single analytical test.

TABLE 3. ACTIVATION LABORATORIES TRACE METALS CODE 6 ANALYSIS ANALYTE SYMBOLS Detection Detection limit Upper limit limit Upper limit Element (µg/L) (µg/L) Element (µg/L) (µg/L) Ag 0.2 00 02000 ___ Na 5 000 30000 ___ Al 2 00 50000 ___ Nb 0.005 As 0.03 0 Nd 0.004 Au 0.002 Ni 0.2 00 30000 ___ Ba 0.1 00 1000 ___ Os 0.002 Be 0.1 00 Pb 0.1 00 10000 ___ Bi 0.3 00 Pd 0.01 0 Br 3 00 Pr 0.001 Ca 50 000 500000 ___ Pt 0.01 0 Cd 0.01 0 1000 ___ Rb 0.01 0 Ce 0.002 Re 0.001 Co 0.005 500 ___ Ru 0.01 0 Cr 0.5 00 50000 ___ Sb 0.01 0 Cs 0.002 Sc 1 00 Cu 0.1 00 20000 ___ Se 0.2 00 Dy 0.001 Si 200 0000 Er 0.001 Sm 0.001 Eu 0.001 Sn 0.1 00 1000 ___ Fe 5 00 50000 ___ Sr 0.04 0 Ga 0.01 0 Ta 0.001 Gd 0.002 Tb 0.001 Ge 0.01 0 Te 0.01 0 Hf 0.002 Th 0.001 Hg 0.2 00 Ti 0.1 00 Ho 0.001 Tl 0.005 1000 ___ I 1 00 Tm 0.001 In 0.001 U 0.001 K 30 000 100000 ___ V 0.05 0 5000 ___ La 0.001 W 0.02 0 Li 1 00 Y 0.003 Lu 0.001 Yb 0.001 Mg 1 000 100000 ___ Zn 0.5 00 50000 ___ Mn 0.5 00 10000 ___ Zr 0.01 0 Mo 0.1 00 1000 ___

“An ICPMS combines a hightemperature ICP… source with a mass spectrometer. The ICP source converts the atoms of the elements in the sample to ions.

TABLE 4. ACTIVATION LABORATORIES ANION CODE 6B AND 6C ANALYSES Detection Limit Element (mg/L) Cl 0.03 2 SO 4 0.03 Alkalinity (as CaCO 3) 2 00 2 CO 3 1 00 HCO 3 1 00

These ions are separated and detected by the mass spectrometer” (Wolf,

2005). The ionization source for the ICPMS instrument is an argon plasma. The “argon gas flows inside the concentric channels of the ICP torch. The [radio frequency] RF load coil is connected to an … RF generator” (Wolf, 2005). Power is supplied by the generator to the load coil, and “oscillating electric and magnetic fields are established at the end of the torch. When a spark is applied to the argon flowing from the ICP torch, electrons are stripped off the argon atoms, forming argon ions. These ions are caught in the oscillating fields and collide with other argon atoms, forming an argon discharge or plasma” (Wolf,

2005).

During analysis, the sample is nebulized (converted from a liquid to an aerosol) into argon gas, and is introduced into the ICP torch, where atoms are

“completely desolvated and the elements in the aerosol are converted first into gaseous atoms and then ionized towards the end of the plasma” (Wolf, 2005). The positive ions in the plasma are then focused down a quadrupole MS through interface cones, a sampler, and a skimmer, which contribute a low pressure region within the MS. “The purpose of these cones is to sample the center portion of the ion beam coming from the ICP torch…”

(Wolf, 2005).

After the ions enter the MS, they are separated according to masstocharge ratio, detected, multiplied and counted. The quadrapole mass filter that MS has alternating AC (alternating current) and DC (direct current) voltages sent through opposite couples of four rods. “These voltages are rapidly switched along with an RF field. The result is that an electrostatic filter is established that only allows ions of a single masstocharge ratio … [to] pass through the rods to the detector at a given time”

(Wolf, 2005).

According to Activation Laboratories (2009a), water samples are spiked with internal standards to correct for matrix differences, and a repeat of every 10th sample is analyzed. Aliquots of the samples, standards or blanks, spiked with internal standards, are introduced into the ICPMS. The intensities of each atomic mass are measured. The elemental concentrations in the samples are calculated using standards and blanks.

Sample introduction, ionization, detection and data output were controlled by the system computer.

Ion Chromatography

Ion chromatography (IC), a form of liquid chromatography, measures constituents by separating them based on charge properties of the molecules and their resulting interactions with a resin. ICs can measure major anions and cations in a solution. In IC, a sample is manually or automatically introduced into a sample loop. A mobile phase buffered aqueous solution carries the sample through a pressurized chromatographic column where ions are absorbed by column constituents. As an ion extraction liquid (known as eluent) runs through the column, the absorbed ions are displaced from the stationary phase in the column (Weiss, 1995). The retention time of

different species distinguishes the ions in the sample. The IC system is controlled by a

chromatography data system that records the data obtained.

Selected water samples were analyzed for chloride and sulfate using IC.

According to Activation Laboratories (2009b), unacidified water samples are analyzed using a DIONEX DX120 Ion Chromatography System to determine and quantify anions.

Measurement uncertainty is evaluated and controlled using an internal quality assurance program. This includes the use of laboratory duplicates of samples and verification of the precision/calibration of the instrument through regular runs of primary dilution standard solutions.

Titrimetry

Titrimetry is a technique used to determine the quantity of an analyte in a

solution using reagents of known concentrations and reaction stoichiometry to determine

how much of an analyte reacts with a known amount of another compound in solution.

During titration, the solution is measured into a reaction vessel using a pipet. An indicator

compound is added to the solution and the reagent is placed in a burette, and is titrated

into the solution. The solution is mixed throughout the titration process to ensure that the

reaction reaches an endpoint, which is determined using an electrochemical device or by

observing color change induced by analyte reaction with the indicator compound.

EQ3NR Aqueous Speciation

EQ3NR determines the distribution of chemical species (i.e., ions, ion pairs,

and minerals) “using standard state themodynamic data and various equations which

describe the thermodynamic activity coefficients of these species” (Wolery, 1992c, p. 1).

The EQ3NR model relies on an iterative NewtonRaphson method to solve governing

equations for a system with assumed chemical equilibrium at a fixed pressure and

temperature (Wolery, 1979). The NewtonRaphson method is supported in EQ3NR by

several algorithms that “create and optimize starting values” (Wolery, 1992b).

EQ3NR uses thermodynamic affinities ( A) and saturation index ( SI ) to

evaluate the extent of disequilibrium for various reactions within the aqueous solution

(e.g., mineral dissolutions and redox reactions). Equations describing A (25) and SI (26)

are (Wolery, 1992c):

Q A = 2.303 RT log ; (25) K and

Q SI = log , (26) K where R is the gas constant (1.98726 cal/molK), T is the temperature ( K), Q is the activity product of a reaction, and K is the thermodynamic equilibrium constant.

To establish the equilibrium state and speciation of an aqueous solution, each

chemical component must have one constraint as input. Constraints may include total

analytical concentration, free concentration, activity, phase equilibrium requirement,

homogeneous equilibria, runspecific values for equilibrium constants, pH, Eh, pe, or

oxygen fugacity (Wolery, 1992c). Other inputs for EQ3NR may include “desired

electrical balancing adjustment and various constraints which impose equilibrium with

specified pure minerals, solid solution endmember components (of specified mole

fractions), and gases (of specified fugacities)” (Wolery, 1992c, p. 1). The most frequent

input is total analytical concentration of an individual constituent.

The EQ3 code simultaneously solves an array of equations that represent mass balance for each component, mass action (i.e., equilibrium) for each relevant reaction

among aqueous species, and charge balance, i.e., electroneutrality (Wolery, 1992b).

Calculations for various inputs are conducted in EQ3NR using the corresponding

mathematical expression that governs a specific input and provides the desired output.

The inputs are largely based on the availability and form of data, and the assumptions

desired by the modeler (Wolery, 1979, 1992b, 1992c).

Mass action is the scientific law that states that, for a chemical reaction at

equilibrium, the equilibrium constant is equal to the activity product of the reactants and products contained in the solution (Wolery, 1992c). For example, take the copper sulfate

ionpair disassociation (27):

2+ 2 CuSO 4 (aq) ↔ Cu + SO 4 . (27)

The corresponding mass action equation for the copper sulfate disassociation reaction

(shown in regular (28) and logarithmic (29) forms) are (Wolery, 1992c):

2+ 2 Cu [SO4 ] KCuSO4(aq) = ; (28) [CuSO4(aq)] and

2+ 2 log (KCuSO4(aq)) = log[Cu ] + log[SO 4 ] – log[CuSO 4(aq)]. (29)

Charge balance is the mass conservation of electrons shown in (30) (Wolery, 1992c):

ST ∑S=1 zsms = 0, (30)

where zs is the electrical charge of a species and ms is the molal concentration of a

chemical species.

Mass balance assures that a chemical element is not created or destroyed in a

reaction. Analytical chemical analysis generally provides a set of data for the total

concentration of a dissolved constituent in an aqueous solution. This total concentration

generally does not provide any data on the various species of the dissolved constituent in

an aqueous solution, but estimates the contributions of all forms of the dissolved

constituent. For example, a mass balance equation (31) for the total molal scale analytical

concentration of manganese (Wolery, 1992c):

m 2+ = m 2+ +m +m +m + + … , (31) T,Mn Mn MnOHaq MnCO3(aq) MnHCO3 where mT, Mn2+ is the total analytical molal scale concentration, and mi is the molality of an individual chemical species contributing to the mass balance.

As output, the EQ3NR code can compute equilibrium values for Eh, pe, Ah

(redox affinity), oxygen fugacity in redox reactions, and fugacities for other gas species.

The EQ3NR output file provides much information, including a list of distribution of aqueous species and their respective molal concentrations and activities. Additionally, a list of major aqueous species contributing to mass balance and their respective molal concentrations and percents, a summary of aqueous redox reactions, summary of stoichiometric mineral saturation states, and the summary of gas fugacities is provided, as is much additional information (depending on the input and output desired). The EQ3NR output includes both an output file and a pickup file so that the output may be used to initialize EQ6 reaction path calculations.

The electroneutrality constraint in EQ3NR is commonly achieved by adjusting the concentration of a selected major component. If the analytical data for the solution are accurate and complete then the adjustment to the concentration of the selected component

should be small relative to the uncertainty in its measurement. Large corrections may be

required for charge balance for a variety of reasons. For instance the chemical analysis

for the solution may be inaccurate or incomplete (it may not have been analyzed for some

important component). Another reason could be if the solution has changed between the

field measurements and when the laboratory measurements are taken (where dissolved

component concentrations are measured).

Given an equilibrium aqueous speciation model for the system, EQ3NR is

used to calculate the saturation state of the model solution with respect to a large number

of minerals that could precipitate from the aqueous solution. It also calculates the pressures of reactive gases (e.g., O 2, CO 2) that would be at equilibrium with the solution.

Often, analytical data for bicarbonate are uncertain because of the potential for

CO 2 volatilization or dissolution during sample handing prior to analysis, or variations in temperature. Bicarbonate is commonly selected to be adjusted to achieve charge balance in EQ3NR speciation due to these possible uncertainties, and because it is typically present in natural surface waters in high concentrations. This is also appropriate because

2 in all of the samples taken in this project, HCO 3 was present, and no CO 3 or H 2CO 3 present above the laboratory MDLs, because of the nearneutral pH.

As used in this study, EQ3NR treats all entered components as if they are at equilibrium in the aqueous phase. Laboratory results for filtered samples only were used for establishing aqueous speciation in this research, because, if the solution analyses include colloidal material, then the equilibrium aqueous solution model will not accurately represent the real conditions. Also, if aqueous reactions are not at equilibrium, then the EQ3NR code will not accurately reflect conditions. Disequilibrium is common in

73 lowtemperature aqueous systems, particularly for species that exist in different oxidation states. For example, disequilibrium is commonly observed in the relations between the concentrations of nitrogen species (e.g., nitrate, nitrite, dissolved nitrogen gas, ammonia) and between other oxidationreduction pairs and the DO content (Stefánsson et al., 2005).

The EQ3NR code is valuable for many reasons. The solutions modeled by the

EQ3NR code produce an evaluation of the completeness and accuracy of analytical data.

They provide an indication of the types of gaswaterrock interactions that control the aqueous solution composition.

The models can help identify conditions of disequilibrium, for example with regard to oxidationreduction reactions and supersaturations with respect to minerals. The models also identify the dominant species (e.g., aqueous complexes) that can transport metals of economic or environmental interest.

CHAPTER IV

FINDINGS AND RESULTS

Introduction

Effects of historic mining on surface water quality within the Lights Creek

Mineral District, primarily within the Moonlight Project, were examined using field and laboratory analyses of samples collected from November 2008 to May 2009. Select samples were also collected from the Walker Mine area (located approximately 25 kilometers southeast of the Moonlight Project) for evaluation of the site as a proximal analog to the Moonlight Project.

Field data measurements included temperature, pH, Eh, DO, and EC.

Commercial laboratory analyses provided data for major and trace element concentrations in filtered and unfiltered samples. Equilibrium aqueous speciation models were generated to evaluate controls on water chemistry for samples taken within the

Moonlight Project, and to develop ‘signature’ of mineaffected waters.

Presentation of the Findings

Field Parameter Data

Temperature . The minimum water temperature observed during monitoring events was at monitoring location MNWAT08 (Lights Creek) on 4 January 2009

(0.3°C). During this time the sampling locations were inaccessible by automobile, and approximately one inch of ice covered the sampling location. A hole was made with a

snowshoeing pole and field parameters were measured after approximately 20 minutes.

The maximum temperature of 16.6°C was observed on 14 May 2009 at monitoring

location MNWAT12 (Feather River at Paxton Road Bridge). Temperatures in adit

entrances were generally higher than those observed at other monitoring locations.

Temperature measurements, which varied seasonally, are presented in Table 5 and Figure

22.

pH . Field measurements of pH ranged from 6.59 to 8.52. No significantly

acidic waters were detected. The Hanna® HI 991200 meter was not calibrating accurately

on 18 October 2009, thus, these results are not reported. Field measurements for pH are presented in Table 6 and Figure 23.

Electrical Conductivity . The EC ranged from 50.0538.8 µS/cm in all water samples taken. Elevated EC levels were observed in adit entrances, except at Walker

Mine. EC field measurements are presented in Table 7 and Figure 24. The EC within adit entrances generally fall in the higher range within the oval, while the EC at other locations generally are lower, and fall within the rectangle.

Dissolved Oxygen . DO measurements ranged from 38.6107.1 percent saturated. Most values indicated waters were nearly 100 percent saturated; however monitoring location MNWAT09 (the adit entrance to Engels Mine) typically displayed low measurements, with an average of 53.2 percent saturated. Low values were also observed at monitoring location MNWAT11 (50 ft downstream of Engels Mine #10

Level), which averaged 55.4 percent saturated. Field measurements of DO are presented in Table 8 and Figure 25.

Oxidation/Reduction Potential . Eh measurements ranged from 266.0 to 387.8

mV during the monitoring period, and are presented in Table 9 and Figure 26.

Laboratory Analytical Data

Discussion of laboratory results for selected data are presented in the following sections. All constituents that were included in laboratory analysis and are regulated by, or have established guidelines promulgated by the EPA, are shown in Table

10. Discussion of particular constituents present in sampled waters above their respective

U. S. Environmental Protection Agency Maximum Contaminant Level (MCLs),

Secondary Maximum Contaminant Levels (SMCLs), or Treatment Technique (TT)

Action Levels for drinking water are discussed in the following sections. Laboratory results are presented in Appendix A.

Quality Assurance/Quality Control

Laboratory results for elemental concentrations detected in the field duplicate

MNWAT13 generally corresponded with those observed at monitoring location

MNWAT16. Laboratory analytical results are presented in Table 11 for major anions at

MNWAT16 v. MNWAT13.

Additionally, sulfate demonstrated a discrepancy that slightly exceeded the

nominal laboratory upper limits of detection. Plots reflecting laboratory elemental

analytical results for monitoring location MNWAT16 v. MNWAT13 at different axis

scales are shown in Figure 27 through Figure 29. As may be observed, results of analysis

of the monitoring location MNWAT16 and the field duplicate MNWAT13 are

generally consistent, demonstrating laboratory accuracy.

TABLE 5. TEMPERATURE DATA, OCTOBER 2008 THROUGH MAY 2009 (°C) 04Jan09 04Jan09 12Oct08 12Oct08 18Oct08 24Apr09 24Apr09 25Apr09 26Dec08 26Dec08 22Mar09 22Mar09 23Mar09 13Nov08 13Nov08 23Nov08 Site ID 14May09 15May09 MNWAT01 07.3 N.D. * 09.3 N.D. * N.D. * 07.1 N.D. * 07.4 N.D. * 09.0 N.D. * 09.1 MNWAT02 07.2 N.D. * N.D. * N.D. * N.D. * N.D. * 5.9 N.D. * N.D. * 07.1 N.D. * N.D. * MNWAT03 05.8 N.D. * 09.2 N.D. * 01.1 N.D. * 3.7 N.D. * 09.4 N.D. * 14.7 N.D. * MNWAT04 07.0 10.5 11.8 N.D. * 01.4 N.D. * 4.9 N.D. * 10.1 N.D. * 14.6 N.D. * MNWAT05 06.8 08.3 08.4 N.D. * N.D.* N.D. * N.D. * N.D. * 09.9 N.D. * 14.9 N.D. * MNWAT06 N.D. * 10.2 10.1 05.7 00.9 N.D. * 6.3 N.D. * 10.3 N.D. * 12.8 N.D. * MNWAT07 N.D. * 09.7 10.2 N.D. * 02.7 N.D. * 5.7 N.D. * 10.0 N.D. * 13.5 N.D. * MNWAT08 05.7 N.D. * 09.9 N.D. * N.D. * 00.3 3.6 N.D. * 09.9 N.D.* 14.2 N.D. * MNWAT09 12.1 N.D. * 14.2 12.6 11.8 N.D. * 5.6 N.D. * N.D. * 11.2 N.D. * 12.6 MNWAT10 07.5 N.D. * 06.1 N.D. * N.D. * N.D. * 4.3 N.D. * 07.8 N.D. * 12.1 N.D. * MNWAT11 N.D. * N.D. * 14.5 12.1 11.7 N.D. * 5.7 N.D. * N.D. * 11.4 N.D. * 12.2 MNWAT12 N.D.* N.D. * 12.1 N.D. * N.D. * N.D. * N.D. * 07.3 N.D. * 10.2 16.6 N.D. * MNWAT14 N.D. * N.D. * 08.0 08.5 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT15 N.D. * N.D. * 08.6 07.8 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT16 N.D. * N.D. * N.D. * N.D. * 03.9 N.D. * N.D. * 05.7 N.D. * 08.9 N.D. * 12.6 MNWAT17 N.D. * N.D. * N.D. * 02.8 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT18 N.D. * N.D. * N.D. * 04.2 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * * N.D. = not determined.

