An Investigation of Metal Concentrations in Waste Rock Piles, Stream Water, Benthic Macroinvertebrates, and Stream Bed Sediments to Assess Long-term Impacts of Intermittent Precipitation Events in the Lefthand Creek Watershed,

Northwestern Boulder County, CO.

By Susan Marie Bautts

B.S., University of Colorado at Boulder, 2003

A thesis submitted to the Faculty of the Graduate School of the University of Colorado

in partial fulfillment of the requirements for the degree of Master of Science Department of Civil Engineering

2006

This thesis entitled:

An Investigation of Metal Concentrations in Waste Rock Piles, Stream Water, Benthic Macroinvertebrates, and Stream Bed Sediments to Assess Long-term Impacts of Intermittent Precipitation Events in the Lefthand Creek Watershed,

Northwestern Boulder County, CO.

written by Susan Marie Bautts has been approved for the Department of Civil Engineering

____ ________ _____ Dr. Joseph N. Ryan

________________________________________Dr. Diane McKnight

___ _______ ____ Dr. JoAnn Silverstein

Date_______________

The final copy of this thesis has been examined by the signatories, and we find that both the content and the form meet acceptable presentation

standards of scholarly work in the above mentioned discipline.

Abstract

Bautts, Susan Marie (M.S., Department of Civil Engineering)

An Investigation of Metal Concentrations in Waste Rock Piles, Stream Water, Benthic Macroinvertebrates, and Stream Bed Sediments to Assess Long-term Impacts of Intermittent Precipitation Events in the Lefthand Creek Watershed, Northwestern Boulder County, CO.

Thesis directed by Professor Joseph N. Ryan

Previous studies conducted by researchers and regulators have examined

the sources of metal toxicity from inactive mine sites in the Lefthand Creek

watershed. To date, there have been no studies conducted to assess the

effects of rain storms and rapid snow melt on stream water quality. A study of

metal concentrations in waste rock piles, in the stream water, in streambed

sediments, and in benthic macroinvertebrates was conducted in areas near

metal sources in the Lefthand, James, and Little James Creeks. It was

hypothesized that correlations exist between metal concentrations in

sediments, benthic macroinvertebrates, and waste rock piles. We expected

that zinc, copper, and lead would follow the patterns of speciation observed in

other streams and soils. In stream water, we expected zinc to be mostly

dissolved, lead mostly bound to colloids, and copper in both fractions.

Prioritizations were made for remediation based on benthic macroinvertebrate

and sediment metal concentrations.

iii

Dedication

This work is dedicated to my husband, David Bautts, for his inspiration, kind

heart and unconditional support and love.

Acknowledgements

Funding for this project was provided by Region VIII of the Environmental

Protection Agency and the Colorado Department of Public Health and the

Environment. I would like to thank all those at the EPA and the University of

Colorado’s Laboratory for Environmental and Geological Studies, for their

expert advice and laboratory analysis. This project could not have been

completed without funding provided through EPA regional grants. I would like

to thank my committee members; Diane McKnight, Joe Ryan, and Joann

Silverstein for their advising and review of this document. Thanks especially

to Joe, for his encouragement and helpful reviews. Special thanks to Isabelle

Lheritier for all of her hard work and companionship in the field. It would have

taken so much longer without you. In addition, I would like to thank Dave,

Rowen and Myles Bautts, Tim Dittrich, Joe Ryan, Brianna Shanklin and Ned

Turner for the long hours of help in the field. To all my friends and family,

thank you for your support and distractions over the past year. You’ve made

it worth it.

v

TABLE OF CONTENTS

Introduction .......................................................................................................... 1

Fate and transport of metals ................................................................................ 5

Bioavailability of Metals........................................................................................ 7

Objectives ............................................................................................................ 9

Materials and Methods....................................................................................... 13

Field research area ............................................................................................ 13

Stream water, benthic macroinvertebrate, and streambed sediment sampling

sites.................................................................................................................... 19

Stream water sampling and analysis.................................................................. 23

Water quality parameters ................................................................................... 26

Water hardness and standards .......................................................................... 26

Benthic macroinvertebrate sampling and analysis ............................................. 28

Sediment sampling and analysis........................................................................ 30

Characterization of Waste Rock Piles ................................................................ 32

Water quality measurements – pH, temperature, and specific conductance...... 35

Dissolved Organic Carbon ................................................................................. 38

Hardness and standards .................................................................................... 41

Stream water iron............................................................................................... 44

Stream water zinc, copper, and lead concentrations.......................................... 47

Lefthand Creek water –zinc, copper, and lead concentrations........................... 48

James Creek water – zinc, copper, and lead concentrations ............................. 49

Little James Creek water – zinc, copper, and lead concentrations..................... 51

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Benthic macroinvertebrate metal concentrations ............................................... 53

Lefthand Creek benthic macroinvertebrates – zinc, copper, and lead................ 55

James Creek benthic macroinvertebrate – zinc, copper, and lead..................... 57

Little James Creek benthic macroinvertebrates – zinc, copper, and lead .......... 59

Streambed sediment investigations ................................................................... 62

Effects of mass on partial digestion efficiency.................................................... 63

Reproducibility of sediment methods using field and lab replicates ................... 65

Lefthand Creek streambed sediments – zinc, copper, and lead......................... 67

James Creek streambed sediments – zinc, copper, and lead............................ 69

Little James Creek streambed sediments – zinc, copper, and lead ................... 70

Streambed sediments – <63 um grain size percentages ................................... 72

Waste rock piles................................................................................................. 75

Waste rock pile sediment metals........................................................................ 75

Waste rock pile elutriation concentrations.......................................................... 77

Discussion.......................................................................................................... 79

Copper, zinc, and lead concentrations in stream water, benthic

macroinvertebrates, and sediments ................................................................... 81

Zinc, copper, and lead inputs from waste rock piles........................................... 88

White Raven waste rock pile .............................................................................. 94

Slide Mine waste rock pile.................................................................................. 96

Metal distribution between water, colloids, and sediments................................. 97

Colloidal metals and Kint ..................................................................................... 99

Colloidal metals and hardness ......................................................................... 100

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Colloidal metals and iron hydroxide surfaces ................................................... 102

Streambed sediment metal partitioning............................................................ 104

Benthic macroinvertebrates as biomonitors ..................................................... 105

Dissolved organic carbon and metal speciation ............................................... 108

Recommendations for remediation .................................................................. 112

Summary and Conclusions .............................................................................. 115

References....................................................................................................... 116

APPENDIX A.................................................................................................... 122

APPENDIX B.................................................................................................... 131

APPENDIX C ................................................................................................... 134

APPENDIX D ................................................................................................... 140

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LIST OF TABLES

Table 1 Lefthand Creek water, sediment, and benthic macroinvertebrate

sampling site descriptions and locations by global position system. ............. 21

Table 2 James Creek water, sediment, and benthic macroinvertebrate

sampling site descriptions and locations by global position system. ............. 22

Table 3 Little James Creek water, sediment, and benthic macroinvertebrate

sampling site descriptions and locations by global position system. ............. 23

Table 4. EPA inorganic target analyte list and contract required quantitation

limits (CRQLs) for methods 200.7 (ICP-AES for water samples), and 200.8

(ICP-MS) for water samples. ......................................................................... 25

Table 5. Colorado Department of Public Health and the Environment

hardness-based equations for chronic and acute value standards for copper,

zinc, and lead. ............................................................................................... 27

Table 6. Locations of waste rock piles in Lefthand Creek watershed........... 33

Table 7. Acute and chronic table value standards (TVS) for aquatic life for

zinc, copper, and lead in Lefthand, James, and Little James Creeks............ 44

Table 8 Field blank metal concentrations measured at site LJ7. BDL is below

detection limits. Because total lead was below detection limits, and dissolved

lead was not, we can assume that dissolved lead is close to detection limits.

...................................................................................................................... 48

Table 9 Benthic macroinvertebrate background concentrations measured at

sites void of previous mining activities. BDL – Below Detection Limits. ........ 54

ix

Table 10 Background metal concentrations were determined as areas

upstream from any previously known mining activities.................................. 63

Table 11 Laboratory method replicate metal concentrations (mg kg-1 dry

weight) in streambed sediments collected at sites LJ4, LJ5, LJ6, LJ10 and J3.

...................................................................................................................... 66

Table 12 Waste rock piles rated in decreasing order of total elutriated zinc,

copper and lead. ........................................................................................... 89

Table 13 The r2 values observed from correlation analysis which tested the

hypothesis that elutriated metals from waste rock piles correlated with

downstream benthic macroinvertebrates and sediments. r2 values for lead in

benthic macroinvertebrates a weak correlation in for both total and dissolved

portions. ........................................................................................................ 91

Table 14 Percent increases in benthic macroinvertebrate and sediment metal

concentrations from above to downstream of the White Raven Mine and

waste rock pile. A negative increase represents a decrease in concentration.

...................................................................................................................... 95

Table 15 Percent increases in benthic macroinvertebrate and sediment metal

concentrations from above to downstream of the Slide Mine site. A negative

increase represents a decrease in concentration.......................................... 96

Table 16 Intrinsic surface complexation constants (Kint ) reported by Dzombak

and Morel (1990)......................................................................................... 100

Table 17 Average observed distribution coefficients between the dissolved

phase and on the streambed....................................................................... 105

x

Table 18 Increases in concentrations of copper, zinc and lead in stream

water, benthic macroinvertebrates, and sediments from above to downstream

of the Big Five tunnel drainage. These sites were sampled on July 8, 2005,

when the drainage was not flowing into Lefthand Creek. Negative values

indicate decreases in concentrations. ......................................................... 108

xi

LIST OF FIGURES

Figure 1. Lefthand Creek Watershed map with significant features. .................... 3

Figure 2. Effect of rainfall on suspended sediment in Lefthand Creek.

Photographs of Lefthand Creek in Rowena, about 8 km downstream of the

Slide Mine, taken at 5:45, 5:52 and 5:57 pm on April 8, 2004 after a relatively

light rainfall that began at 5:10 pm. .................................................................... 11

Figure 3. A map of the Lefthand Creek watershed identifying key streams,

mines (⊗), towns (ϕ) and other features. .......................................................... 14

Figure 4. A bar graph of the average yearly streamflow in Lefthand Creek

from 1929-1980. The selected years were used based on available USGS

data. ................................................................................................................... 16

Figure 5. A bar graph of the monthly mean streamflow recorded from 1929-

1980 in Lefthand Creek. The selected years were used based on available

USGS data. ........................................................................................................ 16

Figure 6. A bar plot of the available monthly mean streamflow recorded from

August 2003 to December 2005. This stream gauge has been monitored by

Colleen Williams of the James Creek Watershed Initiative since August 2003. . 18

Figure 7. A map of the Lefthand Creek watershed indicating sampling sites

for Lefthand Creek (blue circles), James Creek (red circles), and Little James

Creek (green circles). These are sampling sites for stream water, benthic

macroinvertebrates, and sediments. .................................................................. 20

Figure 8. Lefthand Creek pH and specific conductance measured in the field

during macroinvertebrate and water sampling (June 15 – August 2, 2005). ...... 36

xii

Figure 9. James Creek pH and specific conductance measured in the field

during macroinvertebrate and water sampling. .................................................. 37

Figure 10. Little James Creek pH and specific conductance measured in the

field during macroinvertebrate and water sampling............................................ 38

Figure 11. Lefthand Creek dissolved organic carbon represented with

standard deviations determined from 5 samples taken by the TOC analyzer

software (methods analysis)............................................................................... 39

Figure 12. James Creek dissolved organic carbon represented with standard

deviations determined from 5 samples taken by the TOC analyzer software

(methods analysis). ............................................................................................ 40

Figure 13. Little James Creek dissolved organic carbon represented with

standard deviations determined from 5 samples taken by the TOC analyzer

software (methods analysis)............................................................................... 41

Figure 14. Hardness calculated from magnesium and calcium concentrations

in Lefthand Creek for samples taken from June 15-July 22, 2005. .................... 42

Figure 15. Hardness calculated from magnesium and calcium concentrations

in James Creek for samples taken from June 15-July 22, 2005......................... 43

Figure 16. Hardness calculated from magnesium and calcium concentrations

in Little James Creek for samples taken from June 22, - July 18, 2005. ............ 43

Figure 17. Total (•) and dissolved (#) iron along the length of Lefthand

Creek. The chronic aquatic life standard for iron is 1000 μg L-1, which was

not exceeded...................................................................................................... 46

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Figure 18. Total (•) and dissolved (#) iron along the length of James Creek.

The chronic aquatic life standard for iron is 1000 μg/L, which was not

exceeded............................................................................................................ 46

Figure 19. Total (•) and dissolved (#) iron along the length of Little James

Creek. The chronic aquatic life standard for iron is 1000 μg L-1, which was

not exceeded...................................................................................................... 47

Figure 20. Total (•) and dissolved (#) zinc, copper, and lead concentrations

in Lefthand Creek during June 15-July 22, 2005. Closed circles represent

total metals, open circle represent dissolved metals and chronic standards

are a function of hardness and are represented by dashed lines....................... 49

Figure 21. Total (•) and dissolved (#) zinc, copper, and lead concentrations

in James Creek during July 1- August 1, 2005. Black closed circles represent

total metals, open circle represent dissolved metals, grey closed circles are

below detection limits and chronic standards are represented by dashed lines. 51

Figure 22. Total (•) and dissolved (#) zinc, copper, and lead concentrations

in Little James Creek during June 22, - July 18, 2005. Closed circles

represent total metals, open circle represent dissolved metals and chronic

standards are represented by dashed lines. ...................................................... 53

Figure 23. Zinc, copper, and lead concentrations measured in

macroinvertebrates in Lefthand Creek from June 15, - July 22, 2005. ............... 57

xiv

Figure 24. Zinc, copper, and lead concentrations measured in

macroinvertebrates in James Creek from July 1, - August 1, 2005. Missing

data points indicates levels measured below detection limits............................. 59

Figure 25. Zinc, copper, and lead concentrations measured in

macroinvertebrates in Little James Creek from June 22, - July 18, 2005.

Missing data points indicates levels measured below detection limits. Upside

down triangles represent sites with no macroinvertebrates present at the time

of sampling......................................................................................................... 62

Figure 26. Effect of amount of sediment on metal releases from the sediment

collected at site LJ13 (1.59 km) by the partial digestion method. ....................... 64

Figure 27. Effect of amount of sediment on metal releases from the sediment

collected at site LJ7 (2.89 km) by the partial digestion method. ......................... 65

Figure 28. Lefthand Creek Zn, Cu, and Pd in streambed sediments (grain

size <63 μm). Metals released via acid-extraction. Samples were collected

from October 1-October 17, 2005. ..................................................................... 68

Figure 29. Lefthand Creek (11-30 km) Cu, Zn and Pd in streambed

sediments (grain size <63 μm). Metals released via partial digestion methods.. 69

Figure 30. James Creek Zn, Cu, and Pb in sediments (grain size <63 μm).