Temperature (˚C) Temperature 6

0 6Jul09 6Feb09 9Sep08 29Oct08 18Dec08 28Mar09 17May09 Date

MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 22. Temperature Data, October 2008 through May 2009 78

TABLE 6. pH DATA, OCTOBER 2008 THROUGH MAY 2009

Site ID 12Oct08 18Oct08 13Nov08 23Nov08 26Dec08 04Jan09 22Mar09 23Mar09 24Apr09 25Apr09 14May09 15May09 MNWAT01 7.39 N.D. * 7.67 N.D. * N.D. * 7.63 N.D. * 7.82 N.D. * 7.64 N.D. * 8.23 MNWAT02 7.13 N.D. * N.D. * N.D. * N.D. * N.D. * 7.58 N.D. * N.D. * 7.63 N.D. * N.D. * MNWAT03 6.90 N.D. * 7.50 N.D. * 7.74 N.D. * 7.78 N.D. * 7.69 N.D. * 7.84 N.D. * MNWAT04 7.30 N.D. * 6.83 N.D. * 6.59 N.D. * 7.50 N.D. * 7.54 N.D. * 7.40 N.D. * MNWAT05 7.31 N.D. * 7.56 N.D. * N.D. * N.D. * N.D. * 7.98 N.D. * 8.05 N.D. * MNWAT06 N.D. * N.D. * 7.06 7.22 7.40 N.D. * 7.57 N.D. * 7.15 N.D. * 7.65 N.D. * MNWAT07 N.D. * N.D.* 7.57 N.D. * 7.71 N.D. * 7.98 N.D. * 8.21 N.D. * 8.03 N.D. * MNWAT08 7.30 N.D. * 7.55 N.D. * N.D. * 7.35 7.83 N.D. * 7.86 N.D. * 7.99 N.D. * MNWAT09 7.29 N.D. * 6.87 6.88 6.92 N.D. * 7.41 N.D. * N.D. * 7.15 N.D. * 7.37 MNWAT10 7.30 N.D. * 7.54 N.D. * N.D. * N.D. * 7.94 N.D. * 8.05 N.D. * 8.16 N.D. * MNWAT11 N.D. * N.D. * 6.83 7.03 7.08 N.D. * 7.44 N.D. * N.D. * 7.23 N.D. * 7.31 MNWAT12 N.D. * N.D. * 7.65 N.D. * N.D. * N.D. * N.D. * 7.81 N.D. * 8.01 7.73 N.D. * MNWAT14 N.D. * N.D. * 6.73 6.65 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT15 N.D. * N.D. * 6.83 7.68 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT16 N.D. * N.D. * N.D. * N.D. * 7.58 N.D. * N.D. * 8.12 N.D. * 8.05 N.D. * 8.52 MNWAT17 N.D. * N.D. * N.D. * 7.36 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT18 N.D. * N.D. * N.D. * 7.68 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * * N.D. = not determined.

8.5

7.5 pH 7

6.5

6 6Jul09 6Feb09 9Sep08 29Oct08 18Dec08 28Mar09 17May09 Date MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 23. pH Data, October 2008 through May 2009. 80

TABLE 7. ELECTRICAL CONDUCTIVITY DATA, OCTOBER 2008 THROUGH MAY 2009 (µS/cm)

Site ID 12Oct08* 18Oct08* 13Nov08* 23Nov08 26Dec08 04Jan09 22Mar09 23Mar09 24Apr09 25Apr09 14May09 15May09 MNWAT01 469 N.D. † 420 N.D. † N.D. † 523.0 N.D. † 269.1 N.D. † 389.5 N.D. † 410.0 MNWAT02 145 N.D. † N.D. † N.D. † N.D. † 122.7 N.D. † N.D. † 187.9 N.D. † N.D. † MNWAT03 121 N.D. † 103 N.D. † 126.1 N.D. † 091.2 N.D. † 095.6 N.D. † 081.7 N.D. † MNWAT04 127 135 118 N.D. † 142.1 N.D. † 100.5 N.D. † 099.7 N.D. † 087.1 N.D. † MNWAT05 141 143 124 N.D. † N.D. † N.D. † N.D. † N.D. † 156.2 N.D. † 101.0 N.D. † MNWAT06 N.D. † 050 051 083.5 066.1 N.D. † 052.0 N.D. † 069.3 N.D. † 54.4 N.D. † MNWAT07 N.D. † 169 152 N.D. † 189.6 N.D. † 117.9 N.D. † 110.5 N.D. † 098.0 N.D. † MNWAT08 117 N.D. † 103 N.D. † N.D. † 130.6 95.4 N.D.† 101.3 N.D. † 080.1 N.D. † MNWAT09 492 N.D. † 469 528.0 534.0 N.D. † 526.0 N.D. † N.D. † 520.0 N.D. † 497.0 MNWAT10 120 N.D. † 141 N.D. † N.D. † N.D. † 135.0 N.D. † 141.6 N.D. † 129.7 N.D. † MNWAT11 N.D. † N.D. † 464 530.0 528.0 N.D. † 479.0 N.D. † N.D. † 538.8 N.D. † 456.0 MNWAT12 N.D. † N.D. † 196 N.D. † N.D. † N.D. † N.D. † 100.6 N.D. † 089.3 098.1 N.D. † MNWAT14 N.D. † N.D. † 097 127.1 N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † MNWAT15 N.D. † N.D. † 199 292.0 N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † MNWAT16 N.D. † N.D. † N.D. † N.D. † 225.2 N.D. † N.D. † 150.3 N.D. † 137.0 N.D. † 195.9 MNWAT17 N.D. † N.D. † N.D. † 144.2 N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † MNWAT18 N.D. † N.D. † N.D. † 246.4 N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † N.D. † *Indicates that measurements were taken with the Hanna 991300 meter † N.D. = not determined.

600

500

400

300 EC (µS/cm) EC 200

100

0 09 09 May May 6Jul09 6Feb09 9Sep08 29Oct08 18Dec08 28Mar09 Date 17 17 MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 24. Electrical Conductivity Data, October 2008 through May 2009 82

TABLE 8. DISSOLVED OXYGEN DATA, OCTOBER 2008 THROUGH MAY 2009 (PERCENT SATURATED)

Site ID 12Oct08* 18Oct08* 13Nov08* 23Nov08 26Dec08 04Jan09 22Mar09 23Mar09 24Apr09 MNWAT01 N.D. * N.D. * 097.8 N.D. * N.D. * N.D. * 093.5 N.D. * 096.9 MNWAT02 N.D. * N.D. * N.D. * 096.1 N.D. * N.D.* 089.4 N.D. * N.D. * MNWAT03 N.D. * 100.7 N.D. * 097.5 N.D. * 099.2 N.D. * 077.2 N.D. * MNWAT04 N.D. * 093.2 N.D. * 098.8 N.D. * 071.5 N.D. * 069.4 N.D. * MNWAT05 N.D. * N.D. * N.D. * N.D. * N.D. * 098.3 N.D. * 065.5 N.D. * MNWAT06 094.4 105.7 N.D. * N.D. * N.D. * 091.6 N.D. * 084.3 N.D. * MNWAT07 N.D. * 107.1 N.D. * N.D. * N.D. * 102.1 N.D. * 100.7 N.D. * MNWAT08 N.D. * N.D. * 093.6 090.3 N.D. * 100.2 N.D. * 099.3 N.D. * MNWAT09 049.3 055.4 N.D. * N.D. * N.D. * N.D. * 045.6 N.D. * 053.2 MNWAT10 N.D. * N.D. * N.D. * N.D. * N.D. * 091.5 N.D. * 102.2 N.D. * MNWAT11 050.7 071.0 N.D. * N.D. * N.D. * N.D. * 061.3 N.D. * 038.6 MNWAT12 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * 082.4 078.9 N.D. * MNWAT14 095.9 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT15 083.6 N.D. * N.D. * N.D.* N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT16 N.D. * 099.9 N.D. * N.D. * N.D. * N.D. * 102.5 N.D. * 101.6 MNWAT17 094.4 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * MNWAT18 096.5 N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * N.D. * * N.D. = not determined.

115

105

55 Dissolved Oxygen (% saturated) Oxygen Dissolved 45

35 7Jan09 8Mar09 8Nov08 7May09 27Jan09 16Feb09 17Apr09 18Dec08 28Mar09 28Nov08 27May09 Date MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 25. Dissolved Oxygen Data, October 2008 through May 2009. 84

TABLE 9. Eh DATA, APRIL THROUGH MAY 2009 (mV) Site ID 24Apr09 25Apr09 14May09 15May09 MNWAT01 N.D. * 337.5 N.D. * 266.0 MNWAT02 N.D. * 387.8 N.D. * N.D. * MNWAT03 310.7 N.D. * 328.4 N.D. * MNWAT04 267.8 N.D. * 332.9 N.D. * MNWAT05 313.1 N.D. * 273.8 N.D. * MNWAT06 386.9 N.D. * 353.5 N.D. * MNWAT07 276.8 N.D. * 272.0 N.D. * MNWAT08 283.6 N.D. * 272.1 N.D. * MNWAT09 N.D. * 310.3 N.D. * 300.3 MNWAT10 347.4 N.D. * 270.7 N.D. * MNWAT11 N.D. * 274.0 N.D. * 287.5 MNWAT12 N.D. * 387.4 320.0 N.D. * MNWAT14 N.D. * N.D. * N.D. * N.D. * MNWAT15 N.D. * N.D. * N.D. * N.D. * MNWAT16 N.D. * 294.3 N.D. * 273.0 MNWAT17 N.D. * N.D. * N.D. * N.D. * MNWAT18 N.D. * N.D. * N.D. * N.D. * * N.D. = not determined.

However, in Figure 27, which shows concentrations from 016µg/L, some

results for samples collected on May 15, 2009 vary. Explanations for this variance may

include the presence of colloidal materials or sample collection error or laboratory error.

The increasing inconsistency in measurements at lower concentrations may be at least partially explained by the effects of MDLs.

Selected Elemental Data

The occurrence of dissolved and colloidal metals and metalloids in an aqueous

system are of primary importance for determining the extent of contamination from hard

rock mines in surface waters, since they generally are present in high concentrations

when sulfide minerals are leached in AMD.

400

375

350

325 Eh (mV) Eh

300

275

250 2May09 7May09 22Apr09 27Apr09 Date 12May09 17May09 MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 26. Eh, April 2008 through May 2009. 86

TABLE 10. EPA DRINKING WATER MCL, SMCL, OR TT ACTION LEVEL FOR ANALYZED CONSTITUENTS Constituent MCL SMCL TT Action Level (mg/L) § (mg/L) § (mg/L) § Aluminum N.A. † 0.05 to 0.2 N.A. † Antimony 0.006 N.A. † N.A. † Arsenic 0.010 N.A. † N.A. † Barium 2. 00 N.A. † N.A. † Cadmium 0.005 N.A. † N.A. † Copper * N.A. † 1.0 000 1.3 †00 Cyanide (as free Cyanide) 0.2 00 N.A. † N.A. † Iron N.A. † 0.3 000 N.A. † Lead * N.A. † N.A. † 0.015 † Manganese N.A. † 0.05 00 N.A. † Mercury (inorganic) 0.002 N.A. † N.A. † Selenium 0.05 0 N.A. † N.A. † Silver N.A. † 0.10 0 N.A. † Sulfate N.A. † 250. 0000 N.A. † Thallium 0.002 N.A. † N.A. † Uranium 30 µg/L N.A. † N.A. † Zinc N.A. † 5. 00 N.A. † * Lead and copper are regulated by a Treatment Technique that requires systems control the corrosiveness of their water. If more than 10 percent of tap water samples exceed the action level, water systems must take additional steps. † Not applicable, limit does not exist for given constituent. § Units in mg/L, except where otherwise noted.

Data for important metals and other constituents of primary importance for

evaluating potential mining impacts on background environmental conditions at the

Moonlight Project are discussed in the following sections.

Copper . Copper was present above its MDL (0.02 µg/L) in all samples collected at both the Moonlight Project and Walker Mine sites, with the exception of the field duplicate sample MNWAT13 on 23 March 2009 (on which day the MNWAT16

[for which MNWAT13 is a field duplicate] had copper present in a concentration of 4

µg/L ).

TABLE 11. MEASURED MAJOR ANION CONCENTRATIONS IN MNWAT16 (SODA CREEK) AND MNWAT13 (FIELD DUPLICATE) Anion Laboratory MNWAT13 MNWAT16 Detection Limit mg/L mg/L (mg/L) Cl 0.03 0 0 0 0 2 SO 4 0.03 13.4 00 13.3 00 Alkalinity (as CaCO 3) 2 0 88 00 88 00 2 CO 3 1 0 0 0 0 0 HCO 3 1 0 88 00 88 00

Besides the nondetect at MNWAT13, copper in the filtered and unfiltered

water samples collected during the research ranged from 0.4 µg/L at monitoring location

MNWAT16 (Soda Creek) to a maximum that exceeded 800 µg/L at monitoring location

MNWAT01 (Superior Mine #2 Level). Unfiltered/undiluted, and field filtered samples

had copper present over the upper limit of 200 µg/L at MNWAT01 and

unfiltered/undiluted samples at MNWAT11.Unfiltered and diluted samples for MN

WAT01 had copper present in concentrations over the upper method detection limit of

200 µg/L (on March 23 and May 15, 2009). The copper concentration in the filtered MN

WAT01 sample taken on May 15, 2009, also had copper present in concentrations over

the upper method detection limit of 200 µg/L. Therefore, copper concentrations in the

unfiltered samples for MNWAT01 exceeded 800 µg/L on March 23 and May 15, 2009,

and copper concentrations in the filtered sample for MNWAT01 exceeded 400 µg/L on

May 15, 2009. The highest copper concentrations at the Moonlight Project were observed

at monitoring location MNWAT01 (Superior Mine #2 level adit entrance), MNWAT

09 (Engels Mine adit entrance), and monitoring location MNWAT11 (Engels Mine

downstream from the adit entrance).

16 Cu 14

12 Zn 10

8 Ti 6 Pb 4 V I 2

0 0 5 10 15 Concentration of Constituent in MNWAT16 (µg/L) MNWAT16 inConstituent of Concentration Concentration of Constituent in Field Duplicate MN WAT 13 (µg/L) 12/26/2008 3/23/2009 05/15/2009

Figure 27. Measured elemental concentrations, 0 – 16 µg/L MN WAT16 (Soda Creek) v. MNWAT13 (field duplicate) .

A difference in average copper concentrations between the adit entrance locations and other sampling locations (including both filtered and unfiltered sam ples) was apparent. The lower limit on the average copper concentration in adit entrances was

97.6 µg/L and the lower limit on the standard deviation was 31.7 µg/L (because copper was present above the upper limit of detection in some of the samples collec ted in adit entrances, the average and standard deviation are reported as lower limits). The average copper concentration in all non adit locations was 9.1 µg/L with a standard deviation of

17.0 µg/L.

20,000

18,000

16,000

14,000

12,000

10,000

8,000

6,000

4,000

2,000

0 ConcentrationofConstituent in MNWAT16(µg/L) 0 2,000 4,000 6,000 8,000 10,000 12,000 14,000 16,000 18,000 20,000 Concentration of Constituent in Field Duplicate MNWAT13 (µg/L)

12/26/2008 3/23/2009 05/15/2009

Figure 28. Measured elemental concentrations, 0 – 20,000 µg/L MNWAT16 (Soda Creek) v. MNWAT13 (field duplicate).

Although no EPA drinking water MCL exists for copper, the EPA has set a treatment technique level of 1.3 mg/L for copper, which means that water distribution systems must control their concentrations of copper to this level (EPA, 2009).

Gold . Gold is a secondary target of exploration at Moonlight Project. During

the first half of the field study, gold was present in unfiltered samples above its MDL

(0.002 µg/L) at monitoring locations MNWAT01 through MNWAT09, MNWAT11,

MNWAT12, MNWAT15, and MNWAT16. During March through May, gold was

detected in unfiltered samples at monitoring locations MNWAT03, MNWAT04,

MNWAT08, and MNWAT12.

45,000

40,000

35,000

30,000

25,000

20,000

15,000

10,000

5,000

0 ConcentrationofConstituent in MNWAT16(µg/L) 0 5000 10000 15000 20000 25000 30000 35000 40000 45000 Concentration of Constituent in Field Duplicate MNWAT13 (µg/L)

12/26/2008 3/23/2009 05/15/2009

Figure 29. Measured elemental concentrations, 0 – 45,000 µg/L MNWAT16 (Soda Creek) v. MNWAT13 (field duplicate).

In the field filtered samples, gold was present only in monitoring locations

MNWAT04 on May 14, 2009 (0.003 µg/L), indicating that the majority of the gold

detected during analyses was in the colloidal form. Gold in filtered and unfiltered

samples collected during this research project ranged from below its MDL to a maximum

of 0.036 µg/L at monitoring location MNWAT08 (unfiltered sample at China Gulch).

The latter finding may be explained the presence of gold in a solid colloidal form.

Mercury . Mercury was not present above its MDL (0.2 µg/L) in any of the

samples collected during the research project period. The EPA drinking water MCL for

inorganic mercury (which is biotoxic and bioaccumulative) is 2 µg/L.

Arsenic . Arsenic in the filtered and unfiltered water samples during the research project ranged from 0.9 µg/L to 23.2 µg/L at monitoring location MNWAT09

(Engels Mine adit entrance). The concentration of arsenic at adit openings is elevated, with an average concentration of 17.2 µg/L, compared to an average concentration of 1.5

µg/L at other sampling locations. The EPA drinking water MCL for arsenic is 10 µg/L

(EPA, 2009). Arsenic concentrations that exceeded the MCL were observed in both filtered and unfiltered samples at several monitoring locations during numerous monitoring events.

Zinc . Zinc concentrations in the filtered and unfiltered water samples

collected during the research project ranged from below its MDL (0.5 µg/L) to a

maximum of 85.6 µg/L at monitoring location MNWAT02 (Blue Copper Mine adit).

As with copper, the concentrations of zinc at adit openings is elevated, with an average

concentration of 24.1 µg/L, compared to an average concentration of 4.3 µg/L at other

sampling locations. Although no EPA drinking water MCL exists for zinc, the EPA has

established a drinking water SMCL of 5 mg/L for zinc (EPA, 2009). Zinc concentrations

in the waters sampled did not exceed the SMCL during the monitoring period.

Silver . Although the Moonlight Project is cited as a coppergoldsilver enterprise, it is known that silver is present in lower amounts compared to copper and gold (Storey, 1978). During the first monitoring period silver was not present above its

MDL (0.02 µg/L) in any of the filtered or unfiltered water samples collected at Moonlight

Project. However, silver was detected in unfiltered samples at monitoring locations MN

WAT14 (0.6 µg/L) and MNWAT15 (12.1 µg/L), which are the adit entrance of Walker

Mine and the drainage culvert by Walker Mine, respectively. Silver was also present

93 above its MDL in filtered samples at MNWAT10 and MNWAT11, although this result is questionable since it was not detected above its MDL in unfiltered samples taken at the same location on the same day. Although no EPA drinking water MCL exists for silver, the EPA has established a drinking water SMCL of 100 µg/L for silver (EPA,

2009). Silver concentrations in the waters sampled did not exceed the SMCL during the monitoring period.

Antimony . The EPA drinking water MCL for antimony is 6 µg/L (EPA,

2009). The antimony concentration at monitoring location MNWAT01 exceeded the

drinking water MCL in all of the samples collected, and exceeded the MCL in field

duplicate MNWAT13 during one monitoring event (although antimony did not exceed

the drinking water MCL at MNWAT16, where the field duplicate was obtained). In

addition, antimony exceeded the MCL in the field filtered sample for monitoring location

MNWAT01.

Lead . Lead was present above its MDL in both the filtered and unfiltered samples at all monitoring locations with the exception of the filtered sample at monitoring location MNWAT01 and the unfiltered sample at MNWAT05. Although no EPA drinking water MCL exists for lead, the EPA has established a TT action level of

15 µg/L for lead (EPA, 2009). Lead concentrations in the waters sampled did not exceed the TT action level during the monitoring period.

Manganese . Manganese was detected in laboratory results for all the field

filtered water samples. The highest concentrations occurred at monitoring locations MN

WAT01, MNWAT09, and MNWAT11, where manganese concentrations of 184

µg/L, 21.2 µg/L, and 25.8µg/L, respectively, were observed on 1415 May 2009. The

EPA has established a drinking water SMCL for manganese of 50 µg/L, which was not exceeded during the monitoring period.

Field measurements of DO using a polarographic meter on 1415 May 2009 at

MNWAT01, MNWAT09, and MNWAT11 were 96.9 percent saturated, 53.2 percent saturated, and 38.6 percent saturated, respectively. However, in cases where dissolved manganese is present in reduced waters (generally groundwater) and are exposed to oxygen (such as when the water exits a mine adit and becomes surface water), the manganese generally oxidizes to form manganese oxide species that precipitate from the surface water. Thus, the presence of manganese dissolved in surface waters that contain DO poses an interesting question, as the metals typically oxidized and precipitate from the solution under the observed conditions (Hem, 1963).

One explanation for the presence of dissolved manganese in the waters is that rocks surrounding the sampling location contain reduced manganese that is being weathered (dissolved) by waters. The DO content of the water is not reflective of the manganese oxidation states in the water.

Correlations . Concentrations of arsenic and copper in water samples demonstrate a strong correlation for unfiltered samples. These concentrations are bimodally distributed, depending on location, as may be observed in Figure 30. Points within the circle represent concentrations in adit entrances and points within the square represent concentrations observed at other sampling locations. No correlation between concentrations of arsenic and copper in filtered water samples is observed (see Figure

31), although this may be due to the limited number of filtered samples collected, and the low concentrations in filtered samples.

450 400 350 300 250 200

Concentration (µg/L) (µg/L) Concentration 150 100

Copper Copper 50 0 0 5 10 15 20 25 Arsenic Concentration (µg/L) MNWAT01 MNWAT02 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT14 MNWAT15 MNWAT16 MNWAT17 MNWAT18

Figure 30. Copper v. arsenic concentration in unfiltered water samples.

Multiple Dilution Concentrations . Quantitatively diluted water samples were prepared from selected locations where elements were previously detected at

concentrations that exceeded their respective upper limits of detection. These elements

included calcium and strontium at monitoring locations MNWAT01, MNWAT09,

MNWAT11, MNWAT16, and MNWAT18, and copper at MNWAT01. Although

some of the analyses demonstrated that these constituents were still present above their

upper limits of detection in the quantitatively diluted samples, several of these samples provided distinct results. Plots of 2 times the quantitatively diluted concentrations v.

undiluted concentrations in the water samples are presented as Figure 32 through Figure

34. As with the case where duplicate analyses were performed, there is a strong

96 correlation, especially at high concentrations, which is an indication of good precision of analytical results.

30 Concentration

20 Copper Copper 10

0 0 5 10 15 20 25 Arsenic Concentration (µg/L) MNWAT01F MNWAT03F MNWAT04F MNWAT05F MNWAT06F MNWAT07F MNWAT08F MNWAT09F MNWAT10F MNWAT12F MNWAT16F 1:1 Line

Figure 31. Copper v. arsenic concentration in filtered water samples.

Filtered and Unfiltered Concentrations . Filtered water samples were obtained

from selected monitoring locations to determine the fractions of colloidal and dissolved

solids in samples. The combination of filtered and unfiltered samples aids in establishing

the overall water chemistry, and determining the extent to which colloids are present in

the unfiltered analyses. Plots showing laboratory elemental analytical results for

unfiltered v. filtered samples at various scales are presented as Figure 35 and Figure 36.

40,000

35,000

30,000

25,000

20,000

15,000

10,000

5,000 2X Diluted Concentrations (µg/L) Diluted Concentrations 2X 0 0 10,000 20,000 30,000 40,000 Undiluted Concentrations (µg/L) MNWAT01 3/23/2009 MNWAT01 5/15/2009 MNWAT09 3/22/2009 MNWAT09 5/15/2009 MNWAT11 3/22/2009 MNWAT11 5/15/09 MNWAT16 3/23/2009 MNWAT16 5/15/09

Figure 32. Quantitatively diluted v. undiluted concentrations of Code 6 metals in water samples, 0 – 40,000 µg/L.

The laboratory results for monitoring location MNWAT05 are inconsistent.

Low sodium, silica, magnesium, and calcium in the unfiltered samples probably represent analytical error, and high potassium and aluminum in the MNWAT05 unfiltered sample could reflect a clay colloid. The anomalous result for copper at monitoring location MN

WAT11 is unexplained, as it reflects that the laboratory detected a higher concentration of copper in the filtered sample than the unfiltered sample. The higher copper concentration in the filtered sample could be due to analytical or sampling error in either the filtered or unfiltered sample (or both).

200 180 160 140 120 100 80 60 40 2X Diluted Concentrations (µg/L) Diluted Concentrations 2X 20 0 0 50 100 150 200 Undiluted Concentrations (µg/L) MNWAT01 3/23/2009 MNWAT01 5/15/2009 MNWAT09 3/22/2009 MNWAT09 5/15/2009 MNWAT11 3/22/2009 MNWAT11 5/15/09 MNWAT16 3/23/2009 MNWAT16 5/15/09

Figure 33. Quantitatively diluted v. undiluted concentrations of Code 6 metals in water samples, 0 – 200 µg/L.

Major Ion Analytical Data

The results of major anion (sulfate, chloride, bicarbonate, carbonate) and

cation (sodium, calcium, potassium, and magnesium) analyses for unfiltered samples

demonstrated general trends in the types of waters sampled. Results indicated calcium bicarbonate type water for all sampled locations, with the exception of monitoring

location MNWAT01 (Superior Mine #2 Level), which results indicate is a calcium

sulfate type water.

5 2X Diluted Concentrations (µg/L) Diluted Concentrations 2X

0 0 5 10 15 20 25 Undiluted Concentrations (µg/L) MNWAT01 3/23/2009 MNWAT01 5/15/2009 MNWAT09 3/22/2009 MNWAT09 5/15/2009 MNWAT11 3/22/2009 MNWAT11 5/15/09 MNWAT16 3/23/2009 MNWAT16 5/15/09

Figure 34. Quantitatively diluted v. undiluted concentrations of Code 6 Metals in water samples, 0 – 25 µg/L.

Results of major ion analysis using filtered samples indicated calcium bicarbonate type water for all sampled locations, with the exception of monitoring location MNWAT01 (Superior Mine #2 Level), which plotted as a calciumsulfate type water.

Alkalinity is a complicated function and is defined in various ways; however, the most conventional definition is that 50 mg/L alkalinity (as CaCO 3) corresponds to 61

mg/L bicarbonate (HCO 3 ) if all of the alkalinity is due to bicarbonate. Data show that the

dominant anion is bicarbonate. This is due to a variety of factors, primary the pH and

100

temperature of the system (which are each also interdependent). Typically, in nearly

2 neutral pH natural waters, there will not be any CO2, CO 3 , or HCO 3 present.

2,000 1,800 MNWAT16: K 1,600 1,400 1,200 1,000 MNWAT06: K 800 600 MNWAT12: K 400 MNWAT11: Cu 200 Concentration Concentration (µg/L) Unfiltered 0 0 500 1,000 1,500 2,000 Concentration Filtered (µg/L) MNWAT01 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT16

Figure 35. Unfiltered v. filtered concentrations, October 2008 through May 2009, 0 – 2,000 µg/L.

The alkalinity was reported (as CaCO 3) by the laboratory to be identical to the bicarbonate concentrations, since the laboratory calculates the bicarbonate concentration

from the alkalinity and pH, which was reported to be significantly elevated. This is likely

due to the time between sample collection and analysis. However, the values for pH

reported by the laboratory varied between 7.8 and 8.1, which does not explain this

discrepancy.

101

45,000 40,000 35,000 30,000 25,000 20,000 15,000 10,000 5,000 Concentration Concentration (µg/L) Unfiltered 0 0 10,000 20,000 30,000 40,000 Concentration Filtered (µg/L) MNWAT01 MNWAT03 MNWAT04 MNWAT05 MNWAT06 MNWAT07 MNWAT08 MNWAT09 MNWAT10 MNWAT11 MNWAT12 MNWAT16

Figure 36. Unfiltered v. filtered concentrations, October 2008 through May 2009, 0 – 45,000 µg/L.

EQ3NR Aqueous Speciation

Data for filtered samples from all monitoring locations were analyzed with

EQ3NR using field values of pH, temperature, and Eh or DO. Adjustment of the

analytical bicarbonate concentration is used to achieve electroneutrality in the model

solutions, with the exception of for MNWAT01F and MNWAT11F. For these

samples, which consistently demonstrated the presence of calcium above its upper limits

of detection (in unfiltered, filtered, and quantitatively diluted samples) 20 mg/L,

adjustments for charge balance were performed using calcium. Adjustments were carried

out on HCO 3 in most samples since it is the dominant anion for the surface waters from

102

the Moonlight Project area, and due to the uncertainty of laboratory bicarbonate

calculations.

To illustrate the EQ3NR aqueous speciation results, laboratory analytical results from MNWAT01F and MNWAT07F are considered to be representative monitoring locations for the two regions of the bimodally distributed data discussed earlier. As such, EQ3NR results for the MNWAT01F and MNWAT07F locations are discussed.

Electrical balancing for MNWAT01F was performed by adjusting calcium.

This resulted in a +11.8 mg/L adjustment in calcium concentration (where the calcium

input was 40 mg/L and the adjusted output was 51.8 mg/L). This calcium adjustment is

consistent with the analytical result that 20 mg/L was a lower limit on the calcium

concentration for the 2x quantitatively diluted sample. The calculated Eh for MNWAT

01F in the EQ3NR trial when log oxygen fugacity was used as the redox constraint

761.0 mV, compared to the field measured Eh, 266.0 mV. The Eh difference indicates

that the DO content of the water was not at equilibrium with the aqueous species that

controlled the Eh electrode measurement.

Electrical balancing was performed by adjusting bicarbonate for MNWAT

07F because all other concentrations were known, because of the possibility of CO 2 volatilization during handing prior to analysis, and because the accuracy of the analytical bicarbonate data were in question. Electrical balancing resulted in a +10.8 mg/L

adjustment in bicarbonate concentration (where the bicarbonate input was 47 mg/L and

the adjusted output was 57.8 mg/L). The bicarbonate result indicates an excess of cations

or a deficiency of anions in the chemical analysis. Similarly, the calculated Eh at MN

103

WAT07F (in the EQ3NR trial when log oxygen fugacity was used as the redox

constraint) was calculated to be 764.5 mV, compared to the field measured Eh, 272.0

mV. An unexplained result in laboratory analyses was the presence of silver in this

location in the filtered, but not the unfiltered sample. Because of this result, the analysis

for silver at MNWAT07F is of questionable accuracy.

These results reflect the general tendency of the relatively reduced metastable

solutions that leave the mine adits to evolve toward more oxidizing conditions at

equilibrium with the atmosphere. The charge balance relations were not significantly

affected by alternate constraints on oxidation potential, and the field measurements of Eh

and DO. Both indicate generally oxidizing conditions control the aqueous speciation.

Distribution of Aqueous Species. Data interpretations with EQ3NR provide

information on how individual dissolved chemical elements (e.g., copper) are distributed

+ 2+ among various minerals (e.g., CuCO 3, CuOH , and Cu ) assuming equilibrium. All aqueous species were in the oxidized state except where manganese was present in both samples MNWAT01F and MNWAT07F, and some selenium was present in sample

MNWAT01F.

As such, although analysis for sulfur was beyond the scope of this research, it

is reasonable to conclude that sulfur compounds were likely present in adit drainages as

metastable compounds.

The only species that demonstrated effects due to alternate redox constraints were manganese and selenium in sample MNWAT01F. The distribution of manganese species at monitoring location MNWAT01F using log oxygen fugacity as the redox

2+ constraint is 70.59 percent Mn , 17.92 percent MnCO 3(aq), 7.19 percent MnSO 4(aq),

104

and 3.50 percent oxidized MnO 4 . Using Eh as the redox constraint, the manganese

2+ speciation is 73.13 percent Mn , 18.57 percent MnCO 3(aq), and 7.45 percent

MnSO 4(aq). The selenium in sample MNWAT01F using log oxygen fugacity as the

2 redox constraint is in the form of SeO 4 , with selenium in the 6+ valence. Using Eh as

2 the redox constraint, the selenium is in the 4+ valence state with 90.29 percent as SeO 3

and 9.71 percent as HSeO 3 . Selenium, a toxic metal, is thus affected by redox conditions in the range observed for MNWAT01F.

The only species that demonstrated an effect of alternate redox constraints in

MNWAT07F was manganese. The distribution of manganese species in MNWAT07

F using log oxygen fugacity as the redox constraint is 85.48 percent Mn 2+ , 10.60 percent

MnCO 3(aq), 0.0645 percent MnSO 4(aq) (in which Mn is in the 2+ valence), and 2.55

percent MnO 4 (with Mn in the 4+ valence). Using Eh as the redox constraint, the

2+ manganese speciation is 87.73 percent Mn , 10.88 percent MnCO 3(aq), and 0.662 percent MnSO 4(aq).

Charge Balance Adjustments and Redox Constraints . Using the log oxygen fugacity redox constraint for aqueous speciation calculations, samples exhibited large supersaturations with respect to oxidized manganese minerals. Dissolved manganese was apparently reduced in the solutions and out of equilibrium with respect to DO. Water samples were shown to be saturated in none of these minerals using field Eh as the redox constraint in aqueous speciation calculations. This suggests that the Eh meter used in field monitoring may be sensitive to the manganese redox couple, i.e., the Eh electrode is responding to the manganese oxidation stat in the water. EQ3NR results suggest manganese and selenium were present in the reduced form, but in such low

105

concentrations that minimal resulting charge balance effects were observed in both MN

WAT01F and MNWAT07F.

Distribution of Copper Species . Speciation results for this study demonstrate

that the copper minerals within the Moonlight Project play an important role, even in

lowtemperature conditions. The majority of copper in solution MNWAT01F occurred

as a neutral oxidized copper carbonate mineral, where 87.61 percent was CuCO 3(aq),

+ 2 2+ 8.81 percent was CuOH , 2.13 percent was Cu(CO 3)2 , and 1.27 percent was Cu . Even for the more reducing redox constraint, copper is fully oxidized.

As with the speciation in sample MNWAT01F, the majority of copper at monitoring location MNWAT07F occurred as a neutral copper carbonate complex and

+ oxidized species, where 84.49 percent was CuCO 3(aq), 12.22 percent was CuOH , and

2.50 percent was Cu 2+ . As was observed for monitoring location MNWAT01, even in the more reducing state, aqueous copper is fully oxidized.

Saturation States with Respect to Other Complexes . Both MNWAT01F and

MNWAT07F samples were modeled to be supersaturated with a variety of aluminum

oxyhydroxides and aluminosilicate minerals, a condition commonly observed for low

temperature surface waters. According to Murphy et al. (1996), aluminum analyses are

often uncertain and may be controlled by analcime, (which is shown to be close to

equilibrium in the speciation for MNWAT07F).

Using the log oxygen fugacity redox constraint both MNWAT01F and MN

WAT07F exhibit drastic supersaturation with respect to birnessite, bixbyite,

hausmannite, pyrolusite, and todorokite, which are all oxidized manganese minerals.

Dissolved manganese is apparently reduced in the solutions and out of equilibrium with

106

respect to DO. Water samples are shown to be saturated in none of the reduced

manganese complexes using field Eh as the redox constraint. The waters are also strongly

supersaturated in Sb 2O5.

Malachite is a bright green carbonate of copper formed through weathering of

sulfide ores (Peters, 1911). Another notable observation is that MNWAT01F was

supersaturated with malachite (Cu 2(OH) 2CO 3) (with an affinity of 0.85 kcal) which is observed at the site, and MNWAT07F (with an affinity of 3.58 kcal) is close to equilibrium with respect to malachite (see Figure 37).

Figure 37. Malachite, shown in the No. 5 Level of the Superior Mine. Malachite is widely observed at the Moonlight Project site.

107

Comparison of Fugacities . Fugacity is a thermodynamic concept presented by

G. N. Lewis (1901) used to represent the behavior of gases in a solution. ‘The name fugacity is derived from the Latin for ‘fleetness’ or the ‘escaping tendency’” (Narayanan,

2004). Fugacity is related to chemical potential, which reflects the tendency of a component to prefer one phase over another. At low temperature and pressure, fugacity represents the partial pressure of a gas i (X):

f = RT ln i (32) i iO f iO where is the chemical potential (equal to the molar Gibbs free energy) of i, is the μi μiO standard state chemical potential of i, is the fugacity of i, and is the fugacity of the fi fiO standard state of i. Comparing calculated fugacities with known atmospheric pressures

3.5 (where fugacity of CO 2 is approximately 10 bar and the fugacity of O 2 is approximately 0.7 bar) can help determine the validity of a model.

3.34 The CO 2 fugacity for MNWAT01F was calculated to be 10 . The CO 2 fugacity for MNWAT07F was calculated at 10 3.39 . Thus, the models show that the waters are all close to equilibrium with atmospheric CO 2. The oxygen fugacity for MN

WAT01F differs significantly depending on the alternate measurements of DO and Eh.

For the redox constraint Eh, the oxygen fugacity is 10 36.0 bar, and for the redox constraint log fugacity oxygen, the calculated oxygen fugacity is 100.72 bar, which shows

approximate equilibrium with the atmosphere. Similarly, in MNWAT07F, for the

redox constraint Eh, the oxygen fugacity is 10 35.34 , and for the redox constraint log

fugacity oxygen, the calculated oxygen fugacity is approximately 10 0.70 bar.