Metals released via acid-extraction. Samples were collected between October

1, - October 17, 2005. ........................................................................................ 70

Figure 31. Little James Creek Zn, Cu, and Pb in sediments (grain size <63

μm). Metals released via partial digestion method. Samples were collected

on September 24, 2005...................................................................................... 72

xv

Figure 32. Left Hand Creek - percent of sediments that are <63μm in size. ..... 74

Figure 33. James Creek - percent of sediments that are <63 um in size. ......... 74

Figure 34. Little James Creek - percent of sediments that are <63 um in size.. 75

Figure 35. Concentrations of metals elutriated from waste rock piles along

Lefthand Creek. Data collected by Amber Roche. White bars represent zinc,

grey bars represent copper, and black bars represent lead. .............................. 76

Figure 36. Concentrations of metals in sediments at waste rock piles along

Little James Creek. Data collected by Amber Roche. ....................................... 76

Figure 37. Lefthand Creek waste rock pile total elutriated metal

concentrations. Error bars represent standard deviations of duplicate

samples.............................................................................................................. 77

Figure 38. Little James Creek waste rock pile total elutriated metal

concentrations. Error bars represent standard deviations of duplicate

samples.............................................................................................................. 78

Figure 39. Comparisons of metals in benthic macroinvertebrates and

dissolved metals in water (left column) and metals in sediments and dissolved

metals in water (right column) for zinc, copper, and lead in Lefthand Creek. ..... 83

Figure 40. Comparisons of metal concentrations in benthic

macroinvertebrates and dissolved metals in water (left column) and metal

concentrations in sediments and stream water (right column) for copper, zinc,

and lead in James Creek.................................................................................... 84

xvi

Figure 41. Comparisons of metal concentrations in macroinvertebrates and

stream water (left column) and metal concentrations in sediments and stream

water (right column) for copper, zinc, and, lead in Little James Creek. .............. 85

Figure 42. Comparisons of metals in benthic macroinvertebrates and metals

in sediments for all of Lefthand Creek (left column) and for only the California

Gulch reach of Lefthand Creek (right column).................................................... 86

Figure 43. Comparisons of metals in benthic macroinvertebrates and metals

in sediments for zinc, copper, and, lead in all of James Creek........................... 87

Figure 44. Comparisons of metals in benthic macroinvertebrates and metals

in sediments for zinc, copper, and lead in all of Little James Creek. .................. 88

Figure 45. A correlation analysis between macroinvertebrate (plots on the

left) and sediment (plots on the right) metal concentrations downstream of

waste rock piles and total elutriated metals (zinc – squares, copper –

triangles, and lead – circles). Dashed lines are the 95% confidence intervals. . 92

Figure 46. A correlation analysis between macroinvertebrate (plots on the

left) and sediment (plots on the right) metal concentrations downstream of

waste rock piles and dissolved elutriated metals (zinc – squares, copper –

triangles, and lead – circles). Dashed lines are the 95% confidence intervals. . 93

Figure 47. The colloidal fraction (fcolloid) of zinc, copper, and lead in the three

creeks of the Lefthand watershed (left column, mean and one standard

deviation shown by error bar), and the dependence of the colloidal fraction on

the pH of the water samples (right column - zinc (circles), copper (triangles),

and lead (squares)). ........................................................................................... 99

xvii

Figure 48. Colloidal fractions of zinc (circles), copper (triangles), and lead

(squares) compared to the logarithms of the intrinsic surface complexation

constants (log Kint) reported by Dzombak and Morel (1990). ........................... 100

Figure 49. Fractions of colloidal metal versus hardness in James (closed

circles), Lefthand (open circles) and Little James (closed triangles creeks. ..... 102

Figure 50. The influence of pH on colloidal fractions of iron (fcolloid) throughout

the watershed................................................................................................... 103

Figure 51. Colloidal fraction of copper, zinc, and lead as a function of

colloidal iron concentration (μmol L-1). Regression analysis determined r2

values of zero for all metals.............................................................................. 104

Figure 52. Logarithms of the distribution coefficients (Kd, L kg-1) for sediment-

water distribution of zinc, copper, and lead for all sampling sites in the

watershed as a function of pH.......................................................................... 105

Figure 53. Concentration of metals in benthic macroinvertebrates as a

function of concentration of dissolved organic carbon (DOC) for all sampling

sites.................................................................................................................. 110

Figure 54. The colloidal fraction of metals (fcolloid) as a function of DOC show

weak correlations (zinc (0.14), copper (0.06), and lead (0.065). ...................... 111

xviii

Introduction

Mining activities around the world have left countless streams, rivers

and lakes contaminated with toxic concentrations of heavy metals (Moore and

Luoma 1990; Davies et al. 1994). In Boulder County, Colorado in the mid-

1800s, a boom of settlers arrived looking to mine and mill precious metals in

Boulder County. The legacy from this era was assessed in 1993 by the

Colorado Geological Survey through the identification of 230 mine openings

and 186 tailings piles, all presently abandoned within the Lefthand Creek

watershed (Sares and Lovekin 1993). It has been determined that these

tailings piles and mines continue to provide a source of toxic metals as

intermittent streams meander through and erode tailings deposits and

transport them into main stream channels threatening human and aquatic life

(LWTF 2002).

Lefthand Creek is a key source of water for the Left Hand Water

District and its 14,000 customers in unincorporated Boulder County. It is the

concern of local citizens, government agencies, and stakeholder groups that

in the event of a catastrophic flood or precipitation event, toxic metals may

contaminate the stream water and subsequently, the water supply. Lefthand

Creek has always been the principal millstream of Boulder County (Cobb

1988). It was considered a “dead creek” by fisherman and nearby residents

until the 1930s (Cobb 1988; LWTF 2002). Around this time, it was reported

that the acid mine drainage and toxic components thereof began to attenuate.

This allowed the creek to support aquatic life once again. However, to this

1

day, there is still significant contamination in various reaches. In July, 2001,

after much deliberation between local communities and federal and local

agencies over concerns of water quality impairment due to abandoned mines,

mills and waste rock piles, the Lefthand Watershed Task Force (LWTF) was

established by Boulder County. In March, 2002, the Task Force issued a

report for the BCHD on the effects of abandoned mines on the upper

Lefthand watershed (west of Highway 36). The report indicated that the most

significant cause of water quality impairment was due to past mining activities

(LWTF 2002). The Little James Creek, a tributary of James Creek, which is a

tributary of Lefthand Creek, was subject to the first documented complaints

concerning water quality in the Lefthand Watershed in the mid-1960s. The

Boulder County Health Department (BCHD) found water samples near the

Burlington Mine (along Little James Creek) to be high in sulfate, total solids

(TS), and various heavy metals (LWTF 2002).

2

Balarat Creek

Burlington Mine

Haldi Diversion

Dew Drop

Little James Creek

Lefthand Creek

Slide Mine

JAMESTOWN

WARD

Indiana Gulch

Lick Skillet Gulch

Nugget Gulch

Lee Hill Gulch

ROWENA

un-named waste

Streamside tailings

Bueno Mtn.

Argo Mine

White Raven

Big Five Tunnel

Spring Gulch

Fairday Mine John Jay mine

Sixmile Creek

Castle

Evening Star

Emmett adit

Loder Smelter

James Creek

Peak to Peak US

Figure 1. Lefthand Creek Watershed map with significant features.

Current activities to improve water quality in the watershed are

occurring at many sites within the watershed including, the Captain Jack Mine

and Mill, the Burlington Mine, the Slide Mine, the “streamside tailings,”

Fairday Mine, and the Golden Age mine.

The Captain Jack Mine and Mill is an EPA Superfund site (includes the

Big Five Tunnel drainage, the Blackjack Mine, the Captain Jack mill, and the

White Raven Mine) located just south of the town of Ward along a segment of

Lefthand Creek referred to locally as “California Gulch.” The site was listed

on the states National Priority List (NPL) in September, 2003, and the

remedial investigation and feasibility study were completed in April, 2006.

3

The Burlington Mine is located along Little James Creek one mile north

of Jamestown. This site was listed as a Voluntary Clean-Up Program (VCUP)

site in April, 2002, and remediation of the Burlington Mine is undergoing. The

remediation and VCUP listing was instigated by Honeywell, Inc., the private

owner.

The Slide Mine encompasses a 3 hectares area located along

Lefthand Creek just upstream of the small town of Rowena (Figure 1). The

Slide Mine has recently been considered for VCUP due to occurrences of

sediment loading into Lefthand Creek during precipitation events and metals

loading.

The Bueno Mine tailings and the “streamside tailings,” located just

west of Jamestown (Figure 1), are being considered for the EPA’s Emergency

Response program. This was due in part to the remedial investigations

conducted by the US Forest Service. The Emergency Response program was

set up by the EPA to protect human and public health during an emergency

involving a threatened release of hazardous waste. Jamestown is

surrounded by steep eroding slopes and recently experienced mudslides in

the early summer of 2005. Bueno Mountain resides just above Jamestown

and the potential exists for the release of toxic metals during a rain storm or

rapid snowmelt.

The US Forest Service has completed reclamation projects at the

Fairday Mine on James Creek, west of Jamestown (Figure 1) and is about to

4

undertake a reclamation of the Golden Age Mine located northeast of

Jamestown.

The Lefthand Watershed Oversight Group (LWOG), a stakeholder

group, was formed as a final recommendation of the Lefthand Watershed

Task Force. The LWOG, along with the aid of researchers from the

University of Colorado, developed a watershed plan to characterize metal

loading in the Lefthand, James, and Little James Creek watersheds and

identified future remediation targets (Wood et al. 2004). The experiments

discussed within this report are an extension of this previous outreach by the

University of Colorado to assist the LWOG in further characterization and

prioritization of toxic metal sources. A list of metals which have exceeded

aquatic life standards in the watershed was compiled by the Lefthand

Watershed Task Force and includes aluminum, cadmium, copper, iron, lead,

manganese and zinc (LWTF 2002). Based on the frequency of aquatic life

standard exceedences and the ability to reinforce metal solubility trends, for

this study, we focused on copper, zinc and lead.

Fate and transport of metals

Metal transport from abandoned mine sites and mining waste piles is a

secondary process to the natural weathering of pyrite exposed to chemical

and biological processes (Evangelou 1995; Adriano 2001). The oxidation of

reduced sulfur in pyrite results in the release of H+ and SO42- ions into soil

solution. The acidity leaches heavy metals from waste rock and mill tailings.

5

Geochemical interactions among surface water, colloidal materials, stream

bed sediments and mineralogy are the essential components for predicting

metal solubility as well as bioavailability (Stumm and Morgan 1996). During

precipitation and snowmelt, low pH runoff from waste rock piles transports

zinc, copper and lead away from metal sources and into nearby streams. The

metals in the acidic runoff remain in solution due to a lower affinity to bind to

surfaces and thus are transported for long distances. Studies have shown

that the stream water quality downstream improves with distance in relation to

abandoned mines and metal sources (Church et al. 1997; Munk et al. 2002).

In neutral waters, metals precipitate or adsorb to mineral surfaces. Mineral

hydroxide surfaces provide adsorption sites for the metals cations. The

surfaces are either protonated, de-protonated or neutral depending upon pH

(Dzombak and Morel 1990; Drever 1997). The pH range going from 0 –

100% adsorption of metal cations to a hydrodixe surface is narrow (about 2

pH units) and varies for each metal (typically 5 -7). Numerous studies have

confirmed the selectivity of metals for adsorption to surfaces follow the

general sequence (Axtmann et al. 1990; Davis and Kent 1990; Dzombak and

Morel 1990; Kimball et al. 1995; Church et al. 1997; Wang et al. 1997; Davis

and Atkins 2001; Covelo et al. 2004):

Cr3+ > Pb2+ > Cu2+ > Zn2+ > Cd2+ > Ca2+.

This sequence has been found to vary not only with pH, but concentration of

individual metals and stream water hardness. The adsorption-desorption

mechanism of a metal cation at a surface can be represented using an

6

intrinsic constant (Kint). The intrinsic constant is a function of the

concentrations of metals near the surface and the nature of the solid surface,

not including surface charge (Singer and Stumm 1970; Dzombak and Morel

1990). Metals that are immobilized by adsorption or precipitation

mechanisms will be retained upon sediments unless all active sites are

loaded or there is a change in the chemical environment (pH, redox potential,

degradation of organics, fluid composition and temperature changes) which in

turn re-mobilizes the metals (Pagnanelli et al. 2003).

Bioavailability of Metals

Elevated metal concentrations have been found in benthic

macroinvertebrates downstream of abandoned mines in the many streams of

the Rocky Mountains and elsewhere. As a consequence of metal pollution in

rivers and streams, benthic macroinvertebrates have been known to

accumulate metals in concentrations that are indicative of their immediate

environment (Hare et al. 1991; Cain et al. 1992; Kiffney and Clements 1992;

Clements and Kiffney 1994). In addition, it has been found that benthic

macroinvertebrate metal concentrations persist great distances downstream

from metal sources (Farag et al. 1998). The metals integrated into the tissues

of benthic macroinvertebrates are an accumulation of varying in-stream water

quality conditions over time (Clements and Kiffney 1994). These

concentrations can be used indirectly to determine the degree of metal

loading by comparing benthic macroinvertebrate metal concentrations at

contaminated sites to background sites (Woodward et al. 1994; Woodward et

7

al. 1995; Farag et al. 1999). Background sites include areas of the

investigated watershed where previous mining activities did not occur and

stream conditions are relatively pristine. The metals that accumulate in the

bodies of benthic macroinvertebrates from water and sediments can also be

ingested by fish, which studies have shown to be their main source of metal

exposure (Farag et al. 1998).

Early studies in the Clark Fork River, Montana showed that with

continual downstream copper concentrations in the water decreasing,

concentrations in benthic macroinvertebrates (as well as sediments)

remained high (Woodward et al. 1994; Lanno et al. 1997; Cain et al. 2000).

Furthermore, during a spring sampling event in the upper Arkansas River in

Colorado, scientists found that copper and zinc concentrations in benthic

macroinvertebrates remained elevated above background levels 45 km

downstream of a tributary containing acidic metal-laden flow from abandoned

mine sites (Clements and Kiffney 1994). In a study conducted in 2000,

copper and lead concentrations in sediments and in the benthic

macroinvertebrate Hydropsyche californica were found to be positively

correlated in a majority of the samples taken in the Sacramento River (Cain et

al. 2000).

It has been found that the leachability of metals from benthic

macroinvertebrates varies considerably between species (Kiffney and

Clements 1992; Clements and Kiffney 1994; Cain et al. 2004; Prusha and

Clements 2004) and that care should be taken when looking at metal

8

concentrations in pooled communities. The benthic macroinvertebrates,

Archtopsyche grandis (Kiffney and Clements 1992; Clements and Kiffney

1994; Maret et al. 2003; Cain et al. 2004; Prusha and Clements 2004) and

Hydropsyche californica (Cain et al. 2000) have been used as target species

of collection for studies using benthic macroinvertebrate metal accumulation

for monitoring metals impacts from abandoned mine sites in Rocky Mountain

streams. Using a single species for monitoring metal impacts in streams

limits variability in metal accumulation due to varying feeding habits and metal

tolerance.

Objectives

One of the suggestions made by the Lefthand Watershed Task Force

was to determine the potential effects on water quality in the event of a

catastrophic storm event or rapid snowmelt. The impacts on streams in

Lefthand Creek are associated with the risk of contaminated sediment moving

downstream gradually over time or instantaneously during periods of high

discharge or flood. In order to determine the outcome of such an event, it is

important to assess the effective methods for measuring the impacts of

intermittent storms. Previous studies conducted by the Lefthand Watershed

Oversight Group and the University of Colorado incorporated tracer dilution

tests to identify metal loading to streams. A tracer study uses a highly

concentrated salt injected at a point in the stream while synoptic sampling at

various locations downstream is conducted. Knowing the initial concentration

of the tracer and by how much it is diluted at all sampling locations, the

9

streamflow can be determined. Using these precise measurements for

stream flow along with samples analyzed for metal concentrations, metal

loading can be calculated. The tracer study was not able to identify metal

loading to the stream as a result of intermittent storm events which erode and

weather waste rock piles and transport metals to the stream. The tracer tests

give only a snapshot in time of the metals transported from an upstream

source. If conducted on a sunny day, these studies miss metal inputs that

would have been present if it was raining or snowing. Anecdotal evidence of

metal loading during a precipitation event is represented in Figure 2 below.

Sediment loading, visualized by muddy brown water, from the Slide Mine

during numerous precipitation events, such as the one in Figure 2 have been

reported by residents downstream of the Slide Mine in the town of Rowena.

We make the assumption that the stream water metal concentration in the

third photograph is greater than in the first and second photo. Conducting a

tracer study during a precipitation event such as this has proved to be

impractical. Using an auto-sampler to collect data over time would be useful,

however due to maintenance and upkeep and the fact that this was an

outreach project with results needed in a timely manner, this option was ruled

out.