108

Hypothesis

In contrast to metal mining sites that contain pyriterich (sulfide based) ores

(e.g., Iron Mountain Mine and Walker Mine), the apparently oxidedominated, low sulfide content of ore in portions of the Moonlight Project appears to limit the generation of AMD. One of the purposes of this research was to determine the extent to which historic mining may have affected surface waters in the Moonlight Project area. This objective was carried out by evaluating water quality hazards that may be indicators of possible negative environmental impacts relating to surface water pollution from the

Moonlight Project.

The research performed was also a step in establishing the various controls on surface water quality at the Moonlight Project, helping to developing a ‘signature’ of affected and unaffected surface waters at the site. Specifically, a description of surface water chemical conditions at locations within the Lights Creek District was provided in this report, including trace and major element concentrations and other water quality parameters, as well as interpretation of the data and generation/ interpretation of aqueous speciation models. This type of research could provide a constraint on the potential environmental effects of future mining operations at the Moonlight Project, and other sulfidedeficient mining sites.

Comments on Overall Results

Field data measurements included temperature, pH, Eh, DO, and EC.

Commercial laboratory analyses provided data for major and trace element concentrations in filtered and unfiltered samples. Equilibrium aqueous speciation models

109

were generated to evaluate controls on water chemistry for samples taken within the

Moonlight Project, and to develop ‘signature’ of mineaffected waters.

Measured pH and concentrations of dissolved metals within the Moonlight

Project are typical of unaffected surface water except for water emerging from adits.

Although adit water has near neutral pH, DO is low, and metal concentrations are

elevated compared to background (upstream) samples and samples from Lights Creek.

Arsenic, antimony, and lead exceeded EPA contaminant level limits for drinking water in

adit water. Model solutions are typically supersaturated with respect to aluminum oxy

hydroxides and aluminosilicates. Equilibrium speciation using redox constraints based on both DO and Eh yields oxidized dissolved metals. However, model adit water exhibits

strong supersaturation with respect to manganese and selenium minerals indicating that

aqueous manganese and selenium occur as metastable reduced species. Copper in

speciated water occurs predominantly as cupric carbonate complexes, and adit solutions

are saturated with respect to malachite, which is widely observed in the District. Analyses

and models for adit water are interpreted to indicate that the discharge had interacted with

sulfide minerals (which are observed in core samples) producing metal concentrations.

Reactions with aluminosilicates and oxygen of atmospheric origin neutralized pH and led

to measureable DO contents, supersaturations with respect to aluminum oxyhydroxides,

and metastable aqueous manganese and selenium.

Results of water sampling for metals and field monitoring parameter

measurements demonstrated that the Walker Mine remediation was successful, since

heavy metals were present in low concentrations and pH measurements were nearly

neutral. The water analyses conducted in this study demonstrated Walker Mine is not a

110 satisfactory proximal analog for the Moonlight Project, as the site geology and hydrogeochemistry differ.

CHAPTER V

SUMMARY, CONCLUSIONS, AND

RECOMMENDATIONS

Introduction

A summary of this research and important conclusions reached in the research are contained in the following sections. Additionally, recommendations for possible future research activities are provided herein.

Research Questions and Hypothesis

One of the purposes of this research was to determine the extent to which historic mining has affected surface waters in the Moonlight Project and Lights Creek region with regard to typical environmental problems at many metal mining sites resulting from AMD. Constraints on the potential environmental effects of future mining operations at this, and other pyritedeficient mining sites were intended to be identified herein.

Field data measurements included temperature, pH, Eh, DO, and EC.

Moonlight Project. All of these activities aided in developing a ‘signature’ of mine

111 112

affected waters to evaluated water quality hazards that may be indicators of negative

environmental impacts from the Moonlight Project.

Conclusions Relevant to Research Questions

The Lights Creek Mineral District at the northern end of the Walker Lane

Mineral Belt in Plumas County, California, is a site of historic mining for copper, gold, and silver. The Walker, Superior, and Engels mines are the largest historical producers within the Lights Creek Mineral District. The Superior and Engels mines are located within an area of the Lights Creek Mineral District called the Moonlight Project, a site of current exploration for copper in oxidedominated ores. Waste rock and mine tailings

(currently being assessed for feasibility of reprocessing to extract additional metal) are deposited along the banks of Lights Creek and in other areas of the Moonlight Project, and water drains into Lights Creek from abandoned adits within the Moonlight Project.

Effects of historic mining on surface water quality within the Lights Creek

Mineral District, primarily within the Moonlight Project, were examined using field and

laboratory analyses of samples collected from November 2008 to May 2009. Additional

samples were collected from the Walker Mine area (located approximately 25 kilometers

southeast of the Moonlight Project) for evaluation as a proximal analog. Field data

measurements included temperature, pH, Eh, dissolved oxygen, and electrical

conductivity. Commercial laboratory analyses provided data for major and trace element

concentrations in filtered and unfiltered samples. Equilibrium aqueous speciation models

were generated to evaluate controls on water chemistry for samples taken within the

Moonlight Project, and to develop a ‘signature’ of mineaffected waters.

113

Results demonstrate that measured pH and concentrations of dissolved metals

within the Moonlight Project are typical of unaffected surface waters except for water

emerging from adits. Although adit water has near neutral pH, dissolved oxygen is low

and metal concentrations are elevated compared to background (upstream) samples and

samples from Lights Creek. Arsenic, antimony, and lead in adit water exceeded United

States EPA contaminant level limits for drinking water. Model solutions are typically

supersaturated with respect to aluminum oxyhydroxides and aluminosilicates.

Equilibrium speciation using redox constraints based on dissolved oxygen and Eh yields

oxidized dissolved metals. Model adit water exhibits strong supersaturation with respect

to manganese and selenium complexes, which indicates that aqueous manganese and

selenium occur as metastable reduced species. Copper in speciated water occurs predominantly as cupric carbonate complexes, and adit solutions are saturated with

respect to malachite, which is widely observed at the Moonlight Project. Analyses and

models for adit water are interpreted to indicate that the discharge interacts with sulfide

minerals (which are observed in core samples) producing elevated sulfate and metal

concentrations. Reactions with aluminosilicates and oxygen of atmospheric origin appear

to have neutralized pH and led to measureable dissolved oxygen content, supersaturation

with respect to aluminum oxyhydroxides, and metastable aqueous manganese and

selenium.

Field measurements and laboratory analyses conducted on surface water

samples from the Walker Mine indicate that the water chemistry and mineralization differ

significantly from that found within the Moonlight Project. As such, the Walker Mine is

not a satisfactory proximal analog for analysis of the Moonlight Project surface waters.

114

The results of this study demonstrate that the apparently oxidedominated,

lowsulfide content of ore in portions of the Moonlight Project appears to limit the

generation of AMD. However, it is important to note that that further research would be

required to characterize the site to conclude that future mining activities would have little

to no acid generating potential. The multitude of other environmental factors that often

affect mining sites must be examined. Such effects include, but are not limited to,

ecological (e.g., plants and animals), hydrological (e.g., groundwater contamination of

the water table), and aesthetic (e.g., waste rock and tailings piles).

Limitations of the Study Design and Procedures

The research contained herein represents a step towards characterization of background water conditions and identification of longterm impacts on surface water

resulting from historic mining at the Moonlight Project. The field and laboratory analyses

and aqueous speciation modeling conducted for this study are useful tools for

advancement of the objective of determining the effects on surface water quality of

mining activities in Moonlight Project or other mining sites with similarly oxidebased

ores. However, characterization of mine waste should be performed by “integrating

results from a variety of characterization techniques over time, rather than a single test or

a onetime series of tests” (Maest et al., 2005, p. i). The degree of confidence in models is

“severely limited in part because the models are so complex… [and]…should always be

reevaluated over time at mines sites and compared to sitespecific water quality

information as it becomes available” (Maest et al., 2005, p. x).

115

The results of this study demonstrate that mining of ores such as those found

at the Moonlight Project appear to produce minimal AMD. However, it is important to

note that that further research would be required to characterize the site to a level that

would be sufficient to conclude that future mining activities would have little to no acid

generating potential. The extent, depth, and location of the oxidedominated ore would

need to be thoroughly described.

Future Research and Recommendations

Many opportunities exist for interpretation of the analytical data obtained

during this research project, and additional research. The following lists potential

research advancement opportunities that could be used to further characterize the

Moonlight Project:

♦ Continue sampling, analyzing, and interpreting surface water chemistry. This could

aid in better evaluation of seasonal variations of water chemistry, could provide further

support for existing analytical data, and could help to more adequately characterize major

ions.

♦ Conduct sampling for stable isotopes to provide information regarding the source and ages of the rocks and/or water sources at the site. This also could provide information that could help to answer other questions, such as where any dissolved sulfur in the surface waters at the Moonlight Project site originates.

♦ Conduct a more comprehensive study of historical water quality data to evaluate

consistencies or differences with current conditions or trends in water quality variation.

116

♦ Search databases (e.g., the California State Water Resources Control Board or

Department of Water Resources) for additional water quality data from the Moonlight

Project. This could help to better evaluate seasonal variations of water chemistry, could provide further support for existing analytical data.

♦ Provide additional analytical data that will allow further interpretation of controls on water chemistry by water/rock interactions at the site, which is of environmental and economic interest.

♦ Provide the opportunity to reconcile questions about ion analyses with the

laboratory, particularly regarding anion analyses.

♦ Refine the interpretation of differences between water that discharges from adits,

that interacts with historical mine wastes, and that water which represents natural

conditions.

♦ Model reaction paths using EQ6 for the evolution of water chemistry as it discharges from mine adits and enters atmospheric conditions. Such reaction path models could aid in resolving questions such as why reduced dissolved manganese is present in apparently oxidized samples.

♦ EQ6 can also be used to study the kinetics of the manganese oxidation that occurs when waters emerge from the adits within the Moonlight Project.

♦ Major chemical species that are present and may be of environmental and economic interest may be more accurately specified.

♦ Aqueous sulfide sampling should be conducted to provide a more adequate model of the geological effects on waters at the Moonlight Project site.

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APPENDIX A

Analyte Symbol Na Li Be Mg Al Si Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 5 1 0.1 1 2 200 Analysis Method Report No. Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 A087761 10182008 11300 7 < 0.1 9730 3 10500 A090094 01042009 10200 7 < 0.1 9180 11 10000 A092283 03232009 5560 4 < 0.1 5160 53 7600 A092610/A092611 05152009 8380 7 < 0.1 7800 5 8500

MNWAT02 A092283 03222009 3140 1 < 0.1 1860 5 9100

MNWAT03 A087761 10182008 6380 < 1 < 0.1 4330 5 12500 A090094 12262008 4610 < 1 < 0.1 3160 37 9800 A092283 03222009 3560 < 1 < 0.1 2610 243 9700 A092610/A092611 05142009 3970 < 1 < 0.1 2620 31 10700

MNWAT04 A087761 10182008 6470 < 1 < 0.1 4510 < 2 12600 A090094 12262008 4450 < 1 < 0.1 3650 14 8600 A092283 03222009 3540 < 1 < 0.1 2680 203 9300 A092610/A092611 05142009 4050 < 1 < 0.1 2800 25 11000

MNWAT05 A087761 10182008 5300 < 1 < 0.1 5030 < 2 7100 A092610/A092611 51409 3820 < 1 < 0.1 2780 19 7100

MNWAT06 A087761 10182008 4990 < 1 < 0.1 1190 11 12500 A090071 11232008 4030 < 1 < 0.1 1010 46 11200 A090094 12262008 3700 < 1 < 0.1 913 100 10300 A092283 03222009 3320 < 1 < 0.1 874 18 9000 A092610/A092611 05142009 3760 < 1 < 0.1 1110 20 10900

MNWAT07 A087761 10182008 8900 2 < 0.1 5560 8 13800 A090094 12262008 7410 2 < 0.1 4860 58 12800 A092283 03222009 5630 2 < 0.1 2790 30 11900 A092610/A092611 05142009 6100 2 < 0.1 2610 17 13000

MNWAT08 A087761 10182008 6110 < 1 < 0.1 4380 2 11700 A090094 01042009 4470 < 1 < 0.1 3130 64 10300 A092283 03222009 3520 < 1 < 0.1 2640 179 10000 A092610/A092611 05142009 3910 < 1 < 0.1 2610 28 11500

MNWAT09 A087761 10182008 19500 12 < 0.1 > 20000 < 2 12300 A090071 11232008 16700 12 < 0.1 17300 34 10900 A090094 12262008 17000 12 < 0.1 17500 40 11400 A092283 03222009 18500 13 < 0.1 18400 < 2 11400 A092610/A092611 05152009 19300 14 < 0.1 19200 2 11800

133 134

Analyte Symbol K Ca Sc Ti V Cr Mn Fe Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 30 700 1 0.1 0.1 0.5 0.1 10 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 830 > 20000 2 0.8 < 0.1 < 0.5 61 40 01042009 740 > 20000 2 1.1 < 0.1 < 0.5 58.7 60 03232009 850 > 20000 1 1.7 0.2 < 0.5 197 90 05152009 850 > 20000 1 1 < 0.1 < 0.5 188 < 10

MNWAT02 03222009 350 15500 1 0.8 < 0.1 < 0.5 44.6 < 10

MNWAT03 10182008 1420 14000 2 1.2 0.8 < 0.5 5 70 12262008 1060 10900 2 2.2 0.6 < 0.5 10.4 100 03222009 1020 9100 1 9.4 1.1 < 0.5 3 130 05142009 1050 8800 2 2 0.9 < 0.5 0.8 30

MNWAT04 10182008 1430 14400 2 1 0.8 < 0.5 2.1 30 12262008 860 12400 1 1.1 0.4 < 0.5 3.2 30 03222009 1010 9300 1 7.8 0.9 < 0.5 2.9 100 05142009 1070 9500 2 1.7 0.9 < 0.5 0.8 20

MNWAT05 10182008 610 19800 1 0.5 0.3 < 0.5 0.5 < 10 51409 1330 12700 1 0.9 0.4 < 0.5 0.7 10

MNWAT06 10182008 1420 5600 2 1.1 0.6 < 0.5 1.7 70 11232008 1780 5500 1 1.2 0.6 < 0.5 13.4 200 12262008 1070 4600 2 3.3 0.8 < 0.5 16.4 380 03222009 1140 4100 1 0.9 0.4 < 0.5 0.1 20 05142009 1300 5100 2 1.3 0.7 < 0.5 0.7 40

MNWAT07 10182008 1800 19100 2 1.1 0.8 < 0.5 5.2 30 12262008 1500 16700 2 2.5 0.7 < 0.5 18.2 90 03222009 1310 11400 2 1.4 0.7 < 0.5 2.5 10 05142009 1310 10900 2 1.3 0.7 < 0.5 0.4 < 10

MNWAT08 10182008 1370 14100 2 0.9 1 < 0.5 3.9 60 01042009 1310 10400 2 2.9 0.9 < 0.5 19.8 100 03222009 1160 9200 1 7.4 1.2 < 0.5 3.2 90 05142009 1370 8500 2 1.7 1.1 < 0.5 0.8 20

MNWAT09 10182008 4380 > 20000 2 0.8 0.2 < 0.5 16.7 < 10 11232008 3910 > 20000 1 0.9 0.2 < 0.5 31 < 10 12262008 3940 > 20000 2 1.7 0.3 < 0.5 44.7 80 03222009 4200 > 20000 2 0.9 0.2 < 0.5 2 < 10 05152009 4480 > 20000 2 1.2 0.2 < 0.5 1.2 < 10

135

Analyte Symbol Co Ni Cu Zn Ga Ge As Se Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 0.005 0.3 0.2 0.5 0.01 0.01 0.03 0.2 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 0.162 0.5 81.1 72.3 < 0.01 0.09 15.9 0.2 01042009 0.223 1 123 35.2 < 0.01 0.09 18.9 < 0.2 03232009 1.42 1.3 > 200 30.9 0.02 0.05 9.78 0.3 05152009 0.896 1.2 > 200 30.4 < 0.01 0.06 9.1 0.3

MNWAT02 03222009 0.503 1.1 169 85.6 < 0.01 0.02 1.95 0.6

MNWAT03 10182008 0.024 < 0.3 3.9 < 0.5 < 0.01 < 0.01 0.77 < 0.2 12262008 0.083 < 0.3 10.8 2.9 0.01 < 0.01 0.53 < 0.2 03222009 0.063 < 0.3 2.6 1 0.06 0.01 0.3 < 0.2 05142009 0.023 < 0.3 1.8 0.9 < 0.01 < 0.01 0.25 < 0.2

MNWAT04 10182008 0.01 < 0.3 3.4 8.9 < 0.01 < 0.01 0.6 < 0.2 12262008 0.038 < 0.3 10.5 2.6 < 0.01 < 0.01 0.25 < 0.2 03222009 0.05 < 0.3 3.3 1.1 0.05 0.01 0.26 < 0.2 05142009 0.018 < 0.3 2.4 1 < 0.01 < 0.01 0.27 < 0.2

MNWAT05 10182008 < 0.005 < 0.3 0.7 6.3 < 0.01 < 0.01 0.29 < 0.2 51409 0.02 < 0.3 5.3 10.8 < 0.01 < 0.01 0.29 < 0.2

MNWAT06 10182008 0.012 < 0.3 3.7 4.6 < 0.01 < 0.01 0.29 < 0.2 11232008 0.102 0.4 12.9 6 < 0.01 < 0.01 0.25 < 0.2 12262008 0.141 < 0.3 10.6 4 0.02 < 0.01 0.3 < 0.2 03222009 0.005 < 0.3 3.8 3 < 0.01 0.01 0.27 < 0.2 05142009 0.016 < 0.3 2 1 < 0.01 < 0.01 0.2 < 0.2

MNWAT07 10182008 0.009 < 0.3 10.7 2.8 < 0.01 0.03 3.36 < 0.2 12262008 0.119 0.3 25.5 5 0.02 0.03 3.37 < 0.2 03222009 0.013 < 0.3 10.9 1.3 0.01 0.01 1.17 < 0.2 05142009 0.008 < 0.3 10.4 1.7 < 0.01 0.01 1.45 < 0.2

MNWAT08 10182008 0.02 < 0.3 0.6 5.2 < 0.01 < 0.01 0.27 < 0.2 01042009 0.167 0.3 8.7 5.4 0.02 < 0.01 0.24 < 0.2 03222009 0.058 < 0.3 1 1.1 0.05 0.01 0.2 < 0.2 05142009 0.025 < 0.3 4.8 3.6 < 0.01 < 0.01 0.17 < 0.2