10

Figure 2. Effect of rainfall on suspended sediment in Lefthand Creek. Photographs of Lefthand Creek in Rowena, about 8 km downstream of the Slide Mine, taken at 5:45, 5:52 and 5:57 pm on April 8, 2004 after a relatively light rainfall that began at 5:10 pm.

The goal of this study is to assess the impacts of these intermittent

precipitation events by measuring metal concentrations, specifically copper,

zinc and lead in the benthic macroinvertebrates, streambed sediments, and

stream water in the Lefthand, Little James and James Creeks. In addition to

these stream-related concentrations, we will also use previous data from

elutriation and weak acid extraction tests conducted on numerous waste rock

pile sediments located along Lefthand and Little James Creeks to determine

origination of metals. This data was collected by Amber Roche, Alice Wood,

and Joseph Ryan of the University of Colorado as part of the current LWOG

investigation.

By completing simple regression analyses on multiple combinations of

paired data sets, we can identify correlations between water, benthic

macroinvertebrates and sediments. Results from both correlative and non-

correlative data-sets will provide insight into which datasets indicate long-term

11

accumulation of metals. In order to assess the impacts of intermittent

sources of toxic metals to streams in the Lefthand Creek watershed, metal

concentrations were measured in the stream water, benthic

macroinvertebrates, stream sediments, and waste rock piles. Our analyses

focused on zinc, copper, and lead because these metals most frequently and

consistently exceed aquatic life standards in the watershed (Lefthand

Watershed Task Force 2002; Wood et al. 2004), and because these metals

behave quite differently with respect to adsorption to minerals, organic matter,

and organisms (Adriano 2001; Prusha and Clements 2004). Typically, zinc is

mainly dissolved and lead is mainly bound to minerals, organic matter, and

organisms, while copper can be found in both dissolved and bound species.

Exposure time to toxic metals and the fate and transport of metals in streams

were key factors in creating hypotheses.

We hypothesized that benthic macroinvertebrates and sediments,

which have proved to be good monitors of metal loading over time (Hare et al.

1991; Woodward et al. 1994), will provide evidence of metal inputs in to the

streams by intermittent tributaries and snow melt. Because both benthic

macroinvertebrates and sediments are expected to be good monitors of metal

loading from intermittent sources, we expect that the metal concentrations in

the benthic macroinvertebrates and the sediments will be correlated, but that

the metal concentrations in the benthic macroinvertebrates and sediments will

not be correlated with the metal concentrations in the stream water. We

expect that zinc, copper, and lead will follow the patterns of speciation

12

observed in other streams and soils (Singer and Stumm 1970; Dzombak and

Morel 1990; Kimball et al. 1995; Farag et al. 1998; Fey et al. 1999; Schemel

et al. 2000; Munk et al. 2002). In the stream water samples, we expect that

zinc will be mostly dissolved, lead would be mostly bound to colloids, and

copper would be found in both fractions. Because of this behavior, we expect

to find more lead and less zinc accumulation in the sediments and benthic

macroinvertebrates. We expect that the amount of dissolved organic matter

in the streams will play a role in the metal distributions between water,

sediments, and benthic macroinvertebrates. Finally, based on findings

produced from testing these hypotheses, we will prioritize abandoned mine

cleanup in the Lefthand Creek watershed.

Materials and Methods

Field research area

The Lefthand Creek watershed (Figure 3) drains an area of

approximately 220 km2. Located at the northern tip of the Colorado Mineral

Belt, the watershed drains mainly Precambrian metamorphic and igneous

formations and glacial and alluvial deposits. The watershed terrain is about

one-half alpine and sub-alpine forest and one-half agricultural and urban on

the high plains east of the front range of the Rocky Mountains. Lefthand

Creek, James Creek, and Little James Creek are the primary streams in the

upper half of the Lefthand Creek watershed.

13

Figure 3. A map of the Lefthand Creek watershed identifying key streams, mines (⊗), towns

(ϕ) and other features.

Lefthand Creek originates in glacial and snow melt waters at an

elevation of approximately 4,200 m in the Indian Peaks Wilderness area near

the Continental Divide and approximately 5 km west of Highway 72 and the

town of Ward, Colorado. It is just east of the town of Ward where Lefthand

Creek flows through portions of the Ward mining district, including the Captain

Jack Mine and Mill Superfund site. This Superfund site is located on a

segment of the stream locally referred to as the California Gulch.

Downstream of California Gulch, Lefthand Creek flows past mine waste rock

piles and receives water from multiple tributaries draining mine sites off the

steep vertical grades of Lefthand Canyon. The Lefthand Creek empties out

14

onto the high plains at an elevation of approximately 1,400 m which is nearly

40 km downstream of its headwaters. Ultimately, Lefthand Creek flows into

the St. Vrain Creek, which eventually feeds the South Platte River.

Annual mean and monthly mean stream flows were recorded in Lefthand

Creek by the United States Geological Survey from 1929 to 1980. The

survey staff gage was located at 40°07'32" north latitude and 105°18'12" west

longitude. The annual mean stream flows in those years ranged from 603 L

s-1 to 1183 L s-1 (Figure 4) while the average monthly stream flow ranged from

90 L s-1 to 4700 L s-1. The peak flows occur in May and June during the

spring snowmelt which is highly characteristic of a mountain stream. During a

recent study in the Lefthand Creek watershed researchers recorded

streamflow in Lefthand Creek ranging from 45 L s-1 at Peak to Peak highway

to 2500 L s-1 at the Haldi diversion gate during the high flow season (Wood

2003). It was also estimated that James Creek adds 550 L s-1 to Lefthand

Creek and is the most significant source of inflow.

15

Lefthand Creek average yearly streamflow (1929-1980)

0

200

400

600

800

1000

1200

1400

1600

1930 1948 1949 1950 1951 1952 1953 1956 1977 1978 1979

Year

Flow

(L/s

)

Figure 4. A bar graph of the average yearly streamflow in Lefthand Creek from 1929-1980. The selected years were used based on available USGS data.

Lefthand Creek monthly mean streamflow in L/s (1929-1980)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Month

Flow

(L/s

)

Figure 5. A bar graph of the monthly mean streamflow recorded from 1929-1980 in Lefthand Creek. The selected years were used based on available USGS data.

16

James Creek is a major tributary of Lefthand Creek which flows

through the Boulder County community of Jamestown and provides its sole

source of drinking water. This sub-watershed is covered entirely by alpine

and sub-alpine forest. James Creek drains an area of approximately 48 km2.

Elevations in the James Creek watershed range from approximately 3,000 m

at the headwaters in the Indian Peaks Wilderness Area to 2,000 m at the

confluence with Lefthand Creek approximately 5 km south of Jamestown. The

annual average streamflow in 2004 and 2005 in James Creek was 1070 L s-1

and 1300 L s-1 respectively. Average monthly flows between August of 2003

until December of 2005 are illustrated in Figure 6 with the maximum

discharge approximately 3000 L s-1 in the month of June. Flows were

measured at a staff gauge station in Jamestown located at 40º06’55.8” north

latitude and 105º23’18.9” west longitude by Colleen Williams of the James

Creek Watershed Initiative. The headwaters of the James Creek watershed

supply only a small fraction of the flow into James Creek. During parts of the

year a diversion of the South St. Vrain Creek contributes nearly all of the flow

of James Creek (CDWR 2002). Snowmelt in the South St. Vrain Creek

headwaters feeds high flows in James Creek. James Creek and its tributaries

drain steep graded mined areas such as the Jamestown Mining District and

the Golden Age Mining District. James Creek is the main source of drinking

water for Jamestown. The creek is diverted to a small treatment plant just

downstream of Bueno Mountain on Ward Street (County Road 102J).

17

James Creek monthly mean streamflow, L/s (August 2003 - December 2005)

0

500

1000

1500

2000

2500

3000

3500

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Month

Flow

(L/s

)

Figure 6. A bar plot of the available monthly mean streamflow recorded from August 2003 to December 2005. This stream gauge has been monitored by Colleen Williams of the James Creek Watershed Initiative since August 2003.

Little James Creek is a tributary of James Creek. The confluence

occurs just downstream of the Jamestown water treatment plant near the

corner of Main Street and Ward Street. Little James Creek drains a

watershed area of approximately 15 km2. Alpine and sub-alpine forests cover

the sub-watershed. Cumulative stream flow data for Little James Creek is

unavailable. However, a University of Colorado research team conducted a

lithium chloride tracer-study which was able to identify streamflow during the

Spring of 2003 and Fall of 2003 (Wood 2003). During the high flow period

(spring 2003), the flow increased from the furthest upstream site at the

headwaters to the lowest downstream site at the confluence with James

18

Creek from 110 L s-1 to 540 L s-1 respectively. Low flow data was determined

to be unreliable and was therefore not reported. Visual reports indicate that

the creek has a tendency to become dry along a large portion of the stream

from its headwaters down to the “streamside tailings” in the summer months.

The James Creek low flow tracer-study conducted by Wood found that there

was not a significant input from the Little James Creek.

Stream water, benthic macroinvertebrate, and streambed sediment

sampling sites

Field sites along Lefthand, James and Little James Creeks were

chosen based upon a University of Colorado report to the LWOG which

ranked areas as low, medium and high priority based on pH, toxic metal

concentrations and metal loading rates (Wood et al. 2004). Field sites

chosen for this study are listed in Table 1, Table 2 and Table 3 including the

sample site name, global positioning system (GPS) site identification (ID), a

brief site description, and the appropriate latitude and longitude locations.

Figure 7 shows the locations of the sampling sites for all three streams.

These sites were sampled for stream water, benthic macroinvertebrates, and

sediments.

On Lefthand Creek the Big Five Tunnel was given a high priority

ranking by Wood et al (2004). Sites ranked for medium priority ranked sites

along Lefthand Creek include the Dew Drop Mine, the White Raven Mine, the

Loder Smelter, various unnamed tributaries downstream of the Loder smelter,

Spring Gulch, and the Slide Mine.

19

Castle Gulch located along James Creek was given a medium priority ranking

while the Fairday Mine and Bueno Mine were given high rankings.

Little James Creek contained the highest number of high priority sites

including Balarat Creek, which drains the Burlington Mine, various un-named

tributaries, and waste rock piles downstream of the confluence of Balarat

Creek and Little James Creek and above Jamestown, and the “streamside

tailings.” The Argo Mine and Evening Star Mine were given a medium priority

ranking on Little James Creek.

Figure 7. A map of the Lefthand Creek watershed indicating sampling sites for Lefthand Creek (blue circles), James Creek (red circles), and Little James Creek (green circles). These are sampling sites for stream water, benthic macroinvertebrates, and sediments.

20

Table 1 Lefthand Creek water, sediment, and benthic macroinvertebrate sampling site descriptions and locations by global position system.

sample site name site ID site description

latitude longitude (º, ‘, “)

LH1 5560A-1 at the Peak-to-Peak Highway 40 04 09.27 N 105 31 00.66 W

LH2 5560A-6 upstream of unnamed tributary that drains mine across Peak-to-Peak

40 03 54.97 N 105 30 47.74 W

LH3 5560A-8 downstream of unnamed tributary that drains mine across Peak-to-Peak

40 03 53.14 N 105 30 42.66 W

LH4 5560A-13 upstream of Big Five Tunnel drainage confluence

40 03 44.21 N 105 30 34.81 W

LH5 5560A-14 downstream of Big Five Tunnel drainage confluence

40 03 42.9 N 105 30 31.54 W

LH6 5560A-17 upstream of White Raven Mine site 40 03 38.45 N 105 30 24.98 W

LH7 5560A-21 downstream of White Raven Mine site

40 03 31.86 N 105 30 21.9 2 W

LH-PU 5560A-PU Puzzler Gulch 40 03 20.28 N 105 30 06.63 W

LH-IN 5560A-IN Indiana Gulch 40 03 21.74 N 105 30 04.3 7 W

LH8 5560A-56 downstream of Indiana Gulch confluence at Sawmill Road.

40 03 20.81 N 105 30 02.4 7 W

LH9 5560A-95-1 above Lickskillet Rd and below tailings

40 04 27.77 N 105 24 47.3 3 W

LH10 5560A-96 below Lickskillet Gulch 40 04 27.69 N 105 24 43.82 W

LH11 5560A-101 150 meters upstream of Slide Mine discharge

40 04 28.60 N 105 24 02.9 8 W

LH-SL 5560A-SL1 slide Mine discharge 40 04 28.53 N 105 24 02.8 9 W

LH12 5560A-103 below Slide Mine 40 04 29.70 N 105 23 53.08 W

LH13 5560A-113 below Rowena 40 04 43.50 N 105 23 01.54 W

LH14 5560A-123 below Nugget Gulch, above “Lee Hill Gulch”

40 05 20.04 N 105 21 46.95 W

LH15 5560A-129 below “Lee Hill Gulch” 40 05 35.69 N 105 21 02.18 W

LH16 5560A-136-2 below James Creek confluence at pull-off

40 06 15.61 N 105 20 16.19 W

LH17 5560A-127 downstream of US Forest Service off-highway vehicle access

40 06 31.77 N 105 19 05.67 W

LH18 5560A-171 at Buckingham Park 40 06 40.07 N 105 18 25.34 W

LH19 5560A-184 at Haldi Head gate, Left Hand Water District intake

40 07 53.07 N 105 17 33.11 W

21

Table 2 James Creek water, sediment, and benthic macroinvertebrate sampling site descriptions and locations by global position system. sample site

name site ID site description latitude longitude (º, ‘, “)

J1 5561A-T1 reference Site above Peak-to-Peak highway

40 05 21.33 N 105 29 46.75 W

J2 5561A-T2 downstream of County Road 100 40 05 31.25 N 105 29 09.56 W

J3 5561A-T3 upstream of Forget-Me-Not Meadow and Fairday drainage

40 05 57.57 N 105 25 59.30 W

J4 5561A-T4 upstream of road crossing, downstream of tailings piles

40 06 04.78 N 105 25 47.83 W

J-FD 5561A-FD Fairday Mine drainage 40 06 40.77 N 105 25 20.26 W

J5 5561A-JOHN Downstream of John Jay mine 40 06 19.70 N 105 25 38.60 W

J6 5561A-10 200 yds downstream of Fairday drainage

40 06 38.40 N 105 25 14.35 W

J7 5561A-16 upstream of Bueno discharge 40 06 50.24 N 105 24 03.13 W

J8 5561A-28 upstream of DW intake, downstream of Bueno discharge

40 06 54.86 N 105 23 31.55 W

J9 5561A-30-582

downstream of Little James confluence in Jamestown

40 06 55.75 N 105 23 18.86 W

J10 5561A-55 upstream of Curie Springs 40 06 28.45 N 105 22 22.16 W

J-CU 5561A-CU Curie Springs 40 06 34.53 N 105 21 33.40 W

J11 5561A-52 downstream of Curie Springs 40 06 34.34 N 105 21 29.95 W

J12 5561A-53 upstream of Castle Gulch, downstream of Curie

40 06 34.34 N 105 21 29.95 W

J-CG 5561A-CG Castle Gulch 40 06 26.36 N 105 21 11.79 W

J13 5561A-61 just downstream of Castle Gulch 40 06 25.78 N 105 21 10.08 W

J14 5561A-62 upstream of confluence with Lefthand Creek

40 06 07.94 N 105 20 33.31 W

22

Table 3 Little James Creek water, sediment, and benthic macroinvertebrate sampling site descriptions and locations by global position system.

sample site name

site ID site description latitude longitude (º, ‘, “)

LJ1 5562A-0 upstream of Argo mine and tailings

40 08 12.91 N 105 24 41.57 W

LJ2 5562A-1 downstream of Evening Star 40 07 52.32 N 105 24 24.41 W

LJ3 5562A-6 upstream of small tailings pile and Argo

40 07 46.70 N 105 24 06.99 W

LJ4 5562A-8 upstream of Argo discharge, upstream of Burlington Mine

40 07 44.75 N 105 24 06.99 W

LJ5 5562A-10 downstream of Argo discharge, upstream of Burlington

40 07 42.02 N 105 24 01.91 W

LJ6 5562A-14 upstream of Balarat, downstream of Emmit

discharge

40 07 35.94 N 105 23 57.3 W

LJ7 5562A-16 upstream of Balarat 40 07 33.74 N 105 23 54.61 W

LJ8 5562A-18-1 upstream of Joe Ryan tailings 40 07 27.03 N 105 23 52.35 W

LJ9 5562A-21 downstream of Joe Ryan Tailings

40 07 24.99 N 105 23 50.84 W

LJ10 5562A-28 upstream of “streamside tailings”

40 07 11.52 N 105 23 39.14 W

LJ11 5562A-32 downstream of “streamside tailings”

40 07 04.02 N 105 23 38.08 W

LJ12 5562A-35 below waterfall GPS not taken

LJ13 5562A-38 upstream of confluence with James Creek

40 06 58.41 N 105 23 28.35 W

Stream water sampling and analysis

Stream water samples were collected from June 15 to August 2 at all

sites listed in Table 1, Table 2, and Table 3 and shown in Figure 7. Site-

specific sampling dates can be found in Appendix A. Duplicate samples were

taken at every tenth site sampled as indicated in the EPA’s sampling and

analysis plan for the Lefthand Creek watershed (Hernandez et al. 2004). Two

water samples were collected at each site to be later analyzed for total and

23

dissolved metals. De-ionized water was brought to the field and filled into a 1

L polypropylene bottle to serve as the field blank.