MNWAT09 10182008 0.009 < 0.3 99.8 9.3 < 0.01 0.21 23.2 0.4 11232008 0.116 0.8 111 13.5 < 0.01 0.22 19.6 0.5 12262008 0.266 0.7 120 15.2 0.01 0.22 23.1 0.4 03222009 < 0.005 < 0.3 85.4 7.7 < 0.01 0.24 22.9 0.6 05152009 < 0.005 0.4 71.1 6.9 < 0.01 0.23 22.7 0.7

136

Analyte Symbol Br Rb Sr Y Zr Nb Mo Ru Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 3 0.005 0.04 0.003 0.01 0.005 0.1 0.01 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 4 4.71 > 200 0.082 < 0.01 < 0.005 1.8 < 0.01 01042009 5 5.26 > 200 0.159 < 0.01 < 0.005 2.5 < 0.01 03232009 6 3.55 97 1.1 0.02 < 0.005 1 < 0.01 05152009 5 4.18 152 0.199 < 0.01 < 0.005 2.1 < 0.01

MNWAT02 03222009 5 1.47 25.6 0.047 < 0.01 < 0.005 0.5 < 0.01

MNWAT03 10182008 < 3 1.55 113 0.048 < 0.01 < 0.005 0.3 < 0.01 12262008 3 1.13 120 0.098 0.01 < 0.005 0.3 < 0.01 03222009 5 0.815 80.2 0.172 0.21 0.01 0.2 < 0.01 05142009 4 0.926 78.5 0.061 0.05 < 0.005 0.2 < 0.01

MNWAT04 10182008 < 3 1.54 116 0.026 < 0.01 < 0.005 0.3 < 0.01 12262008 4 0.657 133 0.041 < 0.01 < 0.005 0.2 < 0.01 03222009 5 0.823 79.4 0.161 0.18 0.009 0.2 < 0.01 05142009 4 0.918 79.8 0.06 0.05 < 0.005 0.2 < 0.01

MNWAT05 10182008 < 3 0.287 135 0.015 < 0.01 < 0.005 < 0.1 < 0.01 51409 4 0.519 86.6 0.023 0.04 < 0.005 < 0.1 < 0.01

MNWAT06 10182008 < 3 0.911 83.1 0.099 < 0.01 < 0.005 0.9 < 0.01 11232008 < 3 0.946 98.5 0.156 0.02 < 0.005 1 < 0.01 12262008 < 3 0.846 92.4 0.23 0.02 < 0.005 0.9 < 0.01 03222009 4 1.01 51.9 0.05 0.02 < 0.005 0.7 < 0.01 05142009 3 0.878 69 0.046 0.03 < 0.005 0.7 < 0.01

MNWAT07 10182008 3 3.37 113 0.035 < 0.01 < 0.005 0.4 < 0.01 12262008 3 3.09 132 0.307 0.01 < 0.005 0.5 < 0.01 03222009 4 1.36 86.1 0.083 0.02 < 0.005 0.3 < 0.01 05142009 4 1.28 84.4 0.036 0.01 < 0.005 0.3 < 0.01

MNWAT08 10182008 < 3 1.36 120 0.029 < 0.01 < 0.005 0.2 < 0.01 01042009 6 1.17 139 0.138 0.05 < 0.005 0.2 < 0.01 03222009 4 0.907 87.7 0.187 0.17 0.008 0.1 < 0.01 05142009 4 1.26 81.3 0.05 0.06 < 0.005 0.2 < 0.01

MNWAT09 10182008 4 15.7 188 0.06 < 0.01 < 0.005 1 < 0.01 11232008 4 16.6 > 200 0.255 < 0.01 < 0.005 0.7 < 0.01 12262008 4 16.7 > 200 0.216 < 0.01 < 0.005 1.4 < 0.01 03222009 5 16.3 181 0.052 < 0.01 < 0.005 1.4 < 0.01 05152009 5 15.8 181 0.067 < 0.01 < 0.005 1.6 < 0.01

137

Analyte Symbol Pd Ag Cd In Sn Sb Te I Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 0.01 0.2 0.01 0.001 0.1 0.01 0.1 1 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 < 0.01 < 0.2 0.14 < 0.001 < 0.1 25.2 < 0.1 < 1 01042009 < 0.01 < 0.2 0.2 < 0.001 0.2 26.9 < 0.1 3 03232009 < 0.01 < 0.2 0.34 < 0.001 < 0.1 9.47 < 0.1 < 1 05152009 < 0.01 < 0.2 0.3 < 0.001 < 0.1 15.9 < 0.1 < 1

MNWAT02 03222009 < 0.01 < 0.2 1.17 < 0.001 < 0.1 0.4 < 0.1 < 1

MNWAT03 10182008 < 0.01 < 0.2 0.01 < 0.001 < 0.1 0.15 < 0.1 < 1 12262008 < 0.01 < 0.2 0.04 < 0.001 < 0.1 0.1 < 0.1 3 03222009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.09 < 0.1 < 1 05142009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.05 < 0.1 < 1

MNWAT04 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.13 < 0.1 < 1 12262008 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.14 < 0.1 2 03222009 < 0.01 < 0.2 0.01 < 0.001 < 0.1 0.07 < 0.1 < 1 05142009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.07 < 0.1 < 1

MNWAT05 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 < 0.01 < 0.1 < 1 51409 < 0.01 < 0.2 0.09 < 0.001 < 0.1 0.1 < 0.1 < 1

MNWAT06 10182008 < 0.01 < 0.2 0.02 < 0.001 < 0.1 < 0.01 < 0.1 < 1 11232008 < 0.01 < 0.2 0.06 < 0.001 < 0.1 0.05 < 0.1 2 12262008 < 0.01 < 0.2 0.08 < 0.001 < 0.1 0.04 < 0.1 3 03222009 < 0.01 < 0.2 0.04 < 0.001 < 0.1 0.07 < 0.1 < 1 05142009 < 0.01 < 0.2 0.03 < 0.001 < 0.1 0.04 < 0.1 < 1

MNWAT07 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.29 < 0.1 < 1 12262008 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.34 < 0.1 4 03222009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.14 < 0.1 < 1 05142009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.11 < 0.1 < 1

MNWAT08 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 < 0.01 < 0.1 < 1 01042009 < 0.01 < 0.2 0.06 < 0.001 < 0.1 0.02 < 0.1 4 03222009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.04 < 0.1 < 1 05142009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.04 < 0.1 < 1

MNWAT09 10182008 < 0.01 < 0.2 0.05 < 0.001 < 0.1 2.06 < 0.1 < 1 11232008 < 0.01 < 0.2 0.17 < 0.001 < 0.1 1.87 < 0.1 3 12262008 < 0.01 < 0.2 0.09 < 0.001 0.1 2.21 < 0.1 5 03222009 < 0.01 < 0.2 0.06 < 0.001 < 0.1 2.4 < 0.1 < 1 05152009 < 0.01 < 0.2 0.07 < 0.001 < 0.1 2.17 < 0.1 < 1

138

Analyte Symbol Cs Ba La Ce Pr Nd Sm Eu Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 0.001 0.1 0.001 0.001 0.001 0.001 0.001 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 7.39 15.6 0.024 0.034 0.005 0.022 0.004 0.002 01042009 7.43 16.3 0.028 0.036 0.006 0.027 0.007 0.002 03232009 3.27 13.5 0.326 0.491 0.077 0.333 0.086 0.018 05152009 5.25 14.1 0.049 0.047 0.007 0.023 0.004 0.001

MNWAT02 03222009 1.77 46.1 0.006 0.013 0.002 0.011 0.002 < 0.001

MNWAT03 10182008 0.115 18 0.024 0.026 0.007 0.03 0.007 0.002 12262008 0.086 17.9 0.059 0.099 0.017 0.058 0.014 0.003 03222009 0.021 21.7 0.095 0.18 0.028 0.115 0.03 0.006 05142009 0.02 15.8 0.025 0.036 0.007 0.037 0.008 0.002

MNWAT04 10182008 0.054 21.3 0.01 0.009 0.003 0.011 0.003 0.001 12262008 0.025 23 0.019 0.028 0.005 0.02 0.004 < 0.001 03222009 0.019 21 0.093 0.163 0.025 0.104 0.023 0.006 05142009 0.018 17.1 0.023 0.031 0.007 0.034 0.006 0.002

MNWAT05 10182008 0.003 37.1 0.004 0.002 0.001 0.005 0.001 0.001 51409 0.008 26.6 0.009 0.014 0.002 0.008 0.003 < 0.001

MNWAT06 10182008 0.008 18.9 0.051 0.048 0.014 0.056 0.012 0.003 11232008 0.011 22.7 0.116 0.178 0.027 0.106 0.023 0.006 12262008 0.017 19.8 0.191 0.313 0.05 0.207 0.042 0.011 03222009 0.005 15 0.02 0.025 0.006 0.025 0.007 < 0.001 05142009 0.003 18.6 0.021 0.032 0.007 0.028 0.007 < 0.001

MNWAT07 10182008 0.87 15.8 0.029 0.036 0.007 0.019 0.004 0.001 12262008 0.863 16.6 0.094 0.155 0.017 0.065 0.015 0.005 03222009 0.246 17.4 0.082 0.089 0.015 0.051 0.01 0.002 05142009 0.303 13.7 0.02 0.024 0.005 0.018 0.002 < 0.001

MNWAT08 10182008 0.017 18 0.014 0.012 0.003 0.011 0.004 0.001 01042009 0.022 20.9 0.084 0.152 0.021 0.088 0.021 0.005 03222009 0.011 25.3 0.123 0.188 0.034 0.143 0.032 0.008 05142009 0.012 15.9 0.021 0.036 0.007 0.028 0.007 0.002

MNWAT09 10182008 7.44 4.9 0.004 0.004 < 0.001 0.005 < 0.001 < 0.001 11232008 7.72 6.3 0.095 0.146 0.023 0.103 0.025 0.007 12262008 7.75 5.8 0.054 0.112 0.014 0.063 0.019 0.004 03222009 8.32 5.5 0.003 0.001 < 0.001 0.002 0.001 < 0.001 05152009 7.94 5.8 0.007 0.008 0.002 0.014 0.003 < 0.001

139

Analyte Symbol Gd Tb Dy Ho Er Tm Yb Lu Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 0.007 0.001 0.008 0.002 0.005 < 0.001 0.006 < 0.001 01042009 0.01 0.002 0.017 0.004 0.015 0.002 0.018 0.004 03232009 0.101 0.021 0.133 0.029 0.091 0.012 0.07 0.012 05152009 0.006 0.001 0.011 0.003 0.01 0.001 0.008 0.001

MNWAT02 03222009 0.005 < 0.001 0.004 < 0.001 0.003 < 0.001 0.003 < 0.001

MNWAT03 10182008 0.008 0.001 0.008 0.001 0.004 < 0.001 0.004 < 0.001 12262008 0.013 0.002 0.014 0.003 0.009 0.001 0.009 0.001 03222009 0.028 0.005 0.03 0.006 0.017 0.003 0.017 0.003 05142009 0.008 0.001 0.01 0.002 0.007 0.001 0.007 0.001

MNWAT04 10182008 0.004 < 0.001 0.003 < 0.001 0.002 < 0.001 0.002 < 0.001 12262008 0.007 < 0.001 0.004 0.001 0.004 < 0.001 0.003 < 0.001 03222009 0.023 0.005 0.025 0.005 0.016 0.002 0.017 0.002 05142009 0.006 0.001 0.008 0.002 0.006 < 0.001 0.005 0.001

MNWAT05 10182008 0.002 < 0.001 < 0.001 < 0.001 0.002 < 0.001 0.001 < 0.001 51409 0.003 < 0.001 0.003 < 0.001 0.002 < 0.001 0.003 < 0.001

MNWAT06 10182008 0.013 0.002 0.011 0.003 0.008 < 0.001 0.009 0.001 11232008 0.023 0.004 0.021 0.004 0.015 0.002 0.016 0.003 12262008 0.043 0.006 0.034 0.007 0.021 0.003 0.022 0.003 03222009 0.007 0.001 0.008 0.002 0.006 < 0.001 0.007 0.001 05142009 0.006 < 0.001 0.007 0.001 0.004 < 0.001 0.006 < 0.001

MNWAT07 10182008 0.007 < 0.001 0.004 0.001 0.003 < 0.001 0.003 < 0.001 12262008 0.021 0.005 0.044 0.011 0.033 0.004 0.029 0.004 03222009 0.01 0.002 0.012 0.003 0.007 0.001 0.008 0.002 05142009 0.004 < 0.001 0.004 0.001 0.004 < 0.001 0.005 < 0.001

MNWAT08 10182008 0.005 < 0.001 0.003 0.001 0.002 < 0.001 0.002 < 0.001 01042009 0.022 0.003 0.018 0.004 0.013 0.002 0.013 0.003 03222009 0.031 0.006 0.031 0.007 0.021 0.002 0.017 0.003 05142009 0.006 0.001 0.008 0.001 0.005 < 0.001 0.007 0.001

MNWAT09 10182008 0.002 < 0.001 0.002 < 0.001 0.002 < 0.001 0.002 < 0.001 11232008 0.03 0.005 0.032 0.006 0.018 0.002 0.017 0.003 12262008 0.021 0.004 0.022 0.005 0.017 0.003 0.02 0.003 03222009 0.001 < 0.001 0.003 < 0.001 0.002 < 0.001 0.002 < 0.001 05152009 0.003 < 0.001 0.005 0.001 0.004 < 0.001 0.004 < 0.001

140

Analyte Symbol Hf Ta W Re Os Pt Au Hg Tl Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 0.001 0.001 0.02 0.001 0.002 0.3 0.002 0.2 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 < 0.001 < 0.001 0.07 0.025 < 0.002 < 0.3 0.002 < 0.2 0.016 01042009 < 0.001 < 0.001 0.05 0.024 < 0.002 < 0.3 0.005 < 0.2 0.016 03232009 0.001 < 0.001 0.03 0.014 < 0.002 < 0.3 < 0.002 < 0.2 0.016 05152009 < 0.001 < 0.001 0.08 0.02 < 0.002 < 0.3 < 0.002 < 0.2 0.019

MNWAT02 03222009 < 0.001 < 0.001 < 0.02 0.002 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT03 10182008 < 0.001 < 0.001 0.02 0.001 < 0.002 < 0.3 0.005 < 0.2 < 0.001 12262008 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.005 < 0.2 < 0.001 03222009 0.005 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.004 < 0.2 0.002 05142009 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT04 10182008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001 12262008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.005 < 0.2 < 0.001 03222009 0.004 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002 05142009 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.007 < 0.2 0.001

MNWAT05 10182008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.003 < 0.2 < 0.001 51409 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT06 10182008 < 0.001 < 0.001 0.05 < 0.001 < 0.002 < 0.3 0.002 < 0.2 < 0.001 11232008 0.001 < 0.001 0.03 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001 12262008 < 0.001 < 0.001 0.04 < 0.001 < 0.002 < 0.3 0.003 < 0.2 0.002 03222009 < 0.001 < 0.001 0.03 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001 05142009 < 0.001 < 0.001 0.03 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT07 10182008 < 0.001 < 0.001 0.12 0.002 < 0.002 < 0.3 0.003 < 0.2 0.001 12262008 < 0.001 < 0.001 0.08 < 0.001 < 0.002 < 0.3 0.007 < 0.2 0.002 03222009 < 0.001 < 0.001 0.07 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001 05142009 < 0.001 < 0.001 0.1 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT08 10182008 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 0.036 < 0.2 < 0.001 01042009 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.006 < 0.2 0.001 03222009 0.005 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.002 < 0.2 0.001 05142009 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT09 10182008 < 0.001 < 0.001 0.04 0.007 < 0.002 < 0.3 0.004 < 0.2 0.007 11232008 < 0.001 < 0.001 < 0.02 0.004 < 0.002 < 0.3 0.004 < 0.2 0.008 12262008 < 0.001 < 0.001 0.04 0.007 < 0.002 < 0.3 0.004 < 0.2 0.007 03222009 < 0.001 < 0.001 0.05 0.008 < 0.002 < 0.3 < 0.002 < 0.2 0.007 05152009 < 0.001 < 0.001 0.06 0.008 < 0.002 < 0.3 < 0.002 < 0.2 0.008

141

Analyte Symbol Pb Bi Th U Unit Symbol µg/L µg/L µg/L µg/L Detection Limit 0.01 0.3 0.001 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS

MNWAT01 10182008 0.33 < 0.3 < 0.001 5.97 01042009 3 < 0.3 < 0.001 5.46 03232009 0.2 < 0.3 0.01 2.79 05152009 0.68 < 0.3 < 0.001 4.22

MNWAT02 03222009 2.08 < 0.3 < 0.001 0.607

MNWAT03 10182008 < 0.01 < 0.3 < 0.001 0.175 12262008 2.5 < 0.3 0.002 0.13 03222009 0.07 < 0.3 0.024 0.063 05142009 0.02 < 0.3 0.005 0.061

MNWAT04 10182008 < 0.01 < 0.3 < 0.001 0.127 12262008 2 < 0.3 < 0.001 0.046 03222009 0.1 < 0.3 0.022 0.064 05142009 0.04 < 0.3 0.004 0.057

MNWAT05 10182008 < 0.01 < 0.3 < 0.001 0.089 51409 0.26 < 0.3 0.002 0.015

MNWAT06 10182008 0.02 < 0.3 < 0.001 0.028 11232008 1.88 < 0.3 0.005 0.033 12262008 1.6 < 0.3 0.009 0.054 03222009 0.03 < 0.3 0.006 0.018 05142009 0.02 < 0.3 0.005 0.023

MNWAT07 10182008 0.01 < 0.3 < 0.001 0.435 12262008 1.8 < 0.3 0.002 0.379 03222009 0.03 < 0.3 0.006 0.312 05142009 0.01 < 0.3 0.005 0.249

MNWAT08 10182008 0.01 < 0.3 < 0.001 0.133 01042009 1.7 < 0.3 0.004 0.111 03222009 0.06 < 0.3 0.02 0.071 05142009 0.36 < 0.3 0.004 0.05

MNWAT09 10182008 < 0.01 < 0.3 < 0.001 1.77 11232008 1.49 < 0.3 < 0.001 1.22 12262008 2.5 < 0.3 0.002 1.72 03222009 0.02 < 0.3 < 0.001 1.94 05152009 0.01 < 0.3 < 0.001 1.9

142

Analyte Symbol Cl SO4 Alk. CO3(2) HCO3() Unit Symbol mg/L mg/L mg/L CaCO3 mg/L mg/L Detection Limit 0.03 0.03 2 1 1 Analysis Method Sampling Date IC IC TITR TITR TITR MNWAT01 10182008 01042009 03232009 0.49 69.8 58 < 1 58 05152009 < 0.03 106 91 < 1 91