All field samples were collected in 1 L polypropylene bottles and

placed in a cooler on ice. In the laboratory, the samples were stored in a

refrigerator at 5ºC. Samples to be analyzed for total metals were immediately

acidified to a pH of less than 2 using a concentrated trace metal grade nitric

acid (Fisher Scientific). Samples to be analyzed for dissolved metals were

filtered with a MAGNA 0.45 μm, nylon membrane (Osmonics, Inc.) prior to

acidification. All samples were filtered using vacuum extraction and a 500 mL

polypropylene, filter apparatus (Nalgene). The difference between total and

dissolved values was used as the concentration of colloidal metals for a

sample. All samples were stored at 5ºC until further EPA metal analysis.

Water samples were sent to a laboratory certified under the EPA’s Contract

Laboratory Program (CLP), where a full suite of analytes (Table 4) were

measured using EPA method 200.7 (inductively coupled plasma-atomic

emission spectrometry, ICP-AES). If cadmium, copper or lead concentrations

were measured below detection limits (BDL) using ICP-AES, then the

laboratory re-analyzed samples using EPA method 200.8 (inductively coupled

plasma-mass spectrometry, ICP-MS). At the time of sample receipt, the

contracted lab checked the pH and modifications were only made if pH

measured below 2.

24

Table 4. EPA inorganic target analyte list and contract required quantitation limits (CRQLs) for methods 200.7 (ICP-AES for water samples), and 200.8 (ICP-MS) for water samples. Analyte ICP-AES CRQL for water (μg L-1) ICP-MS CRQL for water (μg L-1) Aluminum 200 -- Antimony 60 2 Arsenic 10 1 Barium 200 10 Beryllium 5 1 Cadmium 5 1 Calcium 5000 -- Chromium 10 2 Cobalt 50 1 Copper 25 2 Iron 100 -- Lead 10 1 Magnesium 5000 -- Manganese 15 1 Mercury 0.2 -- Nickel 40 1 Potassium 5000 -- Selenium 35 5 Silver 10 1 Sodium 5000 -- Thallium 25 1 Vanadium 50 1 Zinc 60 2

The contract requirement quantitation limits (CRQLs) reported in Table

4 are the minimum standards that EPA contracted laboratories need to

demonstrate the ability to meet prior to analyzing field samples. These values

are reported in the laboratory data if an individual sample is below the

instrumentations method detection limits (MDLs). The laboratories are

required to document methods used to generate analytical results and

determine Malls.

25

Water quality parameters

The field water quality parameters measured include pH, specific

conductance, and temperature. Specific conductance is a measure of the

dissolved ions in the water. A field pH meter (Orion 250A) and combination

electrode (Orion 91-07, low maintenance triode) was used to measure pH,

temperature and specific conductance. The meters were recalibrated every

three hours or every third site, depending upon which came first. The meter

electrodes were rinsed with de-ionized water before and after each

measurement.

Water hardness and standards

Stream water hardness, reported in units of mg CaCO3 L-1, was

determined by adding dissolved calcium (Ca) and dissolved magnesium (Mg)

concentrations in the following equation:

])[]([05.50 22 ++ += MgCaHardness (1)

where [Ca2+] and [Mg2+] are the dissolved concentrations of calcium and

magnesium ions in units of milliequivalents per liter (meq L-1) (CDPHE 2005).

Hardness was calculated for all sites. Water hardness is used as an

indication of differences between the complexation capacity of natural waters

and the corresponding variation of metal toxicity. Traditionally, it has been

accepted that increasing hardness has a decreases the toxicity of some

metals, for example, copper (Erickson et al. 1996). In terms of metal toxicity,

this is interpreted as increasing competition of calcium and magnesium for

26

metal binding sites on the gills of invertebrates or cell membranes (Paquin et

al. 2002). Using mean hardness values, appropriate Colorado of Public

Health and the Environment (CDPHE) chronic (thirty day exposure) and acute

(one-day exposure) aquatic life table value standards (TVS) for zinc, copper,

and lead can be determined. The CDPHE requires use of the mean hardness

during low flow season where there is insufficient paired hardness and flow

data. Mean hardness values from the spring sampling event were used to

calculate appropriate TVS values. Standard deviations and relative standard

deviations were recorded for mean hardness values calculated for each

creek. Using CDPHE equations in Table 5, appropriate chronic and acute

values for zinc, copper, and lead were calculated.

Table 5. Colorado Department of Public Health and the Environment hardness-based equations for chronic and acute value standards for copper, zinc, and lead.

Metal Acute Value (μg L-1)

Zn }0617.1)][ln(8525.0{978.0 +hardnesse

Cu }7408.1)][ln(9422.0{ −hardnesse

Pb }46.1)][ln(273.1{]}145712.0)[ln(46203.1{ −− hardnessehardness

Metal Chronic Value (μg L-1)

Zn }9109.0)][ln(8525.0{986.0 +hardnesse

Cu }7428.1)][ln(8545.0{ −hardnesse

Pb }705.4)][ln(273.1{]}145712.0)[ln(46203.1{ −− hardnessehardness

27

Benthic macroinvertebrate sampling and analysis

Sampling for macroinvertebrates occurred from June 15 to August 2,

2005. Specific dates of sampling for each site along Lefthand, James, and

Little James Creeks are presented in Appendix A. Prior to the collection of

macroinvertebrates, we selected sites along Lefthand, James, and Little

James Creek for monitoring the emergence of Archtopsyche grandis.

Archtopsyche grandis was collected based on its known metal tolerance in

Rocky Mountain streams (Clements and Kiffney 1994). Once it was

determined the target species was present, collection was planned to

progress from lower elevations to higher elevations. This pattern of collection

was based on the emergence patterns of Archtopsyche grandis (LaFontaine

1981). Throughout the entire month of May, the streambeds of sites LH1,

LH7, LH13, LH19, J14, J9, LJ1, LJ10 and LJ13 (Figure 7) were searched

thoroughly for Archtopsyche grandis. We were not able to find signs of

Archtopsyche grandis at either low or high elevations during the entire month

of May; therefore, we decided that representative samples of

macroinvertebrates found at each site would be collected instead of the

individual target species.

Macroinvertebrate collection followed the methods defined in section

3.8.2 of the EPA’s rapid bioassessment protocol (Barbour et al. 1999). These

methods were originally developed for collection of macroinvertebrates for

taxonomic identification. At each field site, streambed sediments and rocks

were kicked and flipped to allow for release of benthic macroinvertebrates into

28

a rectangular kick net. A 30 m stretch of the streambed was sampled from

downstream to upstream in a zig-zag pattern. We periodically emptied the

kick nets into plastic buckets and then transferred portions of the buckets onto

white plastic trays for macroinvertebrate collection. The macroinvertebrates

were collected with plastic forceps and rinsed with deionized water to remove

attached metals and weighed with a battery-powered field balance. A total

wet weight of at least 5 g of benthic macroinvertebrates was collected at each

sampling location. Duplicate samples were collected at every tenth location.

The samples were stored in glass jars and stored on dry ice for transport to

the University of Colorado at Boulder. In the laboratory, the samples were

stored in a laboratory freezer at 5ºC until further analysis.

The digestion of macroinvertebrates followed the methods outlined in

Clements and Kiffney (1994). The samples were dried at 55ºC for 8-10 h.

The total dry weight was recorded and the samples were transferred into 50

mL polypropylene centrifuge tubes. Once in the tubes, the digestion solution

(15 mL), a 1:1 solution of a trace metal-grade concentrated (15.8 M) HNO3

(Fisherbrand) and H2O2 (30 % by volume, Fisherbrand) and deionized water

(10 mL) was added. Samples were placed in a shaking warm water bath

(Sheldon Manufacturing, model 1227) at 60 ºC and shaken at 120 rpm for 2 h.

The samples were removed from the bath and allowed to settle by gravity for

approximately 12 h. 7.5 mL of the supernatant was withdrawn using a 5 mL

Fisherbrand pipette (5 mL and 2.5 mL aliquots) and placed in acid washed

250 mL polypropylene sample bottles for shipping for analysis of metal

29

concentrations. The analytes that were measured and their methods of

analysis are similar to the methods for total and dissolved metals in the water

samples (Table 4). A blank without macroinvertebrates was carried through

the same digestion procedure.

DOC was measured because of its direct correlation with metal

bioaccumulation in the caddisfly Arctopsyche grandis in metal-polluted

streams (Prusha and Clements 2004). Water samples to be analyzed for

dissolved organic carbon (DOC) were taken at each site and stored in 1 L

amber-colored glass bottles. The samples were stored on ice and

transported to the University of Colorado where they were filtered in a 500 mL

Nalgene filter apparatus with a 0.45 μm, Magna, nylon, supported, grid

membrane using vacuum extraction. The filtrate was acidified using

phosphoric acid (85%, Fisherbrand) to a pH < 4 and stored in a laboratory

refrigerator until future analysis. DOC was measured using a total organic

carbon (TOC) analyzer (Ionic-Sievers, model 800) by the persulfate-ultraviolet

oxidation method (Clesceri et al. 1999).

Sediment sampling and analysis

In order to minimize sediment transport in the streams, which would

affect the correlation of metals in sediments to metal sources, we conducted

the sediment sampling in the fall. Mountain streams show characteristic low

flows during the fall. The low flow conditions would give us the best chance of

retaining contaminated sediments nearest to their original sources. Our aim

was to collect sediments right after a large storm event, but this event did not

30

occur and due to time constraints, sampling commenced in late September.

Stream bed sediments were collected from all locations in which water and

macroinvertebrates had been collected from September 24 to October 17,

2005. Specific dates of collection for each site can be found in Appendix E.

The sample collection and partial digestion methods used were outlined by

Church et al. (1997). These sites were chosen based on previous studies

indicating large percentages of fine particles (Wood 2003). Triplicate samples

were taken at field sites LJ1, LJ8, LJ9 and LJ11.

A volume of approximately 1 L of sediment was collected at each site.

Each sample consisted of five to ten sub-samples collected within a 15 m

area. Sediment was collected mainly in depositional areas which were

covered by flow, and only from the upper 5 cm of the stream bed. The entire

sediment sample was wet-sieved in the field through a 4.0 mm (5 mesh)

brass sieve and stored in polyethylene bottles on ice for transport. All

samples were oven-dried at 100 °C within 24 h of collection and dry-sieved

for 30 min with a sieve shaker (W.S. Tyler Company, Ro-tap) through a nest

of stainless steel sieves (2.36mm > 1.70 mm > 1 mm > 500 μm > 125 μm >

63 μm > in order to collect the <63 μm size fraction. Individual samples from

field sites LJ4, LJ5, LJ6, LJ10 and J3 were divided into three parts and

analyzed separately to assess the reproducibility of the analysis method.

Samples from field sites LJ7 and LJ13 were separated into five sub-samples

of 0.25, 0.5, 0.75, 1 and 1.25 g and analyzed to test the accuracy of the

analysis method using varying masses of sediment.

31

A partial digestion was employed to extract leachable ore-related

metals associated with mine wastes from the sediments (Church et al. 1997).

Sterilized 50 mL centrifuge tubes were filled with 1.0 g (±0.1 g) of sediment

from a single sample (with the exception of the five varying weights from LJ7

and LJ13). To each centrifuge tube, 1.5 M trace metal-grade HNO3 (20 mL;

Fisherbrand) and 30% H2O2 (0.2 mL; Fisherbrand) were added. The tubes

were capped, briefly hand-shaken to mix, placed in racks, and shaken at 120

rpm in a hot water bath (Sheldon Manufacturing, model 1227) at 55 - 60 °C.

The samples were centrifuged at 800 rpm for 10 min to segregate remaining

sediment from the digestion solution, and the supernatant was removed and

placed in sterilized 25 mL polypropylene centrifuge tubes. The partial

digestion solutions were analyzed for zinc, copper, and lead by inductively-

coupled plasma-atomic emission spectrophotometry (ICP-AES) in the

Laboratory for Environmental and Geological Studies (LEGS) at the

University of Colorado at Boulder. The metal concentrations in the solutions

were converted to mass of metals per mass of sediment using the recorded

dry weights and dilution factors.

Characterization of Waste Rock Piles

We collected samples from twelve waste rock piles in the Lefthand and

Little James Creek watersheds (Table 6). Each waste rock pile was divided

into a thirty-cell grid of approximately equal area. Equal amounts of sample

(approximately 1 kg) were taken from each cell to obtain a total composite

sample. The samples were air-dried and sieved through a 2 mm nylon mesh

32

screen. Background samples were taken in areas upstream and west of

known historical mining activity and in close proximity to the investigated

stream.

Table 6. Locations of waste rock piles in Lefthand Creek watershed.

site code site name latitude

º, ‘, “ longitude

º, ‘, “

Lefthand Creek 5560-REF Lefthand reference 40 04 09.3 N 105 31 00.7 W

5560-DD Dew Drop 40 03 52.8 N 105 30 56.0 W

5560-WR White Raven (whole pile) 40 03 34.3 N 105 23 48.7 W

5560-WR White Raven (yellow pile) 40 03 34.3 N 105 23 48.7 W

5560-CT Corning Tunnel 40 04 30.0 N 105 24 19.0 W

5560A-UWRP Upper Slide Pile 40 04 28.2 N 105 23 59.4 W

5560A-LWRP Lower Slide Pile 40 04 28.3 N 105 23 59.4 W

Little James Creek

5562-REF Little James Reference 40 08 12.2 N 105 24 41.6 W

5562-ES Evening Star 40 07 56.0 N 105 24 15.6 W

5562 - AR Argo Mine 40 07 44.75 N 105 24 07.0 W

5562-EM Emmett Mine 40 07 35.30 N 105 23 57.0 W

5562-JR JRT 40 07 27.03 N 105 23 52.4 W

5562-BU Bueno Mine 40 06 43.8 N 105 25 22.2 W

In order to characterize metal content of the waste rock samples, an

elutriation process was employed. EPA Method 1312, a synthetic leaching

procedure which includes a partial digestion, was developed by the EPA to

evaluate the degree of contamination and mobility of metals in mine waste.

The waste rock pile study used an alternate field leach method which relies

on the solubility of minerals to reduce testing time and costs (Hageman and

Briggs 2000; Hageman 2004).

33

Metals were elutriated from the waste rock samples (<2 mm grain size)

by combining 50 g of dry sediment with 1000 mL of high-purity water at pH

5.7 in a glass Erlenmeyer flask, vigorously shaken for 5 min, and allowed to

settle for 10 min. The supernatant was removed and divided into two

samples. One of the samples was acidified to a pH <1.5 with HNO3 and used

to identify total metals similarly to those methods used for water and

macroinvertebrate samples. The second sample was filtered through a 0.45

μm diameter nitro-cellulose filter. The filtered samples were also acidified to

pH <1.5 with HNO3. Metal concentrations in the samples were measured by

ICP-AES for all metals and by ICP-MS for metals measured as below

detection limits for ICP-AES. Samples were analyzed for Al, Sb, As, Ba, Be,

Cd, Ca, Cr, Co, Cu, Fe, Pb, Mg, Mn, Hg, Ni, K, Se, Ag, Na, Tl, and Zn by an

EPA laboratory.

Sediments were also collected for a partial digestion following the

Church et al. (1997) method. A 1 L sample of sediment (<2 mm grain size)

was collected, dried at 100ºC and sent to a EPA laboratory for digestion and

metals analysis. Samples were digested using EPA Method 200.2 which

uses a combination of nitric and hydrochloric acid to determine total

recoverable elements (USEPA 1991).

Tabulated results for water quality data and metal concentrations in water,

macroinvertebrates and sediments can be found in Appendices A-D.

Appendix A contains pH, specific conductance, and dissolved organic carbon

(DOC) measured at each site. Appendix B contains concentrations for total

34

and dissolved zinc, copper, and lead concentrations in water samples.

Appendix C contains zinc, copper, and lead concentrations in benthic

macroinvertebrates and Appendix D contains zinc, copper, and lead

concentrations within streambed sediments.

Water quality measurements – pH, temperature, and specific

conductance

Lefthand Creek pH values measured during the spring sampling period

ranged from 6.5 – 7.3 (Figure 8) with the minimum and maximum values

occurring at sites LH7 and LH15, respectively (Figure 7). Lefthand Creek pH

values all fell within the acceptable range according to CDPHE –Water

Quality Control Division (WQCD) standards for a Class I cold-water stream.

Site LH15 also held the highest specific conductance measurement of 115

μS cm-1 (Figure 8), while the lowest measurement of 25.2 μS cm-1 occurred at

site LH4. The average temperature in Lefthand Creek was 12.0±1.2ºC with

the uncertainty representing one standard deviation of the mean temperature.

The pH in James Creek ranged from 6.1 – 6.9. Out of fourteen field

sites along James Creek, ten of those exhibited pH values below the

acceptable range according to CDPHE standards (Figure 9). Specific

conductance increased steadily from 20.5 μS at field site J1 above the Peak

to Peak Highway to 33.6 μS cm-1 at field site J14, just above the confluence

with Little James Creek. The average stream water temperature was 13.9 ±

2.1ºC.

35

Little James Creek exhibited the lowest pH and the highest specific

conductance and temperature values of the three creeks (Figure 10).

pH

4

5

6

7

8

9

10 pH CDPHE minimum standardCDPHE maximum standard

Lefthand Creek Distance Downstream (km)

0 5 10 15 20 25 30

spec

ific

cond

ucta

nce

(uS

cm

-1)

0

20

40

60

80

100

120

140

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Whi

te R

aven

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 8. Lefthand Creek pH and specific conductance measured in the field during macroinvertebrate and water sampling (June 15 – August 2, 2005).

The pH values ranged from 5.4 - 6.7. The maximum specific

conductance was 1620 μS cm-1 downstream of the Burlington Mine. This

value is approximately eight times greater than the specific conductance of

36

the Little James Creek water sampled at the first site (209 μS cm-1). The

average stream water temperature was 16.7 ± 2.8ºC.

pH

4

5

6

7

8

9

10 pH CDPHE minimum standardCDPHE maximum standard

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

tn g

ully

Wat

er T

mt P

lant

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

James Creek Distance Downstream (km)

0 2 4 6 8 10 12 14 16 18 20 22

spec

ific

cond

ucta

nce

(μS

cm

-1)

0

10

20

30

40

Figure 9. James Creek pH and specific conductance measured in the field during macroinvertebrate and water sampling.

37

pH

4

5

6

7

8

9

10 pH CDPHE minmum standard CDPHE maximum standard

Little James Creek Distance Downstream (km)

0.0 0.5 1.0 1.5 2.0 2.5 3.0

spec

ific

cond

ucta

nce

(μS

cm-1

)

0

200

400

600

800

1000

1200

1400

1600

1800

Bac

kgro

und

refe

renc

e

Even

ing

Star

un-n

amed

was

te ro

ck p

ileAr

go M

ine

"Arg

o gu

lly"

Bal

arat

road

Burli

ngto

n M

ine

Emit

Min

e ad

it dr

aina

geBa

lara

t Cre

ek

min

e w

aste

pile

Stre

amsi

de ta

ilings

Buen

o M

tn. g

ully

Yel

low

girl

- nor

thW

ater

fall

Jam

es C

reek

con

fluen

ce

Figure 10. Little James Creek pH and specific conductance measured in the field during macroinvertebrate and water sampling.

Dissolved Organic Carbon

Upstream of the confluence with James Creek, the DOC concentration

measured in Lefthand Creek was approximately 2.8 mg L-1 (Figure 11).

38

Deviations from this value occurring just downstream of the confluence with

the Big Five tunnel drainage, where the DOC concentration increased to 3.3

mg L-1. Downstream of the confluence with James Creek, the DOC drops to

about 2 mg L-1.

Lefthand Creek Distance Downstream (km)

0 5 10 15 20 25 30

Dis

solv

ed O

rgan

ic C

arbo

n (m

g/L)

0

1

2

3

4

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Whi

te R

aven

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 11. Lefthand Creek dissolved organic carbon represented with standard deviations determined from 5 samples taken by the TOC analyzer software (methods analysis).

The DOC concentration in James Creek ranges from 1.7 to 2.8 mg L-1

(Figure 10). The high end of the DOC concentration range occurs just

downstream of the John Jay Mine and the Bueno Mountain gully while the low

end occurs downstream of the confluence with James Creek.

39

James Creek Distance Downstream (km)

0 2 4 6 8 10 12 14 16 18 20

Dis

solv

ed O

rgan

ic C

arbo

n (m

g/L)

220.0

0.5

1.0

1.5

2.0

2.5

3.0

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Porp

hyry

Gul

ch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

Figure 12. James Creek dissolved organic carbon represented with standard deviations determined from 5 samples taken by the TOC analyzer software (methods analysis).

The DOC concentrations measured along Little James Creek ranged

from 1.7-4.4 mg/L (Figure 11). The higher DOC concentrations in Little

James Creek can be attributed to low flow and the prevalence of wetlands

along parts of the creek. DOC decreases in areas of the stream where pH is

low and are most likely due to the type of organic acids composing the DOC.

40

Little James Creek Distance Downstream (km)

0.0 0.5 1.0 1.5 2.0 2.5

Dis

solv

ed O

rgan

ic C

arbo

n (m

g/L)

3.00

1

2

3

4

5

Back

grou

nd re

fere

nce

Even

ing

Star

un-n

amed

was

te ro

ck p

ileAr

go M

ine

"Arg

o gu

lly"

Bal

arat

road

Burli

ngto

n M

ine

Emit

Min

e ad

it dr

aina

geB

alar

at C

reek

min

e w

aste

pile

Stre

amsi

de ta

iling

sBu

eno

Mtn

. gul

lyY

ello

wgi

rl - n

orth

Wat

erfa

ll ab

ove

conf

luen

ce

Jam

es C

reek

con

fluen

ce

Figure 13. Little James Creek dissolved organic carbon represented with standard deviations determined from 5 samples taken by the TOC analyzer software (methods analysis).

The DOC concentrations reported in this section are the averages of 5

samples recorded by the TOC analyzer. The standard deviations of individual

samples are indicated in Figure 11, Figure 12 and Figure 13 with error bars.

The relative standard deviation (RSD), for the entire data set (three creeks),

ranged from 0-2% for al metals in all 3 creeks.

Hardness and standards

In Lefthand Creek, hardness increased downstream of the Big Five

Tunnel and in the area of the Slide Mine. Hardness was diluted by about a

factor of three by the addition of the James Creek water (Figure 14). In

James Creek, hardness increased with distance (Figure 15). The James

41

Creek water was the softest of three creeks. In Little James Creek, the

hardness peaks just downstream of the flows from the Burlington and Emmit

Mines (Figure 16). The hardness downstream of Balarat Creek can be

attributed to fluorite (CaF2) which was extracted from this area during

previous mining activities.

Lefthand Creek distance downstream (km)

0 5 10 15 20 25 30

Har

dnes

s (m

g/L

Ca

CO

3)

0

10

20

30

40

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Whi

te R

aven

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 14. Hardness calculated from magnesium and calcium concentrations in Lefthand Creek for samples taken from June 15-July 22, 2005.

42

James Creek Distance Downstream (km)

0 2 4 6 8 10 12 14 16 18 20

Har

dnes

s ( m

g/L

CaC

O3)

220

2

4

6

8

10

12

Pea

k to

Pea

k H

wy

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

mt P

lant

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

Figure 15. Hardness calculated from magnesium and calcium concentrations in James Creek for samples taken from June 15-July 22, 2005.

Little James Creek distance downstream (km)

0.0 0.5 1.0 1.5 2.0 2.5

Har

dnes

s (m

g/L

CaC

O3)

3.00

100

200

300

400

500

Bac

kgro

und

refe

renc

e

Eve

ning

Sta

r

un-n

amed

was

te ro

ck p

ileA

rgo

Min

e

"Arg

o gu

lly"

Bala

rat r

oad

Bur

lingt

on M

ine

Emit

Min

e ad

it dr

aina

geBa

lara

t Cre

ek

min

e w

aste

pile

Stre

amsi

de ta

iling

sB

ueno

Mtn

. gul

lyYe

llow

girl

- nor

th

Wat

erfa

ll ab

ove

conf

luen

ce

Jam

es C

reek

con

fluen

ce

Figure 16. Hardness calculated from magnesium and calcium concentrations in Little James Creek for samples taken from June 22, - July 18, 2005.

43

Initially, the average chronic and acute TVSs were calculated for each

individual creek using the average hardness throughout the creek (Table 7).

Since hardness varied so much throughout each stream (especially Lefthand

Creek), we decided to calculate the chronic CDPHE TVS for zinc, copper, and

lead at every site in the watershed. These standards are calculated using the

hardness-based equations provided in (Table 5).

Table 7. Acute and chronic table value standards (TVS) for aquatic life for zinc, copper, and lead in Lefthand, James, and Little James Creeks.

acute TVS chronic TVS

creek copper (μg L-1)

lead (μg L-1)

zinc (μg L-1)

copper (μg L-1)

lead (μg L-1)

zinc (μg L-1)

Lefthand Creek 4.2 9.4 44 3.5 0.15 38

James Creek 1.6 2.9 18 1.5 0.050 16

Little James Creek 31 95 268 22 1.5 232

Stream water iron

The concentrations of iron for Lefthand, James, and Little James

Creeks are represented in Figure 17, Figure 18, and Figure 19. The CDPHE

chronic aquatic life standard for iron is 1000 μg L-1. This standard is

exceeded in the Little James Creek only. The reaches of the stream where

this standard is exceeded includes the length of stream just downstream of

Argo Mine and above Porphyry tailings and the length of stream just

downstream of Bueno Mountain gully and just upstream of the confluence

with James Creek. In both James and Lefthand Creek, dissolved iron

remains fairly constant, this indicates that a majority of the iron is in the

44

colloidal form. The average colloidal percentage of iron in Lefthand Creek

was 63±10%, James Creek was 70±8%, and Little James Creek was

36±20%. The high standard deviation in Little James Creek was due to the

extreme differences in the magnitude of total and dissolved iron

concentrations between background and in the stream.

Background total and dissolved iron concentrations in Lefthand Creek

are higher than most in-stream water samples. The drop in iron

concentrations after the Big Five Tunnel drainage is uncharacteristic of this

area. These uncharacteristically low concentrations are most likely due to the

lack of flow coming from the drainage. Previous studies have documented

concentrations above the chronic aquatic life standard (1000 μg L-1) in this

area when the drainage has been flowing. Spikes in iron concentrations in

Lefthand Creek are seen downstream of Sixmile Creek, also the highest total

concentration measured at 277 μg L-1. The highest total iron concentrations

in Little James Creek are seen just downstream of Balarat Creek at 8,130 μg

L-1. The highest concentration of total iron in James Creek measured was

285 μg L-1 and occurred downstream of Curie Springs.

45

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Puzz

ler G

ulch

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Lefthand Creek distance downstream (km)

0 5 10 15 20 25 30

Iron

(μg/

L)

0

50

100

150

200

250

300

Figure 17. Total (•) and dissolved (#) iron along the length of Lefthand Creek. The chronic aquatic life standard for iron is 1000 μg L-1, which was not exceeded.

James Creek distance downstream (km)

0 2 4 6 8 10 12 14 16 18 20 22

Iron

(μg/

L)

0

50

100

150

200

250

300

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

Figure 18. Total (•) and dissolved (#) iron along the length of James Creek. The chronic aquatic life standard for iron is 1000 μg/L, which was not exceeded.

46

Little James Creek distance downstream (km)

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Iron

(μg/

L)

0

2000

4000

6000

8000

10000

Back

grou

nd re

fere

nce

Eve

ning

Sta

r

un-n

amed

was

te ro

ck p

ileAr

go M

ine

"Arg

o gu

lly"

Bala

rat r

oad

Bur

lingt

on M

ine

Em

it M

ine

adit

drai

nage

Bala

rat C

reek

min

e w

aste

pile

Stre

amsi

de ta

ilings

Bue

no M

tn. g

ully

Yel

low

girl

- nor

thW

ater

fall

abov

e co

nflu

ence

Jam

es C

reek

con

fluen

ce

Figure 19. Total (•) and dissolved (#) iron along the length of Little James Creek. The chronic aquatic life standard for iron is 1000 μg L-1, which was not exceeded.

Stream water zinc, copper, and lead concentrations

The single field blank concentrations for zinc, copper, and lead were

mostly below detection limits (Table 8). Total copper and dissolved lead

concentrations in the field blanks were reported as values above, but very

close to the detection limits.

For all of the cases where the dissolved concentrations are higher than

the total, the dissolved will be used in place of the total. In these cases, it

was suggested by EPA laboratory managers that this would indicate

concentrations measured near detection limits. The detection limits were not

reported by the EPA laboratory on the concentration data reports.

Concentrations below detection limits were indicated with a flag (yes – below,

no – above). Multiple efforts to obtain the exact limits were not successful

47

because the detection limits changed with each run of approximately 50

samples.

Table 8 Field blank metal concentrations measured at site LJ7. BDL is below detection limits. Because total lead was below detection limits, and dissolved lead was not, we can assume that dissolved lead is close to detection limits.

Metal Total (μg L-1) Dissolved (μg L-1)

Copper 5 BDL Zinc BDL BDL Lead BDL 2.8

Lefthand Creek water –zinc, copper, and lead concentrations

Total lead in Lefthand creek ranged from 0.25-4.6 μg L-1, with the

maximum concentration occurring just downstream of Slide Mine (Figure 20).

The dissolved fraction of samples was high for all three metals in Lefthand

Creek. Dissolved copper averaged approximately 79% of the total copper,

and zinc averaged 80%. The fraction of dissolved lead was not estimated

because so many of the lead concentrations were measured below detection

limits.

Concentrations of dissolved copper and zinc exceeded chronic TVSs

in Lefthand Creek. For zinc, the exceedance occurred at sites just

downstream the Big Five tunnel drainage and White Raven Mine site. Lead

concentrations exceeded the chronic TVS at all sites including the

background site. Copper exceeded the chronic TVS downstream of the Big

Five tunnel drainage, White Raven Mine site and downstream of the Slide

Mine.

48

Lefthand Creek Distance Downstream (km)

Cop

per (μ g

/L)

0

5

10

15

20

25

30

Lead

(μg/

L)

0

2

4

6

8

10

Zinc

(μg/

L)

0

20

40

60

80

100

120

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Dis

char

gePu

zzle

r Gul

chIn

dian

a G

ulch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 20. Total (•) and dissolved (#) zinc, copper, and lead concentrations in Lefthand Creek during June 15-July 22, 2005. Closed circles represent total metals, open circle represent dissolved metals and chronic standards are a function of hardness and are represented by dashed lines.