MNWAT02 03222009 0.38 18.1 40 < 1 40

MNWAT03 10182008 12262008 03222009 1.41 3.03 45 < 1 45 05142009

MNWAT04 10182008 12262008 03222009 1.18 3.35 43 < 1 43 05142009

MNWAT05 10182008 51409 < 0.03 4.58 48 < 1 48

MNWAT06 10182008 11232008 12262008 03222009 1.15 6.92 20 < 1 20 05142009

MNWAT07 10182008 12262008 03222009 1.13 6.91 50 < 1 50 05142009 < 0.03 5.26 47 < 1 47

MNWAT08 10182008 01042009 03222009 1.25 2.61 45 < 1 45 05142009

MNWAT09 10182008 11232008 12262008 03222009 05152009

143

Analyte Symbol Na Li Be Mg Al Si Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 5 1 0.1 1 2 200 Analysis Method Report No. Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT10 A087761 10182008 6410 < 1 < 0.1 4600 5 14300 A092283 03222009 5250 < 1 < 0.1 3630 5 12300 A092610/A092611 05142009 6220 < 1 < 0.1 4090 6 14100

MNWAT11 A087761 10182008 19200 12 < 0.1 19900 < 2 12300 A090071 11232008 16200 11 < 0.1 16700 12 9800 A090094 12262008 17300 12 < 0.1 17900 8 11600 A092283 03222009 15300 10 < 0.1 14800 < 2 11500 A092610/A092611 05152009 18300 13 < 0.1 17900 < 2 12100

MNWAT12 A087761 10182008 11000 9 < 0.1 7520 14 9300 A092283 03232009 3780 1 < 0.1 3570 209 9200 A092610/A092611 05142009 4490 3 < 0.1 3900 10 8400

MNWAT13 A087761 10182008 11400 7 < 0.1 9880 4 10400 A090094 12262008 2720 1 < 0.1 6810 10 4800 A092283 03232009 2090 < 1 < 0.1 5190 10 5000 A092610/A092611 05152009 3260 1 < 0.1 7790 6 5700

MNWAT14 A090071 11232008 4470 3 < 0.1 4070 27 20100

MNWAT15 A090071 11232008 2810 < 1 < 0.1 6120 29 14800

MNWAT16 A090094 12262008 2730 1 < 0.1 6980 197 5100 A090071 03232009 2130 1 < 0.1 5210 10 5200 A092610/A092611 05152009 3290 1 < 0.1 7960 7 5800

MNWAT17 A090071 11232008 3490 < 1 < 0.1 4010 31 14100

MNWAT18 A090071 11232008 4090 < 1 < 0.1 5050 11 13200

144

MNWAT10 10182008 880 15600 2 1.2 1.6 < 0.5 0.9 < 10 03222009 1080 14000 2 1.1 1.2 < 0.5 0.1 < 10 05142009 1240 15300 2 1.2 1.6 < 0.5 0.4 < 10

MNWAT11 10182008 4370 > 20000 2 0.9 0.2 0.6 7.9 < 10 11232008 4150 > 20000 1 0.7 0.2 < 0.5 15.8 < 10 12262008 4350 > 20000 2 1.2 0.2 < 0.5 6.3 < 10 03222009 3550 > 20000 2 1 0.2 < 0.5 0.3 < 10 05152009 4840 > 20000 2 1 0.2 < 0.5 9.2 < 10

MNWAT12 10182008 1460 18600 1 1.1 1.3 < 0.5 7.8 140 03232009 890 9400 1 7.3 1.4 < 0.5 4.7 170 05142009 1010 10000 1 1 1 < 0.5 2.6 40

MNWAT13 10182008 920 > 20000 2 0.8 < 0.1 < 0.5 67.2 110 12262008 380 > 20000 < 1 0.6 0.5 < 0.5 9.6 30 03232009 360 16800 < 1 0.6 < 0.1 < 0.5 0.2 < 10 05152009 530 > 20000 < 1 0.4 < 0.1 < 0.5 < 0.1 < 10

MNWAT14 11232008 870 11300 1 0.9 0.6 < 0.5 5.4 30

MNWAT15 11232008 1250 13000 1 1.4 0.7 0.6 35.9 260

MNWAT16 12262008 410 > 20000 < 1 4 1.8 < 0.5 42.7 600 03232009 370 17100 < 1 0.6 0.1 < 0.5 0.2 < 10 05152009 1500 > 20000 < 1 0.4 0.1 < 0.5 0.4 < 10

MNWAT17 11232008 1440 11200 1 1.5 0.7 < 0.5 21.5 150

MNWAT18 11232008 2020 > 20000 1 1 0.3 < 0.5 113 320

145

MNWAT10 10182008 0.007 < 0.3 3.7 1.4 < 0.01 < 0.01 0.11 < 0.2 03222009 < 0.005 < 0.3 4 3.5 < 0.01 < 0.01 0.2 < 0.2 05142009 0.009 < 0.3 7.4 4 < 0.01 < 0.01 0.25 < 0.2

MNWAT11 10182008 < 0.005 < 0.3 77.6 13.6 < 0.01 0.21 21.2 0.5 11232008 0.036 5.1 81.5 12.7 < 0.01 0.2 18.4 0.5 12262008 0.02 0.3 79.7 9.2 < 0.01 0.2 21.2 0.5 03222009 < 0.005 < 0.3 46.3 7 < 0.01 0.18 17.9 0.5 05152009 < 0.005 < 0.3 82.3 8.2 < 0.01 0.19 18 0.5

MNWAT12 10182008 0.029 0.4 0.9 1.7 < 0.01 0.03 10.5 < 0.2 03232009 0.059 1.2 2 1 0.05 0.01 0.87 < 0.2 05142009 0.025 0.7 1.4 1.6 < 0.01 < 0.01 1.83 0.3

MNWAT13 10182008 0.155 0.4 103 43.4 < 0.01 0.08 18.8 < 0.2 12262008 0.079 0.6 7.1 5.3 < 0.01 < 0.01 2.09 < 0.2 03232009 < 0.005 < 0.3 < 0.2 1.2 < 0.01 < 0.01 0.93 < 0.2 05152009 < 0.005 < 0.3 0.5 2.3 < 0.01 < 0.01 1.79 < 0.2

MNWAT14 11232008 0.409 < 0.3 138 28 < 0.01 < 0.01 11 < 0.2

MNWAT15 11232008 0.285 0.3 33 5.8 0.01 < 0.01 0.09 < 0.2

MNWAT16 12262008 0.67 0.8 12.5 9.1 0.04 < 0.01 2.4 < 0.2 03232009 < 0.005 < 0.3 0.4 1.3 < 0.01 0.01 0.96 < 0.2 05152009 < 0.005 < 0.3 0.8 2.8 < 0.01 < 0.01 1.77 0.3

MNWAT17 11232008 0.21 < 0.3 7.1 2.3 0.01 < 0.01 0.12 < 0.2

MNWAT18 11232008 0.12 < 0.3 12.3 4.6 < 0.01 < 0.01 0.13 < 0.2

146

MNWAT10 10182008 < 3 0.555 116 0.036 < 0.01 < 0.005 < 0.1 < 0.01 03222009 4 0.592 103 0.039 0.02 < 0.005 0.1 < 0.01 05142009 4 0.689 112 0.035 0.02 < 0.005 0.1 < 0.01

MNWAT11 10182008 4 15.4 188 0.047 < 0.01 < 0.005 1 < 0.01 11232008 4 16.4 > 200 0.083 < 0.01 < 0.005 1 < 0.01 12262008 4 17.8 > 200 0.064 < 0.01 < 0.005 1.5 < 0.01 03222009 4 13.4 149 0.057 < 0.01 < 0.005 1.2 < 0.01 05152009 4 14.5 165 0.052 < 0.01 < 0.005 1.5 < 0.01

MNWAT12 10182008 10 2.89 121 0.072 0.01 < 0.005 0.2 < 0.01 03232009 5 0.76 65.9 0.175 0.21 0.008 0.2 < 0.01 05142009 6 0.889 71.4 0.035 0.02 < 0.005 0.2 < 0.01

MNWAT13 10182008 4 4.84 > 200 0.101 < 0.01 < 0.005 1.7 < 0.01 12262008 < 3 0.199 124 0.032 < 0.01 < 0.005 < 0.1 < 0.01 03232009 < 3 0.167 64.3 0.009 0.01 < 0.005 < 0.1 < 0.01 05152009 < 3 0.255 95 0.005 < 0.01 < 0.005 < 0.1 < 0.01

MNWAT14 11232008 4 0.207 170 0.045 < 0.01 < 0.005 < 0.1 < 0.01

MNWAT15 11232008 < 3 1.7 178 0.049 0.03 < 0.005 < 0.1 < 0.01

MNWAT16 12262008 < 3 0.319 133 0.387 0.03 < 0.005 < 0.1 < 0.01 03232009 < 3 0.168 64.9 0.012 0.01 < 0.005 < 0.1 < 0.01 05152009 < 3 0.302 95 0.01 < 0.01 < 0.005 0.1 < 0.01

MNWAT17 11232008 < 3 2.49 168 0.057 0.04 < 0.005 < 0.1 < 0.01

MNWAT18 11232008 4 1.98 > 200 0.041 0.02 < 0.005 0.1 < 0.01

147

MNWAT10 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 < 0.01 < 0.1 < 1 03222009 < 0.01 < 0.2 0.06 < 0.001 < 0.1 0.03 < 0.1 < 1 05142009 < 0.01 < 0.2 0.01 < 0.001 < 0.1 0.03 < 0.1 < 1

MNWAT11 10182008 < 0.01 < 0.2 0.06 < 0.001 < 0.1 2.05 < 0.1 < 1 11232008 < 0.01 < 0.2 0.22 < 0.001 < 0.1 1.96 < 0.1 3 12262008 < 0.01 < 0.2 0.08 < 0.001 < 0.1 2.23 < 0.1 5 03222009 < 0.01 < 0.2 0.05 < 0.001 < 0.1 1.94 < 0.1 < 1 05152009 < 0.01 < 0.2 0.06 < 0.001 < 0.1 1.87 < 0.1 < 1

MNWAT12 10182008 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 < 0.01 < 0.1 4 03232009 < 0.01 < 0.2 0.01 < 0.001 < 0.1 0.06 < 0.1 1 05142009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.06 < 0.1 < 1

MNWAT13 10182008 < 0.01 < 0.2 0.13 < 0.001 < 0.1 24.3 < 0.1 < 1 12262008 < 0.01 < 0.2 0.04 < 0.001 < 0.1 0.04 < 0.1 1 03232009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.05 < 0.1 < 1 05152009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.06 < 0.1 < 1

MNWAT14 11232008 < 0.01 0.6 0.06 < 0.001 < 0.1 0.42 < 0.1 2

MNWAT15 11232008 < 0.01 12.1 0.02 < 0.001 0.3 0.06 < 0.1 < 1

MNWAT16 12262008 < 0.01 < 0.2 0.04 < 0.001 < 0.1 0.09 < 0.1 2 03232009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.07 < 0.1 < 1 05152009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.1 < 0.1 < 1

MNWAT17 11232008 < 0.01 < 0.2 0.02 < 0.001 < 0.1 < 0.01 < 0.1 1

MNWAT18 11232008 < 0.01 < 0.2 0.01 < 0.001 < 0.1 0.3 < 0.1 8

148

MNWAT10 10182008 0.013 6.2 0.015 0.016 0.004 0.019 0.004 0.001 03222009 0.008 8.6 0.012 0.008 0.003 0.013 0.004 < 0.001 05142009 0.011 8.5 0.012 0.011 0.003 0.018 0.003 < 0.001

MNWAT11 10182008 7.39 5.3 0.005 0.004 < 0.001 0.005 < 0.001 < 0.001 11232008 7.57 6.8 0.015 0.02 0.003 0.016 0.004 < 0.001 12262008 7.72 5.7 0.011 0.016 0.002 0.008 0.002 < 0.001 03222009 6.49 5.1 0.008 0.005 0.002 0.009 0.002 < 0.001 05152009 6.99 5.8 0.007 0.004 0.002 0.009 0.001 < 0.001

MNWAT12 10182008 0.502 33.8 0.039 0.062 0.011 0.045 0.012 0.004 03232009 0.045 24.2 0.098 0.165 0.026 0.122 0.024 0.006 05142009 0.074 20.6 0.017 0.024 0.004 0.019 0.005 < 0.001

MNWAT13 10182008 7.39 15.2 0.044 0.046 0.007 0.033 0.008 0.003 12262008 0.004 19.4 0.014 0.021 0.003 0.012 0.003 < 0.001 03232009 0.002 15.6 0.003 0.004 0.001 0.005 0.001 < 0.001 05152009 0.01 19.8 0.001 < 0.001 < 0.001 0.003 < 0.001 < 0.001

MNWAT14 11232008 0.005 90 0.009 0.02 0.002 0.007 0.002 < 0.001

MNWAT15 11232008 0.013 37.9 0.02 0.039 0.005 0.027 0.006 0.002

MNWAT16 12262008 0.197 21.4 0.218 0.475 0.062 0.278 0.07 0.019 03232009 0.002 16 0.004 0.004 0.001 0.005 < 0.001 < 0.001 05152009 0.01 20.1 0.003 0.003 < 0.001 0.004 < 0.001 < 0.001

MNWAT17 11232008 0.008 18.7 0.023 0.033 0.006 0.028 0.006 0.001

MNWAT18 11232008 0.011 183 0.016 0.02 0.004 0.02 0.005 < 0.001

149

MNWAT10 10182008 0.005 < 0.001 0.005 < 0.001 0.003 < 0.001 0.003 < 0.001 03222009 0.005 < 0.001 0.005 0.001 0.004 < 0.001 0.004 < 0.001 05142009 0.003 < 0.001 0.006 0.001 0.003 < 0.001 0.003 < 0.001

MNWAT11 10182008 0.002 < 0.001 0.001 < 0.001 0.002 < 0.001 0.002 < 0.001 11232008 0.006 < 0.001 0.007 0.002 0.006 < 0.001 0.007 0.001 12262008 0.003 < 0.001 0.005 < 0.001 0.003 < 0.001 0.003 < 0.001 03222009 0.004 < 0.001 0.004 0.001 0.004 < 0.001 0.004 < 0.001 05152009 0.002 < 0.001 0.004 < 0.001 0.003 < 0.001 0.003 < 0.001

MNWAT12 10182008 0.013 0.002 0.01 0.002 0.007 < 0.001 0.006 < 0.001 03232009 0.027 0.005 0.026 0.006 0.016 0.003 0.016 0.003 05142009 0.005 < 0.001 0.006 0.001 0.004 < 0.001 0.004 < 0.001

MNWAT13 10182008 0.011 0.002 0.009 0.002 0.006 < 0.001 0.004 < 0.001 12262008 0.004 < 0.001 0.004 < 0.001 0.003 < 0.001 0.004 < 0.001 03232009 0.002 < 0.001 0.002 < 0.001 < 0.001 < 0.001 0.002 < 0.001 05152009 < 0.001 < 0.001 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001

MNWAT14 11232008 0.002 < 0.001 0.003 < 0.001 0.002 < 0.001 0.002 < 0.001

MNWAT15 11232008 0.007 0.001 0.006 0.001 0.004 < 0.001 0.004 < 0.001

MNWAT16 12262008 0.07 0.011 0.065 0.012 0.036 0.005 0.031 0.005 03232009 0.003 < 0.001 0.002 < 0.001 0.001 < 0.001 0.002 < 0.001 05152009 < 0.001 < 0.001 0.002 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001

MNWAT17 11232008 0.008 0.001 0.006 0.001 0.006 < 0.001 0.008 0.001

MNWAT18 11232008 0.006 < 0.001 0.004 0.001 0.003 < 0.001 0.003 < 0.001

150

MNWAT10 10182008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001 03222009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001 05142009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT11 10182008 < 0.001 < 0.001 0.03 0.007 < 0.002 < 0.3 0.005 < 0.2 0.006 11232008 0.001 < 0.001 0.02 0.005 < 0.002 < 0.3 0.002 < 0.2 0.006 12262008 < 0.001 < 0.001 0.03 0.007 < 0.002 < 0.3 0.004 < 0.2 0.006 03222009 < 0.001 < 0.001 0.03 0.007 < 0.002 < 0.3 < 0.002 < 0.2 0.006 05152009 < 0.001 < 0.001 0.04 0.007 < 0.002 < 0.3 < 0.002 < 0.2 0.006

MNWAT12 10182008 < 0.001 < 0.001 0.03 < 0.001 < 0.002 < 0.3 0.006 < 0.2 0.001 03232009 0.006 < 0.001 0.04 < 0.001 < 0.002 < 0.3 0.002 < 0.2 0.001 05142009 < 0.001 < 0.001 0.04 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT13 10182008 < 0.001 < 0.001 0.06 0.024 < 0.002 < 0.3 0.002 < 0.2 0.018 12262008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.004 < 0.2 0.002 03232009 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002 05152009 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT14 11232008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT15 11232008 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.003 < 0.2 < 0.001

MNWAT16 12262008 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.004 < 0.2 0.002 03232009 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002 05152009 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT17 11232008 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT18 11232008 0.002 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

151

Analyte Symbol Pb Bi Th U Unit Symbol µg/L µg/L µg/L µg/L Detection Limit 0.01 0.3 0.001 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS

MNWAT10 10182008 < 0.01 < 0.3 < 0.001 0.109 03222009 0.01 < 0.3 0.001 0.072 05142009 0.01 < 0.3 0.002 0.085

MNWAT11 10182008 < 0.01 < 0.3 < 0.001 1.77 11232008 1.34 < 0.3 < 0.001 1 12262008 1.4 < 0.3 < 0.001 1.6 03222009 0.04 < 0.3 < 0.001 1.53 05152009 < 0.01 < 0.3 < 0.001 1.61

MNWAT12 10182008 0.02 < 0.3 < 0.001 0.341 03232009 0.05 < 0.3 0.015 0.167 05142009 0.02 < 0.3 0.001 0.163

MNWAT13 10182008 0.15 < 0.3 < 0.001 6.01 12262008 1.75 < 0.3 < 0.001 0.184 03232009 < 0.01 < 0.3 < 0.001 0.096 05152009 < 0.01 < 0.3 < 0.001 0.165

MNWAT14 11232008 1.21 < 0.3 < 0.001 0.082

MNWAT15 11232008 3.29 < 0.3 0.002 0.104

MNWAT16 12262008 3.5 < 0.3 0.002 0.274 03232009 0.01 < 0.3 < 0.001 0.096 05152009 0.02 < 0.3 < 0.001 0.168

MNWAT17 11232008 1.54 < 0.3 0.002 0.167

MNWAT18 11232008 1.24 < 0.3 < 0.001 2.19

152

Analyte Symbol Cl SO4 Alk. CO3(2) HCO3() Unit Symbol mg/L mg/L mg/L CaCO3 mg/L mg/L Detection Limit 0.03 0.03 2 1 1 Analysis Method Sampling Date IC IC TITR TITR TITR