James Creek water – zinc, copper, and lead concentrations

The maximum total concentrations for copper, zinc, and lead were

lowest in James Creek (Figure 21). Zinc was present mostly in the dissolved

form (76%). Chronic standards were never exceeded for Zn. The maximum

49

concentration of copper in James Creek occurred just downstream of the

Bueno Mountain gully and exceeded chronic table value standards here as

well.

Lead concentrations were also fairly low compared to other creeks in

the watershed; however, the chronic standard was exceeded at all times

because the stream water is so soft. Total lead concentrations ranged from

0.36-0.73 μg L-1 and colloidal concentrations were highest among all metals

(75%). Most dissolved concentrations measured below detection limits,

which is why the trends for lead in Figure 25 are dominated by total

concentrations and not dissolved.

Dissolved concentrations in James Creek comprised most of the total

samples for zinc, copper, and lead. This is somewhat uncertain for lead

because of a majority of the samples measured close to detection limits. The

average percentage of dissolved Cu per sample was 67%.

50

James Creek Distance Downstream (km)

Cop

per (μ g

/L)

0

3

6

9

12

15

18

21

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

0 2 4 6 8 10 12 14 16 18 20 22

Lead

(μg/

L)

0

1

2

3

4

Zinc

(μg/

L)

0

4

8

12

16

20

Figure 21. Total (•) and dissolved (#) zinc, copper, and lead concentrations in James Creek during July 1- August 1, 2005. Black closed circles represent total metals, open circle represent dissolved metals, grey closed circles are below detection limits and chronic standards are represented by dashed lines.

Little James Creek water – zinc, copper, and lead concentrations

The highest concentrations of zinc, copper, and lead occurred along

Little James Creek (Figure 22). Concentrations of total zinc ranged from 95.4

to 1440 μg L-1 with the peak total zinc concentration occurring just

downstream of Balarat Creek, which delivers the acid mine drainage from the

51

Burlington Mine to Little James Creek. Both lead and zinc concentrations

show similar trends to each other along James Creek with background levels

at site locations upstream of Argo Mine increasing concentrations

downstream. Both lead and zinc reach peak concentrations after the

Burlington Mine and Emmit Mine adit and decline before entering Jamestown.

Copper concentrations at the background reference point are below the

detection limit. Approximately 0.25 km downstream from the reference site

and downstream of the Evening Star Mine, total copper climbs to 48 μg L-1.

At this site, total zinc claims the highest concentration at 117 μg L-1, while

lead is still below detection limits.

Zinc and copper exceeded both chronic and acute standards

periodically along Little James Creek. As with both James and Lefthand

Creek, Little James Creek always exceeds the chronic standard for lead.

High concentrations of metals are indicative of a low flow stream such as

Little James Creek.

52

Little James Creek Distance Downstream (km)

Cop

per (μ g

/L)

0

50

100

150

200

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Lead

(μg/

L)

0

50

100

150

200

Zinc

(μg/

L)

0

500

1000

1500

2000

Back

grou

nd re

fere

nce

Even

ing

Star

un-n

amed

was

te ro

ck p

ileA

rgo

Min

e

"Arg

o gu

lly"

Bala

rat r

oad

Burli

ngto

n M

ine

Em

it M

ine

adit

drai

nage

Bal

arat

Cre

ek

min

e w

aste

pile

Stre

amsi

de ta

iling

sB

ueno

Mtn

. gul

lyYe

llow

girl

- nor

thW

ater

fall

abov

e co

nflu

ence

Jam

es C

reek

con

fluen

ce

Figure 22. Total (•) and dissolved (#) zinc, copper, and lead concentrations in Little James Creek during June 22, - July 18, 2005. Closed circles represent total metals, open circle represent dissolved metals and chronic standards are represented by dashed lines.

Benthic macroinvertebrate metal concentrations

In order to avoid complexity of species diversity within each individual

site sample, as well as to save time in the field, local taxonomic evaluations

were not completed. Metal concentrations are discussed in terms of the

entire sample comprised of many individual species representative of each

53

field site. However, in the case of Little James Creek, a majority of the sites

were inhabited by a single species, the caddisfly, Dicosmoecus atripes. In

this case, metal concentrations will be discussed in terms of the individual

species where appropriate. Little James Creek was also unique in its lack of

benthic macroinvertebrates at seven out of thirteen sites. Benthic

macroinvertebrate metal concentrations are discussed in mg kg-1 sample with

the sample consisting of multiple individuals and entire body. Laboratory

blanks did not indicate confounding effects of the reagents used to digest the

benthic macroinvertebrates. This was deduced by concentrations for copper,

zinc, and lead measuring below detection limits. Duplicate sample locations

are identical to those taken for stream water in each creek and are

represented once again on the associated figures.

Background concentrations are reported for comparison for each creek

in Table 9 below. Background concentrations for lead are lowest for all

streams. However, in Little James Creek, lead is substantially higher than in

Lefthand and James Creeks. Lead measured at the James Creek

background site was below detection limits.

Table 9 Benthic macroinvertebrate background concentrations measured at sites void of previous mining activities. BDL – Below Detection Limits.

Creek Site Name Cu (μg g-1) Pb (μg g-1) Zn (μg g-1) Lefthand LH1 44.9 0.63 387

James J1 33.6 BDL 251 Little James LJ1 27.5 21.7 267

54

Lefthand Creek benthic macroinvertebrates – zinc, copper, and lead

The concentrations of metals in the benthic macroinvertebrates in

Lefthand Creek increased in the order of zinc > copper > lead (Figure 23).

Duplicate samples taken at site LH10, downstream of Spring Gulch, indicated

excellent reproducibility of results for the benthic macroinvertebrate analysis

as indicated in Figure 23.

Zinc concentrations in benthic macroinvertebrates steadily increased

from 390 μg g-1 at the reference site, north of Peak to Peak Highway, to 1300

μg g-1 downstream of the Big Five tunnel drainage (LH5). The zinc

concentration in benthic macroinvertebrates upstream of the White Raven

Mine at site (LH6, 0.2 km downstream of LH5) decreased to 1100 μg g-1. The

zinc concentration in benthic macroinvertebrates increased again to 2000 μg

g-1 from site LH6 to downstream of the White Raven Mine (LH7). The zinc

concentration in benthic macroinvertebrates in California Gulch (sites LH3 –

LH8) was highest at Sawmill Road (site LH8, 2200 μg g-1). The highest zinc

concentrations in benthic macroinvertebrates were found between sites LH9

(above Lickskillet Road, 2400 μg g-1) and LH14 (downstream of Nugget

Gulch, 3100 μg g-1). Zinc concentrations in benthic macroinvertebrates

steadily decrease from site LH15 (downstream of Lee Hill Gulch, 2000 μg g-1)

to LH19 (above Haldi water intake, 830 μg g-1). The zinc concentration in

benthic macroinvertebrates at the furthest downstream site along Lefthand

Creek (above the Haldi water intake) was comparable to zinc concentration in

benthic macroinvertebrates downstream of the Dew Drop Mine.

55

The copper and lead concentrations in benthic macroinvertebrates at

the reference site were 45 μg g-1 and 0.6 μg g-1 respectively. Copper and

lead concentrations in benthic macroinvertebrates follow similar trends in

California Gulch (Figure 23). The increases and decreases in copper and

zinc concentrations in benthic macroinvertebrates from sites LH1 (above

Peak to Peak highway) to LH7 (downstream of the White Raven Mine) in

California Gulch are similar to those discussed for zinc. However, in contrast

to zinc, copper and lead concentrations in benthic macroinvertebrates

decrease from the site downstream of the White Raven Mine (copper – 670

μg g-1, lead - 27 μg g-1) to the site at Sawmill Road (copper – 290 μg g-1, lead

- 5.9 μg g-1).

The copper concentrations in benthic macroinvertebrates steadily

decline from the site just above Lickskillet Road (220 μg g-1) to the site above

the Haldi water intake (59 μg g-1). Just before the Haldi water intake, the

copper concentration in benthic macroinvertebrates is observed to be close to

the reference site concentration, with a difference of about 10 μg g-1 higher at

the intake.

Lead concentrations in benthic macroinvertebrates generally increase

from the site just above Lickskillet Road (7.0 μg g-1) to the site 5 km

downstream, downstream of the town of Rowena (16 μg g-1). Downstream of

Rowena the lead concentration in benthic macroinvertebrates generally

decreases from 16 μg g-1 to 5 μg g-1. The single deviation from this general

56

decrease in lead concentrations in benthic macroinvertebrates is indicated by

a small peak which occurs downstream of Lee Hill Gulch.

Lefthand Creek Distance Downstream (km)

Cop

per (μ g

/g)

0

200

400

600

800

0 5 10 15 20 25 30

Lead

(μg/

g)

0

5

10

15

20

25

30

Zinc

(μg/

g)

0

500

1000

1500

2000

2500

3000

3500

Peak

to P

eak

Hw

yDew

Dro

p M

ine

trib

Big

Fiv

e Tu

nnel

Dis

char

gePu

zzle

r Gul

chIn

dian

a G

ulch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke Figure 23. Zinc, copper, and lead concentrations measured in macroinvertebrates in Lefthand Creek from June 15, - July 22, 2005.

James Creek benthic macroinvertebrate – zinc, copper, and lead

Duplicate samples taken at sites J8 (downstream of the Jamestown

water treatment plant) and J13 (above the confluence with Lefthand Creek)

57

indicate excellent reproducibility of results for the benthic macroinvertebrate

laboratory analysis. These duplicates are difficult to see in

Figure 24 because of the overlaying of points. The results can also be found

in Appendix C, Table C. 4.

A unifying trend is observed between metal concentrations in benthic

macroinvertebrates in James Creek along the 10 km reach downstream of the

Bueno Mountain gully to the confluence with Lefthand Creek (Figure 24).

Zinc concentrations ranged from 250 – 1370 μg g-1 displaying a steady

increase from the background reference location at Peak-to-Peak Highway to

the confluence with Lefthand Creek.

Copper concentrations were among the lowest in the watershed

ranging from 34 μg g-1 (site J1, reference site at Peak to Peak highway) to

86 μg g-1(J12, downstream of Curie Springs). The second highest copper

concentrations in macroinvertebrates in James Creek occurs downstream of

County Road 102J (site J3, 84 μg g-1). Fluctuations in copper concentrations

in benthic macroinvertebrates were not observed for the stream reach

between and including sites J4 – J11.

Lead concentrations in benthic macroinvertebrates were significantly

lower in James Creek as compared to all other sites and creeks sampled in

the watershed. Lead concentrations in macroinvertebrates measured below

detection limits at six out of fourteen locations along James Creek. Lead

concentrations in benthic macroinvertebrates show a steady increase from

the site downstream of the Bueno Mountain gully (1.6 μg g-1) to the site just

58

above the confluence with Lefthand Creek (8.8 μg g-1). The tributaries and

discharges to James Creek along this reach include the Bueno Mountain

gully, Little James Creek, Porphyry Gulch, Curie Springs, and Castle Gulch.

James Creek Distance DOwnstream (km)

Cop

per (μ g

/g)

30

40

50

60

70

80

90

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

0 2 4 6 8 10 12 14 16 18 20 22

Lead

(μg/

g)

0

4

8

12

16

20

Zinc

(μg/

g)

0

200

400

600

800

1000

1200

1400

1600

Figure 24. Zinc, copper, and lead concentrations measured in macroinvertebrates in James Creek from July 1, - August 1, 2005. Missing data points indicates levels measured below detection limits.

Little James Creek benthic macroinvertebrates – zinc, copper, and lead

The duplicate samples taken at site LJ5 (downstream of the Argo gully)

indicated moderate reproducibility of results for copper (160 and 140 μg g-1)

59

and zinc (210 and 160 μg g-1) concentrations in benthic macroinvertebrates

for Little James Creek (Table C. 6 and Figure 25). The same duplicate

samples indicated that the reproducibility of results for the lead concentration

in benthic macroinvertebrates was poor for Little James Creek (290 and 180

μg g-1).

The observed zinc concentration in benthic macroinvertebrates at the

reference site was 140 μg g-1 in Little James Creek was the lowest

background zinc concentration among the three investigated creeks. The

highest zinc concentration in benthic macroinvertebrates along Little James

Creek occurred just downstream of the Evening Star mine (1600 μg g-1). This

was the only site where zinc concentrations were found to be well above the

background concentration.

The observed background copper concentration in benthic

macroinvertebrates at the reference site was 14 μg g-1 and similar to the

background zinc concentration in Little James Creek, was the lowest

background copper concentration among the three investigated creeks. The

copper concentration in benthic macroinvertebrates increases from 14 μg g-1

at the reference site to 120 μg g-1 0.25 km downstream, downstream of the

Evening Star Mine. The concentration of copper in benthic

macroinvertebrates are highest between the downstream of the Argo Mine

tailings pile (170 μg g-1) and downstream of the Argo Mine (160 μg g-1).

There were no macroinvertebrates present from downstream of Balarat Creek

to just upstream of the Porphyry Mountain tailings pile.

60

The observed lead concentration in benthic macroinvertebrates at the

reference site was 11 μg g-1. Lead concentrations in benthic

macroinvertebrates remained near the background concentration for the first

0.92 km downstream of the reference site. The first significant increase in

lead concentrations in macroinvertebrates occurred just downstream of the

Argo Mine gully (duplicate samples, 290 μg g-1 and 180 μg g-1). The second

highest lead concentration in benthic macroinvertebrates in Little James

Creek occurred just upstream of the Porphyry Mountain tailings pile (210 mg

kg-1). Besides this record, trends are difficult to infer from the data with no

benthic macroinvertebrates at half of the sites. However, these sites may

indicate water quality impairment which directly effects aquatic life.

Between the Porphyry Mountain tailings pile and the confluence with

James Creek, only site LJ9 (0.5 km downstream of Porphyry Mountain

tailings and just upstream of “streamside tailings”) contained benthic

macroinvertebrate life. In relation to the closest upstream site sampled (LJ5,

downstream of Argo Mine), the concentration of zinc in benthic

macroinvertebrates decreased (160 to 140 μg g-1), copper in benthic

macroinvertebrates decreased (140 to 60 μg g-1), and lead in benthic

macroinvertebrates increased slightly (180 to 210 μg g-1).

61

Little James Creek (km)

Cop

per (μ g

/g)

0

50

100

150

200

Back

grou

nd re

fere

nce

Eve

ning

Sta

r

un-n

amed

was

te ro

ck p

ileArg

o M

ine

"Arg

o gu

lly"

Bal

arat

road

Burli

ngto

n M

ine

Emit

Min

e ad

it dr

aina

geBal

arat

Cre

ek

min

e w

aste

pile

Stre

amsi

de ta

iling

sBue

no M

tn. g

ully

Yel

low

girl

- nor

thW

ater

fall

abov

e co

nflu

ence

Jam

es C

reek

con

fluen

ce

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Lead

(μg/

g)

0

100

200

300

400

Zinc

(μg/

g)

0

200

400

600

800

1000

1200

1400

1600

1800

Figure 25. Zinc, copper, and lead concentrations measured in macroinvertebrates in Little James Creek from June 22, - July 18, 2005. Missing data points indicates levels measured below detection limits. Upside down triangles represent sites with no macroinvertebrates present at the time of sampling.

Streambed sediment investigations

Widely accepted standards for metals in stream sediments do not exist

at this time. Background concentrations for the three investigated streams

are reported in Table 10 below. Little James and James Creeks have similar

background sediment concentrations, indicating similar geology, while

62

Lefthand Creek background concentrations are much less for all investigated

metals.

Table 10 Background metal concentrations were determined as areas upstream from any previously known mining activities.

Creek Cu (mg kg-1) Pb (mg kg-1) Zn (mg kg-1)

Lefthand Creek 12.3 26.3 35 James Creek 41.8 59.6 72.7

Little James Creek 48.3 64.8 77.4

Effects of mass on partial digestion efficiency

The results from the variable mass study at sites LJ13 (just above the

confluence with James Creek on Little James Creek) and LJ7 (just

downstream of Balarat Creek) indicate that the mass of copper removed from

the sediments using the partial digestion method does not depend upon the

mass of sediment digested. It was the assumption that the volumes of digest

solutions and their concentrations were enough to digest variable amounts of

mass (0.25 – 1.3 g), and if the sediments were homogeneous, the results

would be the same for each sample. Copper concentrations in sediments

were not dependent upon the mass of sediment digested as indicated by the

reported relative standard deviations (site LJ13, 1%; LJ7, 2%).

In contrast, the study suggests that the mass of zinc and lead

removed from the sediments using the partial digestion method do depend

upon the mass of sediment digested (Figure 26 and Figure 27). These

conclusions were made as a result of the high relative standard deviations

observed for zinc concentrations in sediments (site LJ13, 12%; site LJ7, 11%)

63

and lead concentrations in sediments (site LJ13, 12%; site LJ7, 9%) using

variable amounts of sediment mass.

These findings could possibly be attributed to the source of metals in

the stream. Zinc and lead may originate partially from mineral complexes

within the sediments while copper is more available and possibly loosely

adsorbed to mineral surfaces. When smaller amounts of mass are digested,

the surfaces are available for longer periods of time allowing more rigorous

contact with the digest solution and thus further breakdown of the mineral

complexes. An interesting future analysis may be to include variable times of

mixing to try and diminish the variance between masses of sediment

digested.

Site LJ 13 Variable mass digested

0.25 g

0.25 g

0.25 g

0.5 g

0.5 g

0.5 g

0.75 g

0.75 g

0.75 g

1.0 g

1.0 g

1.0 g

1.25 g

1.25 g

1.25 g

0.0

100.0

200.0

300.0

400.0

500.0

600.0

Zinc Copper Lead

Mass of dry sediment digested (g)

Met

al (m

g/kg

)

Figure 26. Effect of amount of sediment on metal releases from the sediment collected at site LJ13 (1.59 km) by the partial digestion method.

64

Site LJ7 Variable mass digested

0.25

0.25

0.25

0.50.5

0.5

0.750.75

0.75

1.01.0

1.0

1.251.25

1.25

0.0

100.0

200.0

300.0

400.0

500.0

600.0

Zinc Copper Lead

Mass of dry sediment digested (g)

Met

al (m

g/kg

)

Figure 27. Effect of amount of sediment on metal releases from the sediment collected at site LJ7 (2.89 km) by the partial digestion method.

Reproducibility of sediment methods using field and lab replicates

Field replicate samples taken at sites LH18 (at Buckingham Park), LJ1

(Little James Creek reference), LJ8 (upstream of Porphyry Mountain tailings

pile), LJ9 (downstream of Porphyry Mountain tailings pile) and LJ11

(downstream of “streamside tailings”) indicated uniformity of metals over the

sample area of all individual sites except for the concentration of copper in

sediment at site LJ1. At this site, copper concentrations in sediment ranged

from 20 mg kg-1 to 77 mg kg-1 with a high relative standard deviation of 54%.

The relative standard deviation among triplicate samples at site LJ1 among

zinc concentrations was 10% while the relative standard deviation among

65

lead concentrations was 5%. The other four sites had extremely low relative

standard deviations between samples for all metals ranging from 1-4%, which

indicated good reproducibility for field sampling.

Laboratory procedure replicates indicated good reproducibility of the

partial digestion method for sites LJ4 (upstream of the Argo Mine), LJ5

(downstream of the Argo Mine), LJ6 (upstream of Emmit Mine), LJ10

(upstream of the “streamside tailings” pile), and J3 (Downstream of tailings

pile, just upstream of John Jay Mine). Averages and standard deviations are

reported for each metal and indicate variations of metal concentrations within

individual samples (Table 11). Relative standard deviations for all metals of

all five samples were low, ranging from 1 – 4%, not including replicates from

the sample taken at site LJ10 which ranged between 5-10% (in the order lead

> zinc > copper). This indicates that samples were homogenous for the most

part and that the partial digestion methods produce consistent results.

Average metal concentrations will be used for these sites for the remaining

portions of the text in the appropriate sections.

Table 11 Laboratory method replicate metal concentrations (mg kg-1 dry weight) in streambed sediments collected at sites LJ4, LJ5, LJ6, LJ10 and J3.

Site Name Element LJ4 LJ5 LJ6 LJ10 J3 Zinc 1430 ± 40 39.7 ± 0.8 74.7± 1.7 289 ± 22 51.2 ± 1.3 Copper 1480 ± 50 14.4 ± 0.3 31.5 ± 0.9 243 ± 12 29.6 ± 0.4 Lead 253 ± 9 66.3 ± 0.6 137 ± 3 738 ± 71 65.2 ± 0.8

66

Lefthand Creek streambed sediments – zinc, copper, and lead

Similarities in metal concentration changes along Lefthand Creek are

observed between zinc, copper, and lead (Figure 28). The concentrations of

copper, zinc, and lead in the sediments downstream of California Gulch (11-

32 km) are represented separately in Figure 29 in order to observe the

distribution of the investigated heavy metals on a smaller scale.

In Lefthand Creek, zinc concentrations ranged from 35 mg kg-1 at the

reference site (site LJ1upstream of Peak to Peak highway) to 4900 mg kg-1

downstream of the White Raven Mine site (site LJ7). Copper concentrations

in the sediments ranged from 12 mg kg-1 at the reference site (site LJ1) to

4900 mg kg-1 downstream of the White Raven Mine site (site LJ7). Lead

concentrations in the sediments of Lefthand Creek ranged from 26 mg kg-1 at

the reference site (site LJ1) to 2600 mg kg-1 downstream of the White Raven

Mine site (site LJ7). The concentrations of zinc, copper, and lead in the

sediments downstream of the White Raven Mine site were the highest among

all sites tested in the watershed. Approximately 0.7 km downstream of the

White Raven Mine at Sawmill Road (site LJ8), all metal concentrations are

observed to be lower in the sediments. In Lefthand Creek at Sawmill Road,

the zinc concentration in the sediment is 5 times lower (950 mg kg-) than at

White Raven, 0.7 km upstream (LJ7), while the copper concentration in the

sediment is 7 times lower (670 mg kg-1), and the lead concentration in the

sediment is 10 times lower (260 mg kg-1). In California gulch, the fractions of

67

the investigated metals in the sediments are dominated by zinc, less by

copper, and the least by lead.

Lefthamd Creek Distance Downstream (km)

Cop

per (

mg/

kg)

0

1000

2000

3000

4000

5000

6000

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Puzz

ler G

ulch

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

0 5 10 15 20 25 30

Lead

(mg/

kg)

0

1000

2000

3000

4000

5000

6000

Zinc

(mg/

kg)

0

1000

2000

3000

4000

5000

6000

Figure 28. Lefthand Creek Zn, Cu, and Pd in streambed sediments (grain size <63 μm). Metals released via acid-extraction. Samples were collected from October 1-October 17, 2005.

68

Lefthand Creek distance downstream (km)

11 13 15 17 19 21 23 25 27 29 31

Met

al c

once

ntra

tion

in s

edim

ents

(mg/

kg)

0

100

200

300

400

500

600

700

Copper (mg/kg) Lead (mg/kg) Zinc (mg/kg) Copper from Slide MineLead From Slide MineZinc from Slide Mine

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 29. Lefthand Creek (11-30 km) Cu, Zn and Pd in streambed sediments (grain size <63 μm). Metals released via partial digestion methods.

James Creek streambed sediments – zinc, copper, and lead

The concentrations of zinc in the sediments along James Creek

ranged from 42.3 mg kg-1 just downstream of Castle Gulch to 286 mg kg-1 just

upstream of the confluence with Lefthand Creek. Copper concentrations in

the sediments along James Creek ranged from 21.1 mg kg-1 downstream of

the treatment plant to 345.4 mg kg-1 just upstream of the confluence with

Lefthand Creek. Lead concentrations in the sediments along Lefthand Creek

ranged from 51.6 mg kg-1 just below Castle Gulch to 319 mg kg-1 just

upstream of the confluence with Lefthand Creek. The background reference

concentrations of metals in sediments sampled just upstream of Peak to Peak

highway were higher than concentrations measured downstream of known

abandoned mine and mill sites and waste rock piles. This site did show the

69

lowest metal concentrations in the stream water and benthic

macroinvertebrates and was expected to show the lowest metal

concentrations in sediments. These metal concentrations in the sediments

are most likely a result of the local mineralogy and geology in the watershed.

James Creek Distance Downstream (km)

Cop

per (

mg/

kg)

0

50

100

150

200

250

300

350

400

James Creek distance downstream (km)

0 2 4 6 8 10 12 14 16 18 20 22

Lead

(mg/

kg)

0

50

100

150

200

250

300

350

Zinc

(mg/

kg)

0

50

100

150

200

250

300

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Bue

no M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

Figure 30. James Creek Zn, Cu, and Pb in sediments (grain size <63 μm). Metals released via acid-extraction. Samples were collected between October 1, - October 17, 2005.

Little James Creek streambed sediments – zinc, copper, and lead

The concentrations of zinc in the sediments of Little James Creek ranged

from 40 mg kg-1 downstream of the Argo mine to 1400 mg kg-1 just upstream

70

of the Argo mine. The concentrations of copper in the sediments ranged from

14 mg kg-1 below the Argo Mine to 250 mg kg-1 just upstream of the

“streamside tailings.” The concentrations of lead in the sediments of Little

James Creek ranged from 60 mg kg-1 at the background reference location

(2.3 k m north of Jamestown) to 690 mg kg-1 just downstream of the

“streamside tailings” and the Bueno Mountain gully.

The concentrations of copper and zinc in the streambed sediments in Little

James Creek show distinctly similar increases and decreases along the entire

stream length. The minimum concentrations of copper and zinc occurred just

downstream of the Argo Mine. Near the confluence with James Creek,

concentrations of copper (50 mg kg-1) and zinc (80 mg kg-1) return to

concentrations measured at the background reference site, while lead

remains above background level concentrations (373 mg kg-1).

71

Little James Creek Distance Downstream (km)

Cop

per (

,g/k

g)

0

200

400

600

800

1000

1200

1400

1600

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Lead

(mg/

kg)

0

100

200

300

400

500

600

700

800

Zinc

(mg/

kg)

0

200

400

600

800

1000

1200

1400

1600

Bac

kgro

und

refe

renc

e

Even

ing

Sta

r

un-n

amed

was

te ro

ck p

ileArg

o M

ine

"Arg

o gu

lly"

Bala

rat r

oad

Bur

lingt

on M

ine

Em

it M

ine

adit

drai

nage

Bala

rat C

reek

min

e w

aste

pile

Stre

amsi

de ta

ilings

Bue

no M

tn. g

ully

Yel

low

girl

- nor

thW

ater

fall

Jam

es C

reek

con

fluen

ce

Figure 31. Little James Creek Zn, Cu, and Pb in sediments (grain size <63 μm). Metals released via partial digestion method. Samples were collected on September 24, 2005.

Streambed sediments – <63 um grain size percentages

Interestingly, sites along the California Gulch segment of Lefthand

Creek which were characteristic of high sediment metal concentrations show

the lowest percentage of fine grain (<63 μm) size fractions. On the other

hand, along areas of Little James Creek where concentrations of the

investigated metals were also among the highest in the watershed, grain size

72

percentages of fine particles were the highest. These results indicate that

grain size percentage is intrinsic of the natural settings along and within the

stream and not metal contributions. Higher percentages of these finer grain

sizes may indicate higher sediment loading near these reaches of the stream.

Areas of possible sediment loading can be assessed by looking at the percent

of small grain sizes per sample (Looking at Figure 32, Figure 33 and Figure

34). Along Lefthand Creek these include areas above Peak to Peak highway,

downstream of Lickskillet Road, downstream of Slide Mine, downstream of

Lee Hill Road and Sixmile Creek. Along James Creek, we see elevated fine

grain size percentages downstream of County Road 102J, and along Ward

Road between Main Street and the Forest Service road with restricted access

(no motor vehicles). Little James Creek has the highest fine grain size

percentages on average and these incidences occur downstream of the Argo

Mine, Balarat Creek, and the “streamside tailings,.”

73

Lefthand Creek Distance Downstream (km)

0 5 10 15 20 25 30

% o

f <63

μm

sed

imen

ts in

sam

ple

0.0%

0.2%

0.4%

0.6%

0.8%

1.0%

Peak

to P

eak

Hw

yD

ew D

rop

Min

e tr

ibB

ig F

ive

Tunn

el D

isch

arge

Puzz

ler G

ulch

Indi

ana

Gul

ch

unna

med

trib

- so

uth

unna

med

trib

- so

uth

Sprin

g G

ulch

Lick

Ski

llet G

ulch

Slid

e M

ine

Row

ena

Nug

get G

ulch

Lee

Hill

Gul

ch

Jam

es C

reek

unna

med

trib

- so

uth

off-r

oad

vehi

cle

area

Car

nage

Can

yon

Sixm

ile C

reek

Spru

ce G

ulch

Hal

di w

ater

inta

ke

Figure 32. Left Hand Creek - percent of sediments that are <63μm in size.

James Creek Distance Downstream (km)0 5 10 15 20

% o

f <63

μm

sed

imen

ts in

sam

ple

0.0%

0.5%

1.0%

1.5%

2.0%

Pea

k to

Pea

k H

ighw

ay

Cou

nty

Roa

d 10

0

Cou

nty

Roa

d 10

2JJo

hn J

ay m

ine

Faird

ay M

ine

Buen

o M

ount

ain

gully

Wat

er T

reat

men

t Pla

nt

Littl

e Ja

mes

Cre

ek

Jam

esto

wn

Por

phyr

y G

ulch

Cur

ie S

prin

gs

Cas

tle G

ulch

Lefh

and

Cre

ek

Figure 33. James Creek - percent of sediments that are <63 um in size.

74

James Creek distance downstream (km)

0.0 0.5 1.0 1.5 2.0 2.5 3.0

% o

f <63

μm

sed

imen

ts in

sam

ple

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

3.5%

4.0%

Bac

kgro

und

refe

renc

e

Eve

ning

Sta

r

un-n

amed

was

te ro

ck p

ileAr

go M

ine

"Arg

o gu

lly"

Bal

arat

road

Bur

lingt

on M

ine

Em

it M

ine

adit

drai

nage

Bal

arat

Cre

ek

min

e w

aste

pile

Stre

amsi

de ta

ilings

Buen

o M

tn. g

ully

Yel

low

girl

- nor

thW

ater

fall

abov

e co

nflu

ence

Jam

es C

reek

con

fluen

ce

Figure 34. Little James Creek - percent of sediments that are <63 um in size.

Waste rock piles

Waste rock pile sediment metals

As expected, metal concentrations measured via weak acid extraction

from waste rock pile sediments exceeded elutriated metal concentrations.

Concentrations of lead released from sediments via partial digestion were

highest among waste rock piles along Lefthand Creek including the waste

rock piles at the Dew Drop Mine, the White Raven Mine, and the lower Slide

Mine. The lead concentrations in the whole and yellow piles at the White

Raven site were highest among the waste rock piles samples in the

watershed. Waste piles along Little James which were high in lead include

75

those at the Evening Star Mine, Emmit mine and Bueno Mine. Elevated zinc

levels were also measured within the Evening Star waste rock sediments.

Copper concentrations were highest in the sediments at the Corning Tunnel.

0

50

100

150

200

250

300

350

400

450

Lefth

and

Ref

eren

ce

Dew

Dro

p

Big

Fiv

e (g

rey)

Big

Fiv

e(y

ello

w)

Whi

te R

aven

Lick

Ski

llet

Cor

ning

Tun

nel

Upp

er S

lide

Pile

Low

er S

lide

Pile

M

etal

con

cent

ratio

n (m

g/kg

)

Figure 35. Concentrations of metals elutriated from waste rock piles along Lefthand Creek. Data collected by Amber Roche. White bars represent zinc, grey bars represent copper, and black bars represent lead.