MNWAT10 10182008 03222009 05142009 < 0.03 2.04 69 < 1 69

MNWAT11 10182008 11232008 12262008 03222009 05152009 < 0.03 59.9 194 < 1 194

MNWAT12 10182008 03232009 05142009 < 0.03 2.12 48 < 1 48

MNWAT13 10182008 12262008 03232009 05152009 < 0.03 13.3 88 < 1 88

MNWAT14 11232008

MNWAT15 11232008

MNWAT16 12262008 03232009 05152009 < 0.03 13.4 88 < 1 88

MNWAT17 11232008

MNWAT18 11232008

153

Analyte Symbol Na Li Be Mg Al Si Unit Symbol µg/L µg/L µg/L µg/L µg/L µg/L Detection Limit 5 1 0.1 1 2 200 Analysis Method Report No. Sampling Date ICPMS ICPMS ICPMS ICPMS ICPMS ICPMS

MNWAT01X A090071 03232009 2620 2 < 0.1 2470 65 3700 A092610/A092611 05152009 4440 3 < 0.1 4210 4 4400

MNWAT09X A092283 03232009 8940 6 < 0.1 9120 < 2 5700 A092610/A092611 05152009 9900 7 < 0.1 10100 < 2 5900

MNWAT11X A092283 03232009 7130 5 < 0.1 6960 < 2 5500 A092610/A092611 05152009 9280 6 < 0.1 9460 4 6000

MNWAT16X A092283 03232009 1080 < 1 < 0.1 2640 6 2700 A092610/A092611 05152009 1660 < 1 < 0.1 3950 4 3000

MNWAT01F A092610/A092611 05152009 8840 7 < 0.1 8390 < 2 8900

MNWAT03F A092610/A092611 05142009 4080 1 < 0.1 2710 10 10600

MNWAT04F A092610/A092611 05142009 4160 < 1 < 0.1 2830 8 10600

MNWAT05F A092610/A092611 05142009 4020 < 1 < 0.1 2890 8 7200

MNWAT06F A092610/A092611 05142009 3840 1 < 0.1 1140 11 10800

MNWAT07F A092610/A092611 05142009 6200 2 < 0.1 2560 12 12700

MNWAT08F A092610/A092611 05142009 3970 < 1 < 0.1 2590 10 11100

MNWAT09F A092610/A092611 05152009 19300 14 < 0.1 19800 11 11800

MNWAT10F A092610/A092611 05142009 6330 < 1 < 0.1 4190 22 14100

MNWAT11F A092610/A092611 05152009 18200 12 < 0.1 17500 4 11800

MNWAT12F A092610/A092611 05142009 4740 2 < 0.1 4000 4 8500

MNWAT16F A092610/A092611 05152009 3290 1 < 0.1 7790 6 5800

154

MNWAT01X 03232009 400 17400 < 1 2 0.2 < 0.5 95.3 50 05152009 1250 > 20000 < 1 0.3 < 0.1 < 0.5 94.3 < 10

MNWAT09X 03232009 2110 > 20000 < 1 0.5 < 0.1 < 0.5 0.1 < 10 05152009 2370 > 20000 < 1 0.4 0.1 < 0.5 8 < 10

MNWAT11X 03232009 1660 > 20000 < 1 0.6 0.1 < 0.5 0.2 < 10 05152009 2400 > 20000 < 1 0.4 0.1 < 0.5 3 < 10

MNWAT16X 03232009 190 9000 < 1 0.3 < 0.1 < 0.5 0.4 < 10 05152009 290 13200 < 1 0.1 < 0.1 < 0.5 0.3 < 10

MNWAT01F 05152009 870 > 20000 1 0.7 0.1 < 0.5 184 < 10

MNWAT03F 05142009 1060 8900 2 1 0.8 < 0.5 5.7 10

MNWAT04F 05142009 1120 9600 2 0.9 0.8 < 0.5 5 < 10

MNWAT05F 05142009 1320 13000 1 0.6 0.4 < 0.5 1.4 < 10

MNWAT06F 05142009 1620 5200 2 0.9 0.6 < 0.5 2 30

MNWAT07F 05142009 1480 10500 2 1 0.8 < 0.5 3.2 < 10

MNWAT08F 05142009 1420 8400 1 0.9 1 < 0.5 4.2 < 10

MNWAT09F 05152009 4710 > 20000 2 0.9 0.2 < 0.5 21.2 < 10

MNWAT10F 05142009 1340 15900 2 1 1.6 < 0.5 1.2 < 10

MNWAT11F 05152009 4340 > 20000 2 0.8 0.2 < 0.5 25.8 < 10

MNWAT12F 05142009 1190 10800 1 0.6 0.9 < 0.5 5.2 20

MNWAT16F 05152009 930 > 20000 < 1 0.3 0.1 < 0.5 0.5 < 10

155

MNWAT01X 03232009 0.669 1 > 200 28.3 0.03 0.03 5.23 < 0.2 05152009 0.454 7.2 > 200 28.2 < 0.01 0.03 5.06 < 0.2

MNWAT09X 03232009 < 0.005 0.4 43.5 15.4 < 0.01 0.12 10.6 0.2 05152009 0.009 7.2 49.8 19 < 0.01 0.11 11 0.3

MNWAT11X 03232009 < 0.005 0.5 24.1 16.8 < 0.01 0.08 7.33 < 0.2 05152009 0.01 6.6 130 15.5 < 0.01 0.1 9.52 0.3

MNWAT16X 03232009 0.005 0.5 4.9 11 < 0.01 < 0.01 0.53 < 0.2 05152009 0.015 6.9 10 13.8 < 0.01 < 0.01 0.87 < 0.2

MNWAT01F 05152009 0.865 1.3 > 200 24.5 < 0.01 0.06 8.54 0.4

MNWAT03F 05142009 0.028 < 0.3 23.6 2 < 0.01 < 0.01 0.66 < 0.2

MNWAT04F 05142009 0.025 < 0.3 22.9 3.7 < 0.01 < 0.01 0.52 < 0.2

MNWAT05F 05142009 0.013 0.4 5.1 11.4 < 0.01 < 0.01 0.31 < 0.2

MNWAT06F 05142009 0.014 0.3 3.9 3 < 0.01 < 0.01 0.2 0.2

MNWAT07F 05142009 0.011 0.3 6.8 2.6 < 0.01 0.01 1.2 < 0.2

MNWAT08F 05142009 0.039 < 0.3 29.5 4 < 0.01 < 0.01 0.71 < 0.2

MNWAT09F 05152009 0.029 0.7 48.7 7.5 < 0.01 0.22 20 0.5

MNWAT10F 05142009 0.013 0.4 7.5 3.8 < 0.01 < 0.01 0.3 < 0.2

MNWAT11F 05152009 0.026 0.6 > 200 12.2 < 0.01 0.18 17.5 0.4

MNWAT12F 05142009 0.019 1 8.7 6.7 < 0.01 < 0.01 1.86 < 0.2

MNWAT16F 05152009 < 0.005 0.5 7.2 6.5 < 0.01 < 0.01 1.8 0.2

156

MNWAT01X 03232009 < 3 1.74 48.4 0.656 0.02 < 0.005 0.5 < 0.01 05152009 < 3 2.2 80.4 0.072 < 0.01 < 0.005 1 < 0.01

MNWAT09X 03232009 < 3 8.15 89.6 0.024 < 0.01 < 0.005 0.7 < 0.01 05152009 < 3 7.86 92.6 0.033 < 0.01 < 0.005 0.8 < 0.01

MNWAT11X 03232009 < 3 6.12 67.8 0.029 < 0.01 < 0.005 0.5 < 0.01 05152009 < 3 7.44 83.2 0.056 < 0.01 < 0.005 0.7 < 0.01

MNWAT16X 03232009 < 3 0.112 33.8 0.009 0.01 < 0.005 < 0.1 < 0.01 05152009 < 3 0.145 48.5 0.004 < 0.01 < 0.005 < 0.1 < 0.01

MNWAT01F 05152009 5 4.14 159 0.141 < 0.01 < 0.005 2.1 < 0.01

MNWAT03F 05142009 3 0.963 78.9 0.062 0.03 < 0.005 0.2 < 0.01

MNWAT04F 05142009 3 0.908 80.7 0.06 0.02 < 0.005 0.2 < 0.01

MNWAT05F 05142009 4 0.551 91.3 0.032 0.04 < 0.005 < 0.1 < 0.01

MNWAT06F 05142009 3 0.886 66.6 0.045 0.01 < 0.005 0.7 < 0.01

MNWAT07F 05142009 3 1.31 83.5 0.025 < 0.01 < 0.005 0.3 < 0.01

MNWAT08F 05142009 3 1.28 81.3 0.061 0.05 < 0.005 0.1 < 0.01

MNWAT09F 05152009 4 15.3 183 0.049 < 0.01 < 0.005 1.6 < 0.01

MNWAT10F 05142009 4 0.865 112 0.034 0.02 < 0.005 0.1 < 0.01

MNWAT11F 05152009 4 13.9 165 0.086 < 0.01 < 0.005 1.4 < 0.01

MNWAT12F 05142009 5 1.2 72 0.029 0.02 < 0.005 0.2 < 0.01

MNWAT16F 05152009 < 3 0.44 95.8 0.011 0.01 < 0.005 0.1 < 0.01

157

MNWAT01X 03232009 < 0.01 < 0.2 0.18 < 0.001 < 0.1 5.17 < 0.1 < 1 05152009 < 0.01 < 0.2 0.18 < 0.001 < 0.1 8.08 < 0.1 < 1

MNWAT09X 03232009 < 0.01 < 0.2 0.05 < 0.001 < 0.1 1.22 < 0.1 < 1 05152009 < 0.01 < 0.2 0.05 < 0.001 < 0.1 1.08 < 0.1 < 1

MNWAT11X 03232009 < 0.01 < 0.2 0.03 < 0.001 < 0.1 0.98 < 0.1 < 1 05152009 < 0.01 < 0.2 0.04 < 0.001 < 0.1 0.97 < 0.1 < 1

MNWAT16X 03232009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.04 < 0.1 < 1 05152009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.04 < 0.1 < 1

MNWAT01F 05152009 < 0.01 < 0.2 0.26 < 0.001 < 0.1 16 < 0.1 < 1

MNWAT03F 05142009 < 0.01 < 0.2 < 0.01 < 0.001 < 0.1 0.07 < 0.1 < 1

MNWAT04F 05142009 < 0.01 < 0.2 0.03 < 0.001 < 0.1 0.07 < 0.1 < 1

MNWAT05F 05142009 < 0.01 < 0.2 0.09 < 0.001 < 0.1 0.09 < 0.1 < 1

MNWAT06F 05142009 < 0.01 < 0.2 0.03 < 0.001 < 0.1 0.04 < 0.1 < 1

MNWAT07F 05142009 < 0.01 0.2 0.01 < 0.001 < 0.1 0.12 < 0.1 < 1

MNWAT08F 05142009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.05 < 0.1 < 1

MNWAT09F 05152009 < 0.01 < 0.2 0.07 < 0.001 < 0.1 2.15 < 0.1 < 1

MNWAT10F 05142009 < 0.01 11.3 0.04 < 0.001 < 0.1 0.04 < 0.1 < 1

MNWAT11F 05152009 < 0.01 0.5 0.08 < 0.001 < 0.1 1.86 < 0.1 < 1

MNWAT12F 05142009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.08 < 0.1 < 1

MNWAT16F 05152009 < 0.01 < 0.2 0.02 < 0.001 < 0.1 0.07 < 0.1 < 1

158

MNWAT01X 03232009 1.8 7.8 0.204 0.328 0.049 0.237 0.052 0.013 05152009 2.58 7.9 0.022 0.023 0.004 0.015 0.003 < 0.001

MNWAT09X 03232009 4.2 3.1 0.002 0.001 < 0.001 0.003 < 0.001 < 0.001 05152009 3.97 3.5 0.006 0.009 0.001 0.009 < 0.001 < 0.001

MNWAT11X 03232009 3.18 2.9 0.005 0.004 0.001 0.008 0.002 < 0.001 05152009 3.54 3.3 0.013 0.015 0.003 0.012 0.002 < 0.001

MNWAT16X 03232009 0.022 8.4 0.003 0.005 < 0.001 0.006 0.002 < 0.001 05152009 0.029 10.1 0.001 0.001 < 0.001 0.002 < 0.001 < 0.001

MNWAT01F 05152009 4.67 17 0.029 0.026 0.004 0.017 0.003 < 0.001

MNWAT03F 05142009 0.127 15.5 0.024 0.028 0.007 0.027 0.006 0.001

MNWAT04F 05142009 0.041 17.1 0.017 0.024 0.005 0.028 0.005 0.001

MNWAT05F 05142009 0.027 26.7 0.01 0.011 0.003 0.014 0.003 < 0.001

MNWAT06F 05142009 0.014 18.3 0.019 0.022 0.006 0.027 0.005 0.001

MNWAT07F 05142009 0.237 15.2 0.008 0.011 0.002 0.011 0.002 < 0.001

MNWAT08F 05142009 0.113 15.9 0.023 0.028 0.006 0.03 0.006 0.001

MNWAT09F 05152009 7.41 9.4 0.006 0.007 0.001 0.006 < 0.001 < 0.001

MNWAT10F 05142009 0.16 9.2 0.021 0.02 0.003 0.013 0.004 < 0.001

MNWAT11F 05152009 6.47 7.2 0.013 0.015 0.002 0.012 0.002 < 0.001

MNWAT12F 05142009 0.27 19.3 0.011 0.015 0.003 0.016 0.003 < 0.001

MNWAT16F 05152009 0.111 20.3 0.002 0.002 < 0.001 0.003 < 0.001 < 0.001

159

MNWAT01X 03232009 0.065 0.013 0.082 0.018 0.059 0.008 0.048 0.008 05152009 0.004 < 0.001 0.005 0.001 0.004 < 0.001 0.003 < 0.001

MNWAT09X 03232009 0.001 < 0.001 0.001 < 0.001 0.001 < 0.001 0.001 < 0.001 05152009 0.001 < 0.001 0.004 < 0.001 0.002 < 0.001 0.002 < 0.001

MNWAT11X 03232009 0.002 < 0.001 0.003 < 0.001 0.002 < 0.001 0.003 < 0.001 05152009 0.003 < 0.001 0.005 0.001 0.004 < 0.001 0.003 < 0.001

MNWAT16X 03232009 0.002 < 0.001 0.002 < 0.001 0.001 < 0.001 < 0.001 < 0.001 05152009 < 0.001 < 0.001 0.001 < 0.001 < 0.001 < 0.001 < 0.001 < 0.001

MNWAT01F 05152009 0.004 < 0.001 0.009 0.002 0.008 < 0.001 0.006 < 0.001

MNWAT03F 05142009 0.007 0.001 0.008 0.002 0.006 < 0.001 0.006 0.001

MNWAT04F 05142009 0.008 0.001 0.009 0.002 0.006 < 0.001 0.008 0.001

MNWAT05F 05142009 0.003 < 0.001 0.004 0.001 0.003 < 0.001 0.004 < 0.001

MNWAT06F 05142009 0.005 0.001 0.007 0.001 0.005 < 0.001 0.006 < 0.001

MNWAT07F 05142009 0.003 < 0.001 0.004 < 0.001 0.003 < 0.001 0.004 < 0.001

MNWAT08F 05142009 0.006 0.001 0.009 0.002 0.007 < 0.001 0.007 0.001

MNWAT09F 05152009 < 0.001 < 0.001 0.004 < 0.001 0.002 < 0.001 0.002 < 0.001

MNWAT10F 05142009 0.003 < 0.001 0.004 < 0.001 0.004 < 0.001 0.004 < 0.001

MNWAT11F 05152009 0.003 < 0.001 0.007 0.002 0.007 0.001 0.008 0.001

MNWAT12F 05142009 0.004 < 0.001 0.005 < 0.001 0.003 < 0.001 0.003 < 0.001

MNWAT16F 05152009 < 0.001 < 0.001 0.002 < 0.001 0.001 < 0.001 < 0.001 < 0.001

160

MNWAT01X 03232009 0.001 < 0.001 < 0.02 0.006 < 0.002 < 0.3 0.002 < 0.2 0.008 05152009 < 0.001 < 0.001 0.04 0.01 < 0.002 < 0.3 < 0.002 < 0.2 0.009

MNWAT09X 03232009 < 0.001 < 0.001 0.02 0.004 < 0.002 < 0.3 < 0.002 < 0.2 0.003 05152009 < 0.001 < 0.001 0.03 0.004 < 0.002 < 0.3 < 0.002 < 0.2 0.003

MNWAT11X 03232009 < 0.001 < 0.001 < 0.02 0.003 < 0.002 < 0.3 < 0.002 < 0.2 0.003 05152009 < 0.001 < 0.001 < 0.02 0.004 < 0.002 < 0.3 < 0.002 < 0.2 0.003

MNWAT16X 03232009 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.003 < 0.2 0.001 05152009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT01F 05152009 < 0.001 < 0.001 0.08 0.02 < 0.002 < 0.3 < 0.002 < 0.2 0.017

MNWAT03F 05142009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT04F 05142009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 0.003 < 0.2 0.001

MNWAT05F 05142009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT06F 05142009 < 0.001 < 0.001 0.03 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT07F 05142009 < 0.001 < 0.001 0.11 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT08F 05142009 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

MNWAT09F 05152009 < 0.001 < 0.001 0.06 0.007 < 0.002 < 0.3 < 0.002 < 0.2 0.007

MNWAT10F 05142009 < 0.001 < 0.001 < 0.02 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 < 0.001

MNWAT11F 05152009 < 0.001 < 0.001 0.04 0.008 < 0.002 < 0.3 < 0.002 < 0.2 0.006

MNWAT12F 05142009 < 0.001 < 0.001 0.05 < 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.001

MNWAT16F 05152009 < 0.001 < 0.001 < 0.02 0.001 < 0.002 < 0.3 < 0.002 < 0.2 0.002

161

Analyte Symbol Pb Bi Th U Unit Symbol µg/L µg/L µg/L µg/L Detection Limit 0.01 0.3 0.001 0.001 Analysis Method Sampling Date ICPMS ICPMS ICPMS ICPMS

MNWAT01X 03232009 0.68 < 0.3 0.008 1.43 05152009 0.2 < 0.3 < 0.001 1.99

MNWAT09X 03232009 0.08 < 0.3 < 0.001 0.97 05152009 0.44 < 0.3 < 0.001 0.932

MNWAT11X 03232009 0.22 < 0.3 < 0.001 0.76 05152009 0.1 < 0.3 < 0.001 0.928

MNWAT16X 03232009 0.35 < 0.3 < 0.001 0.054 05152009 1.63 < 0.3 < 0.001 0.086

MNWAT01F 05152009 < 0.01 < 0.3 < 0.001 4.26

MNWAT03F 05142009 0.01 < 0.3 0.003 0.071

MNWAT04F 05142009 0.66 < 0.3 0.002 0.074

MNWAT05F 05142009 0.02 < 0.3 < 0.001 0.016

MNWAT06F 05142009 0.06 < 0.3 0.004 0.025

MNWAT07F 05142009 0.53 < 0.3 0.002 0.208

MNWAT08F 05142009 0.03 < 0.3 0.003 0.063

MNWAT09F 05152009 0.01 < 0.3 < 0.001 1.81

MNWAT10F 05142009 0.81 < 0.3 0.001 0.092

MNWAT11F 05152009 1.96 < 0.3 < 0.001 1.69

MNWAT12F 05142009 0.03 < 0.3 < 0.001 0.172

MNWAT16F 05152009 0.01 < 0.3 < 0.001 0.17

APPENDIX B

MNWAT01F

Aqueous species accounting for 99% or more of Ba++

Species Factor Molality Per Cent

Ba++ 1.00 1.2359E07 99.84 Total 1.2379E07 99.84

Aqueous species accounting for 99% or more of Br

Species Factor Molality Per Cent

Br 1.00 6.2574E08 100.00 Total 6.2575E08 100.00

Aqueous species accounting for 99% or more of Ca++

Species Factor Molality Per Cent

Ca++ 1.00 1.1930E03 92.29 CaSO4(aq) 1.00 7.5675E05 5.85 CaHCO3+ 1.00 1.4383E05 1.11 Total 1.2927E03 99.26

Aqueous species accounting for 99% or more of Cd++

Species Factor Molality Per Cent

Cd++ 1.00 2.1973E09 95.00 CdHCO3+ 1.00 7.2137E11 3.12 CdOH+ 1.00 2.4761E11 1.07 Total 2.3129E09 99.19

Aqueous species accounting for 99% or more of Ce+++

Species Factor Molality Per Cent

Ce++ 1.00 1.8556E10 100.00 Total 1.8556E10 100.00 163 164

Aqueous species accounting for 99% or more of Co++

Species Factor Molality Per Cent

HCoO2 1.00 1.3362E08 91.04 Co2(OH)3+ 2.00 6.5485E10 8.92 Total 1.4678E08 99.96

Aqueous species accounting for 99% or more of Cs+

Species Factor Molality Per Cent

Cs+ 1.00 3.5138E08 100.00 Total 3.5138E08 100.00

Aqueous species accounting for 99% or more of Cu++

Species Factor Molality Per Cent

CuCO3(aq) 1.00 5.5146E06 87.61 CuOH+ 1.00 5.5471E07 8.81 Cu(CO3)2 1.00 1.3375E07 2.12 Cu++ 1.00 7.9724E08 1.27 Total 6.2947E06 99.81

Aqueous species accounting for 99% or more of Dy+++

Species Factor Molality Per Cent

Dy++ 1.00 5.5385E11 100.00 Total 5.5385E11 100.00

Aqueous species accounting for 99% or more of Er+++

Species Factor Molality Per Cent

Er++ 1.00 4.7830E11 100.00 Total 4.7830E11 100.00

165

Aqueous species accounting for 99% or more of Gd+++

Species Factor Molality Per Cent

Gd++ 1.00 2.5437E11 100.00 Total 2.5437E11 100.00

Aqueous species accounting for 99% or more of H2AsO4

Species Factor Molality Per Cent

HAsO4 1.00 1.1060E07 97.06 H2AsO4 1.00 3.3103E09 2.90 Total 1.1395E07 99.96

Aqueous species accounting for 99% or more of HCO3

Species Factor Molality Per Cent

HCO3 1.00 1.4223E03 95.37 CO2(aq) 1.00 2.3016E05 1.54 CaHCO3+ 1.00 1.4383E05 9.644E01 CO3 1.00 9.6976E06 6.502E01 CaCO3(aq) 1.00 9.5982E06 6.436E01 Total 1.4914E03 99.17

Aqueous species accounting for 99% or more of Ho+++

Species Factor Molality Per Cent

Ho++ 1.00 1.2126E11 100.00 Total 1.2126E11 100.00

Aqueous species accounting for 99% or more of K+

Species Factor Molality Per Cent

K+ 1.00 2.2133E05 99.46 Total 2.2252E05 99.46

166

Aqueous species accounting for 99% or more of La+++

Species Factor Molality Per Cent

La++ 1.00 2.0878E10 100.00 Total 2.0878E10 100.00

Aqueous species accounting for 99% or more of Li+

Species Factor Molality Per Cent

Li+ 1.00 1.0042E06 99.57 Total 1.0085E06 99.57

Aqueous species accounting for 99% or more of Mg++

Species Factor Molality Per Cent

Mg++ 1.00 3.1147E04 90.23 MgSO4(aq) 1.00 2.8717E05 8.32 MgHCO3+ 1.00 3.6763E06 1.06 Total 3.4520E04 99.61

Aqueous species accounting for 99% or more of Mn++

Species Factor Molality Per Cent

Mn++ 1.00 2.4498E06 73.14 MnCO3(aq) 1.00 6.2194E07 18.57 MnSO4(aq) 1.00 2.4949E07 7.45 Total 3.3492E06 99.16

Aqueous species accounting for 99% or more of MoO4

Species Factor Molality Per Cent

MoO4 1.00 2.1890E08 100.00 Total 2.1890E08 100.00

Aqueous species accounting for 99% or more of Na+

167

Species Factor Molality Per Cent

Na+ 1.00 3.8171E04 99.27 Total 3.8452E04 99.27

Aqueous species accounting for 99% or more of Nd+++

Species Factor Molality Per Cent

Nd++ 1.00 1.1786E10 100.00 Total 1.1786E10 100.00

Aqueous species accounting for 99% or more of Ni++

Species Factor Molality Per Cent

Ni++ 1.00 2.0718E08 93.53 NiSO4(aq) 1.00 1.4282E09 6.45 Total 2.2150E08 99.98

Aqueous species accounting for 99% or more of Pr+++

Species Factor Molality Per Cent

Pr++ 1.00 2.8387E11 100.00 Total 2.8387E11 100.00

Aqueous species accounting for 99% or more of Rb+

Species Factor Molality Per Cent

Rb+ 1.00 4.8439E08 100.00 Total 4.8439E08 100.00

Aqueous species accounting for 99% or more of ReO4

Species Factor Molality Per Cent

ReO4 1.00 1.0741E10 100.00

168

Total 1.0741E10 100.00

Aqueous species accounting for 99% or more of SO4

Species Factor Molality Per Cent

SO4 1.00 9.9664E04 90.32 CaSO4(aq) 1.00 7.5675E05 6.86 MgSO4(aq) 1.00 2.8717E05 2.60 Total 1.1034E03 99.78

Aqueous species accounting for 99% or more of Sb(OH)3(aq)

Species Factor Molality Per Cent

Sb(OH)3(aq) 1.00 1.3144E07 99.99 Total 1.3144E07 99.99

Aqueous species accounting for 99% or more of Sc+++

Species Factor Molality Per Cent

Sc+++ 1.00 2.2244E08 100.00 Total 2.2244E08 100.00

Aqueous species accounting for 99% or more of SeO3

Species Factor Molality Per Cent

SeO3 1.00 4.5740E09 90.29 HSeO3 1.00 4.9175E10 9.71 Total 5.0658E09 100.00

Aqueous species accounting for 99% or more of SiO2(aq)

Species Factor Molality Per Cent

SiO2(aq) 1.00 3.1309E04 98.80 HSiO3 1.00 3.7201E06 1.17

169

Total 3.1689E04 99.98

Aqueous species accounting for 99% or more of Sm+++

Species Factor Molality Per Cent

SmCO3+ 1.00 1.0808E11 54.17 Sm(CO3)2 1.00 9.0858E12 45.54 Total 1.9952E11 99.71

Aqueous species accounting for 99% or more of Sr++

Species Factor Molality Per Cent

Sr++ 1.00 1.6381E06 90.27 SrSO4(aq) 1.00 1.7231E07 9.50 Total 1.8147E06 99.76

Aqueous species accounting for 99% or more of Ti(OH)4(aq)

Species Factor Molality Per Cent

Ti(OH)4(aq) 1.00 1.4623E08 100.00 Total 1.4623E08 100.00

Aqueous species accounting for 99% or more of Tl+

Species Factor Molality Per Cent

Tl+ 1.00 8.3177E11 100.00 Total 8.3177E11 100.00

Aqueous species accounting for 99% or more of UO2++

Species Factor Molality Per Cent

UO2(CO3)3 1.00 1.2387E08 69.21 UO2(CO3)2 1.00 3.8834E09 21.70 UO2(OH)2(aq) 1.00 1.2921E09 7.22 UO2(OH)3 1.00 2.9363E10 1.64

170

Total 1.7898E08 99.77

Aqueous species accounting for 99% or more of VO++

Species Factor Molality Per Cent

VO3OH 1.00 1.0809E09 55.06 VO2(OH)2 1.00 4.0586E10 20.67 HVO4 1.00 2.6666E10 13.58 H2VO4 1.00 2.0963E10 10.68 Total 1.9631E09 100.00

Aqueous species accounting for 99% or more of WO4

Species Factor Molality Per Cent

WO4 1.00 4.3515E10 100.00 Total 4.3515E10 100.00

Aqueous species accounting for 99% or more of Y+++

Species Factor Molality Per Cent

Y(CO3)2 1.00 1.0275E09 64.79 YCO3+ 1.00 5.5392E10 34.93 Total 1.5859E09 99.72

Aqueous species accounting for 99% or more of Yb+++

Species Factor Molality Per Cent

Yb(CO3)2 1.00 2.2024E11 63.52 YbCO3+ 1.00 1.2617E11 36.39 Total 3.4674E11 99.90

Aqueous species accounting for 99% or more of Zn++

Species Factor Molality Per Cent

Zn++ 1.00 2.8699E07 76.60 Zn(OH)2(aq) 1.00 2.8429E08 7.59

171

ZnSO4(aq) 1.00 2.2697E08 6.06 ZnCO3(aq) 1.00 1.7478E08 4.66 ZnOH+ 1.00 1.2472E08 3.33 ZnHCO3+ 1.00 6.5949E09 1.76 Total 3.7468E07 100.00

APPENDIX C

EQ3NR OUTPUT: MNWAT07F

Aqueous species accounting for 99% or more of Ag+

Species Factor Molality Per Cent

Ag+ 1.00 1.8499E09 99.77 Total 1.8541E09 99.77

Aqueous species accounting for 99% or more of Al+++

Species Factor Molality Per Cent

AlO2 1.00 4.2467E07 95.48 HAlO2(aq) 1.00 1.9783E08 4.45 Total 4.4475E07 99.93

Aqueous species accounting for 99% or more of Ba++

Species Factor Molality Per Cent

Ba++ 1.00 1.1058E07 99.90 Total 1.1068E07 99.90

Aqueous species accounting for 99% or more of Br

Species Factor Molality Per Cent

Br 1.00 3.7545E08 100.00 Total 3.7545E08 100.00

Aqueous species accounting for 99% or more of Ca++

Species Factor Molality Per Cent

Ca++ 1.00 2.5731E04 98.21 CaHCO3+ 1.00 2.2582E06 8.620E01 Total 2.6199E04 99.07 173 174

Aqueous species accounting for 99% or more of Cd++

Species Factor Molality Per Cent

Cd++ 1.00 8.5837E11 96.49 CdHCO3+ 1.00 2.1065E12 2.37 CdOH+ 1.00 6.8295E13 7.677E01 Total 8.8959E11 99.63

Aqueous species accounting for 99% or more of Ce+++

Species Factor Molality Per Cent

Ce++ 1.00 7.8507E11 100.00 Total 7.8507E11 100.00

Aqueous species accounting for 99% or more of Co++

Species Factor Molality Per Cent

HCoO2 1.00 1.8532E10 99.28 Total 1.8665E10 99.28

Aqueous species accounting for 99% or more of Cs+

Species Factor Molality Per Cent

Cs+ 1.00 1.7832E09 100.00 Total 1.7832E09 100.00

Aqueous species accounting for 99% or more of Cu++

Species Factor Molality Per Cent

CuCO3(aq) 1.00 9.0410E08 84.49 CuOH+ 1.00 1.3080E08 12.22 Cu++ 1.00 2.6759E09 2.50 Total 1.0701E07 99.21

175

Aqueous species accounting for 99% or more of Dy+++

Species Factor Molality Per Cent

Dy++ 1.00 2.4615E11 100.00 Total 2.4615E11 100.00

Aqueous species accounting for 99% or more of Er+++

Species Factor Molality Per Cent

Er++ 1.00 1.7936E11 100.00 Total 1.7936E11 100.00

Aqueous species accounting for 99% or more of Gd+++

Species Factor Molality Per Cent

Gd++ 1.00 1.9078E11 100.00 Total 1.9078E11 100.00

Aqueous species accounting for 99% or more of H2AsO4

Species Factor Molality Per Cent

HAsO4 1.00 1.5234E08 95.13 H2AsO4 1.00 7.7648E10 4.85 Total 1.6014E08 99.98

Aqueous species accounting for 99% or more of HCO3

Species Factor Molality Per Cent

HCO3 1.00 9.1614E04 96.70 CO2(aq) 1.00 2.2110E05 2.33 Total 9.4738E04 99.04

Aqueous species accounting for 99% or more of K+

176

Species Factor Molality Per Cent

K+ 1.00 3.7841E05 99.97 Total 3.7853E05 99.97

Aqueous species accounting for 99% or more of La+++

Species Factor Molality Per Cent

La++ 1.00 5.7593E11 100.00 Total 5.7593E11 100.00

Aqueous species accounting for 99% or more of Li+

Species Factor Molality Per Cent

Li+ 1.00 2.8807E07 99.97 Total 2.8814E07 99.97

Aqueous species accounting for 99% or more of Mg++

Species Factor Molality Per Cent

Mg++ 1.00 1.0344E04 98.21 MgHCO3+ 1.00 8.8207E07 8.375E01 Total 1.0533E04 99.05

Aqueous species accounting for 99% or more of Mn++

Species Factor Molality Per Cent

Mn++ 1.00 5.1098E08 87.73 MnCO3(aq) 1.00 6.3367E09 10.88 MnSO4(aq) 1.00 3.8557E10 6.620E01 Total 5.8247E08 99.27

Aqueous species accounting for 99% or more of MoO4

177

Species Factor Molality Per Cent

MoO4 1.00 3.1267E09 100.00 Total 3.1267E09 100.00

Aqueous species accounting for 99% or more of Na+

Species Factor Molality Per Cent

Na+ 1.00 2.6914E04 99.80 Total 2.6969E04 99.80

Aqueous species accounting for 99% or more of Nd+++

Species Factor Molality Per Cent

Nd++ 1.00 7.6262E11 100.00 Total 7.6262E11 100.00

Aqueous species accounting for 99% or more of Ni++

Species Factor Molality Per Cent

Ni++ 1.00 5.0860E09 99.50 Total 5.1116E09 99.50

Aqueous species accounting for 99% or more of Pb++

Species Factor Molality Per Cent

PbCO3(aq) 1.00 2.1074E09 82.39 PbOH+ 1.00 2.8304E10 11.07 Pb++ 1.00 1.4844E10 5.80 Total 2.5579E09 99.26

Aqueous species accounting for 99% or more of Pr+++

Species Factor Molality Per Cent

178

Pr++ 1.00 1.4194E11 100.00 Total 1.4194E11 100.00

Aqueous species accounting for 99% or more of Rb+

Species Factor Molality Per Cent

Rb+ 1.00 1.5327E08 100.00 Total 1.5327E08 100.00

Aqueous species accounting for 99% or more of SO4

Species Factor Molality Per Cent

SO4 1.00 5.2723E05 96.29 CaSO4(aq) 1.00 1.1808E06 2.16 MgSO4(aq) 1.00 7.5191E07 1.37 Total 5.4755E05 99.82

Aqueous species accounting for 99% or more of Sb(OH)3(aq)

Species Factor Molality Per Cent

Sb(OH)3(aq) 1.00 9.8558E10 99.99 Total 9.8563E10 99.99

Aqueous species accounting for 99% or more of Sc+++

Species Factor Molality Per Cent

Sc+++ 1.00 4.4488E08 100.00 Total 4.4488E08 100.00

Aqueous species accounting for 99% or more of SiO2(aq)

Species Factor Molality Per Cent

179

SiO2(aq) 1.00 4.4837E04 99.15 Total 4.5219E04 99.15

Aqueous species accounting for 99% or more of Sm+++

Species Factor Molality Per Cent

SmCO3+ 1.00 9.7034E12 72.95 Sm(CO3)2 1.00 3.5422E12 26.63 Total 1.3301E11 99.58

Aqueous species accounting for 99% or more of Sr++

Species Factor Molality Per Cent

Sr++ 1.00 9.4436E07 99.10 Total 9.5298E07 99.10

Aqueous species accounting for 99% or more of Th++++

Species Factor Molality Per Cent

Th(OH)4(aq) 1.00 8.6127E12 99.92 Total 8.6193E12 99.92

Aqueous species accounting for 99% or more of Ti(OH)4(aq)

Species Factor Molality Per Cent

Ti(OH)4(aq) 1.00 2.0887E08 100.00 Total 2.0887E08 100.00

Aqueous species accounting for 99% or more of Tl+

Species Factor Molality Per Cent

Tl+ 1.00 4.8928E12 100.00 Total 4.8928E12 100.00

180

Aqueous species accounting for 99% or more of UO2++

Species Factor Molality Per Cent

UO2(CO3)2 1.00 3.6571E10 41.85 UO2(CO3)3 1.00 2.3542E10 26.94 UO2(OH)2(aq) 1.00 2.3367E10 26.74 UO2(OH)3 1.00 3.2307E11 3.70 Total 8.7384E10 99.23

Aqueous species accounting for 99% or more of VO++

Species Factor Molality Per Cent

VO3OH 1.00 8.8126E09 56.13 VO2(OH)2 1.00 2.9851E09 19.01 H2VO4 1.00 2.1613E09 13.77 HVO4 1.00 1.7413E09 11.09 Total 1.5700E08 100.00

Aqueous species accounting for 99% or more of WO4

Species Factor Molality Per Cent

WO4 1.00 5.9831E10 100.00 Total 5.9831E10 100.00

Aqueous species accounting for 99% or more of Y+++

Species Factor Molality Per Cent

YCO3+ 1.00 1.5674E10 55.74 Y(CO3)2 1.00 1.2299E10 43.74 Total 2.8120E10 99.48

Aqueous species accounting for 99% or more of Yb+++

Species Factor Molality Per Cent

181

YbCO3+ 1.00 1.2964E11 56.08 Yb(CO3)2 1.00 1.0113E11 43.75 Total 2.3116E11 99.83

Aqueous species accounting for 99% or more of Zn++

Species Factor Molality Per Cent

Zn++ 1.00 3.4794E08 87.51 Zn(OH)2(aq) 1.00 1.5902E09 4.00 ZnOH+ 1.00 1.5047E09 3.78 ZnCO3(aq) 1.00 1.0350E09 2.60 ZnHCO3+ 1.00 6.2465E10 1.57 Total 3.9761E08 99.46