0

50

100

150

200

250

300

350

400

450

LittleJames

Reference

EveningStar

Upper ArgoPile

Lower ArgoPile

Emmett StreamSide

Porpyhry Bueno

M

etal

con

cent

ratio

n (m

g/kg

)

Figure 36. Concentrations of metals in sediments at waste rock piles along Little James Creek. Data collected by Amber Roche.

76

Waste rock pile elutriation concentrations

The elutriated waste rock piles sediments with the highest metal content were

consistent with downstream water, benthic macroinvertebrate and sediment

concentrations. These waste rock piles include the Big Five Tunnel, White

Raven and the Slide Mine upper pile.

The investigated metals concentrations (units of mg kg-1) elutriated from

waste rock pile sediments for Lefthand Creek and Little James Creek are

represented in Figure 37 and Figure 38 respectively. Along Lefthand Creek,

concentrations in the tailings pile at the White Raven mine site and less

evidently at the tailings piles at the Slide Mine indicate high concentrations of

lead elutriated from waste rock piles. Copper and zinc are highest in the

tailings pile at the White Raven site and the tailings pile near the Big Five

tunnel.

0

50

100

150

200

250

300

350

400

450

Lefth

and

Ref

eren

ce

Dew

Dro

p

Big

Fiv

e (g

rey)

Big

Fiv

e(y

ello

w)

Whi

te R

aven

Lick

Ski

llet

Cor

ning

Tun

nel

Upp

er S

lide

Pile

Low

er S

lide

Pile

Copper (mg/kg) Lead (mg/kg) Zinc (mg/kg)

M

etal

con

cent

ratio

n (m

g/kg

)

Figure 37. Lefthand Creek waste rock pile total elutriated metal concentrations. Error bars represent standard deviations of duplicate samples.

77

Along Little James Creek the waste rock piles with the highest elutriated lead

concentrations in decreasing order occur at the Evening Star Mine > Upper

Argo Mine > “streamside tailings” > Bueno Mountain. Lead concentrations

dominate the elutriated metals from the respective waste rock piles.

Elutriated zinc is highest in decreasing order at Evening Star >Streamside

tailings > Bueno Mountain. These four waste rock piles will be the focus of

discussion for Little James Creek.

0

50

100

150

200

250

300

350

400

450

LittleJames

Reference

EveningStar

Upper ArgoPile

Lower ArgoPile

Emmett StreamSide

JRT Bueno

Cu Pb Zn

M

etal

con

cent

ratio

n (m

g/kg

)

Figure 38. Little James Creek waste rock pile total elutriated metal concentrations. Error bars represent standard deviations of duplicate samples.

78

Discussion

In order to assess the impacts of intermittent sources of toxic metals to

streams in the Lefthand Creek watershed, metal concentrations were

measured in the stream water, benthic macroinvertebrates, stream

sediments, and waste rock piles. Our analyses focused on zinc, copper, and

lead because these metals most frequently and consistently exceed aquatic

life standards in the watershed (Lefthand Watershed Task Force 2002; Wood

et al. 2004), and because these metals behave quite differently with respect

to adsorption to minerals, organic matter, and organisms (Dzombak and

Morel 1990; Erickson et al. 1996; Farag et al. 1998; Galan et al. 2003).

Exposure time to toxic metals and the fate and transport of metals in streams

were key factors in creating hypotheses.

We hypothesized that benthic macroinvertebrates and sediments,

which have proved to be good monitors of metal loading over time (Hare et al.

1991; Woodward et al. 1994), would provide evidence of metal inputs in to the

streams by intermittent tributaries and snow melt. We examined the data for

spatial correlations between metal concentrations in the benthic

macroinvertebrates and the sediments and metal concentrations in

elutriations of waste rock piles at expected metal sources, the mine and mill

sites in the watersheds.

Because both benthic macroinvertebrates and sediments are expected

to be good monitors of metal loading from intermittent sources, we expected

that the metal concentrations in the benthic macroinvertebrates and the

79

sediments would be correlated, but that the metal concentrations in the

benthic macroinvertebrates and sediments would not be correlated with the

metal concentrations in the stream water. We examined the data for these

correlations in order to test this hypothesis. We expected that zinc, copper,

and lead would follow the patterns of speciation observed in other streams

and soils (Kimball et al. 1995; Farag et al. 1998; Fey et al. 1999; Schemel et

al. 2000; Adriano 2001; Munk et al. 2002). In the stream water samples, we

expected that zinc would be mostly dissolved, lead would be mostly bound to

colloids, and copper would be found in both fractions. Because of this

behavior, we expected to find more lead and less zinc accumulation in the

sediments and benthic macroinvertebrates as a fraction of the total amount of

metals in the streams. We expected that the amount of dissolved organic

matter in the streams would play a role in the metal distributions between

water, sediments, and benthic macroinvertebrates as well – more organic

matter would increase the amount of metals in the dissolved fraction. We

tested these hypotheses by assessing dissolved and colloidal metal

concentrations and correlations between dissolved metal and organic matter

concentrations.

The final section of the Discussion contains our analysis of the implications of

these finding for prioritization of abandoned mine cleanup in the Lefthand

Creek watershed.

80

Copper, zinc, and lead concentrations in stream water, benthic macroinvertebrates, and sediments

Regression analyses for were completed between stream water metal

concentrations and benthic macroinvertebrates and stream water metal

concentrations and sediments in order to find correlations among media

(Figure 39-Figure 41 ). Few strong correlations were found using this analysis

and all but one existed in Lefthand Creek. A single positive correlation in

Little James Creek was found between lead in benthic macroinvertebrates

and stream water samples (r2 = 0.74). In addition to this correlation, the

absence of macroinvertebrates in seven of the thirteen sampling sites in Little

James Creek, and nearby benthic macroinvertebrate lead concentrations

highest in the watershed, it appears that lead impairs the stream water

quality. Concentrations of zinc and copper were ruled out as targets of

impairment due to similar concentrations found in the watershed which

contained an abundance of macroinvertebrates (i.e., downstream of the White

Raven Mine and the Big Five Tunnel drainage). Besides this single

comparison, water concentrations did not show strong correlations with

macroinvertebrate or sediment concentrations within the watershed.

Regression analyses for were completed between stream water metal

concentrations and benthic macroinvertebrates and stream water metal

concentrations and sediments in order to find correlations among media

(Figure 42 - Figure 44). Along the entire length of Lefthand Creek, strong

correlations were observed between macroinvertebrates and sediments for

81

copper (r2 = 0.80) and lead (r2 = 0.64). These were a result of the strong

correlations found within California gulch, and not representative of the entire

stream. For the California Gulch segment of Lefthand Creek, correlations

between macroinvertebrates and sediments improve to r2 = 0.82 for copper

and r2 = 0.90 for lead. Copper and lead have a higher affinity to bind to

surfaces and form complexes than does zinc in the pH range found in

Lefthand Creek which end up in the sediments.

82

0 5 10 15 20 25 30

Mac

roin

verte

brat

e co

pper

(μg

g-1)

0

200

400

600

800

r ² = 0.38

Lefthand Creek Macroinvertebrate vs. Water

0 5 10 15 20 25 30

Sedi

men

t cop

per (

mg

kg-1

)

0

1000

2000

3000

4000

5000

6000

Lefthand Creek Sediment vs. Water

Cu Cu

0 1 2 3 4 50

5

10

15

20

0 1 2 3 4 5

Sed

imen

t lea

d (m

g kg

-1)

0

200

400

600

800

1000

1200

1400

Pb Pb

r ² = 0.50

Dissolved metal (μg/L)

0 20 40 60 80 100 1200

500

1000

1500

2000

2500

3000

3500

r ² = 0.10

r ² = 0.16

Dissolved metal (μg/g)

0 20 40 60 80 100 120

Sedi

men

t zin

c (m

g kg

-1)

0

1000

2000

3000

4000

5000

6000

ZnZn

r ² = 0.68

r ² = 0.02

Mac

roin

verte

brat

e le

ad (μ

g g-1

)M

acro

inve

rtebr

atez

inc

(μg

g-1)

Figure 39. Comparisons of metals in benthic macroinvertebrates and dissolved metals in water (left column) and metals in sediments and dissolved metals in water (right column) for zinc, copper, and lead in Lefthand Creek.

83

0 5 10 15 20 25 30

Mac

roin

verte

brat

e co

pper

(μg

g-1 )

0

20

40

60

80

100

James Creek Macroinvertebrate vs. Water

0 5 10 15 20 25 30

Sed

imen

t cop

per (

mg

kg-1

)

0

100

200

300

400

James Creek Sediment vs. Water

CuCu

0.3 0.4 0.5 0.6 0.7 0.80

2

4

6

8

10

0.3 0.4 0.5 0.6 0.7 0.8

Sed

imen

t lea

d (m

g kg

-1)

0

50

100

150

200

250

300

350Pb Pb

Dissolved metal (μg/L)

0 2 4 6 8 100

200

400

600

800

1000

1200

1400

1600

Dissolved metal (μg/g)

0 2 4 6 8 10

Sed

imen

t zin

c (m

g kg

-1)

0

50

100

150

200

250

300ZnZn

r ² = 0r ² = 0.35

r ² = 0.16 r ² = 0.12

r ² = 0.06 r ² = 0.16

Mac

roin

verte

brat

e le

ad (μ

g g-

1 )M

acro

inve

rtebr

ate

zinc

(μg

g-1 )

Figure 40. Comparisons of metal concentrations in benthic macroinvertebrates and dissolved metals in water (left column) and metal concentrations in sediments and stream water (right column) for copper, zinc, and lead in James Creek.

84

0 20 40 60 80

Mac

roin

verte

brat

e co

pper

(μg

g-1

)

0

25

50

75

100

125

150

175

200

Little James Creek Macroinvertebrate vs. Water

0 5 10 15 20 25 30

Sed

imen

t cop

per

(mg

kg-1

)

0

200

400

600

800

1000

1200

1400

1600

Little James Creek Sediment vs. Water

Cu Cu

0 10 20 30 40 50 600

50

100

150

200

250

300

350

0 10 20 30 40 50 600

100

200

300

400

500

600

700

800Pb Pb

Dissolved metal (μg/L)

0 200 400 600 800 1000 12000

200

400

600

800

1000

1200

1400

1600

1800

Dissolved metal (μg/g)

0 200 400 600 800 1000 1200 14000

200

400

600

800

1000

1200

1400

1600ZnZn

r ² = 0.13

r ² = 0

r ² = 0.74

r ² = 0.10

r ² = 0.14 r ² = 0.12

Mac

roin

verte

brat

e zi

nc (μg

g-1

)M

acro

inve

rtebr

ate

lead

(μg

g-1 )

Sed

imen

t zin

c (m

g kg

-1)

Sed

imen

t lea

d (m

g kg

-1)

Figure 41. Comparisons of metal concentrations in macroinvertebrates and stream water (left column) and metal concentrations in sediments and stream water (right column) for copper, zinc, and, lead in Little James Creek.

85

Lefthand CreekMacroinvertebrate tissue vs. Sediment

0 1000 2000 3000 4000 5000 6000

Mac

roin

verte

brat

e co

pper

( μg

g-1)

0

200

400

600

800

1000

Lefthand Creek - California GulchMacroinvertebrate tissue vs. Sediment

0 1000 2000 3000 4000 5000 6000

Sed

imen

t cop

per (

mg

kg-1

)

0

200

400

600

800

1000Cu Cu

r ² = 0.82

0 500 1000 1500 2000 2500 30000

5

10

15

20

25

30

35

r ² = 0.64

0 500 1000 1500 2000 2500 30000

5

10

15

20

25

30

35

r ² = 0.89

Sediment (μg/g)

0 1000 2000 3000 4000 5000 60000

500

1000

1500

2000

2500

3000

3500

Sediment (μg/g)

0 1000 2000 3000 4000 5000 60000

500

1000

1500

2000

2500

r ² = 0.40

Pb Pb

Zn Zn

r ² = 0.02

r ² = 0.80

Mac

roin

verte

brat

e le

ad ( μ

g g-1

)M

acro

inve

rtebr

ate

zinc

(μg

g-1)

Sed

imen

t lea

d (m

g kg

-1)

Sed

imen

t zin

c (m

g kg

-1)

Figure 42. Comparisons of metals in benthic macroinvertebrates and metals in sediments for all of Lefthand Creek (left column) and for only the California Gulch reach of Lefthand Creek (right column).

86

James CreekMacroinvertebrate tissue vs. Sediment

0 20 40 60 80 100 120 140 160 180 200

Mac

roin

verte

brat

e co

pper

( μg

g-1)

0

20

40

60

80

100Cu

0 50 100 150 200 250 300 3500

2

4

6

8

10

0 50 100 150 200 250 3000

200

400

600

800

1000

1200

1400

1600Zn

Pb

Sediment lead (mg kg-1)

r ² = 0.28

r ² = 0 r ² = 0.13

Mac

roin

verte

brat

e zi

nc ( μ

g g-1

)

Mac

roin

verte

brat

e le

ad (μ

g g-1

)

Sediment zinc (mg kg-1)

Sediment copper (mg kg-1)

Figure 43. Comparisons of metals in benthic macroinvertebrates and metals in sediments for zinc, copper, and, lead in all of James Creek.

87

0 200 400 600 800 1000 1200 1400 16000

20

40

60

80

100

120

140

160

180Cu

0 200 400 600 8000

50

100

150

200

250

300

350

0 200 400 600 800 1000 1200 1400 16000

200

400

600

800

1000

1200

1400

1600

1800Zn

Pb

r ² = 0 r ² = 0.09

r ² = 0.08

Little James CreekMacorinvertebrate tissue vs. Sediment

Mac

roin

verte

brat

e co

pper

(μg

g-1

)M

acro

inve

rtebr

ate

zinc

(μg

g-1

)

Mac

roin

verte

brat

e le

ad ( μ

g g-

1 )

Sediment copper (μg g-1)

Sediment zinc (μg g-1)

Sediment lead (μg g-1)

Figure 44. Comparisons of metals in benthic macroinvertebrates and metals in sediments for zinc, copper, and lead in all of Little James Creek.

Zinc, copper, and lead inputs from waste rock piles

We observed a significant difference in concentrations between metals

dissolved from waste rock by the partial digestion and by elutriation was seen

among all samples (Figure 35 - Figure 38). The weak acid extraction method

provides insight into the more tightly bound metals to the sediments in the

waste rock piles, while the elutriation method indicates what portion of metals

may be removed during rainfall and snow melt events. The sixteen waste rock

88

piles analyzed using this method and are listed in Table 12 in decreasing

order of elutriated concentrations of copper, zinc, and lead. We listed these

in decreasing order to get a sense of which metals are attributed to each

tailings pile.

Table 12 Waste rock piles rated in decreasing order of total elutriated zinc, copper and lead.

Rating total Zn mg kg-1 site

total copper mg kg-1 site

total lead

mg kg-1 site 1 118 Evening Star 46.7 White Raven 417 White Raven

2 46.4 Stream Side 30.4 Evening Star 164 Upper Argo Pile

3 44.0 White Raven 27.6 Stream Side 143 Evening Star

4 15.4 Dew Drop 21.9 Upper Argo Pile

114 Stream Side

5 13.4 Bueno 17.9 Big Five (grey portion)

78.2 Bueno

6 13.4 Lower Argo Pile

12.7 Bueno 53.7 Lower Slide Pile

7 10.1 Emmit 12.4 Dew Drop 32.4 Corning Tunnel

8 9.34 Upper Argo Pile

9.84 Emmit 20.2 Emmit

9 8.96 Big Five (yellow portion)

8.20 Big Five (yellow portion)

19.2 Big Five (yellow portion)

10 8.86 Big Five (grey portion)

7.58 Lower Argo Pile

17.5 Lower Argo Pile

11 7.95 Lower Slide Pile

7.28 Corning Tunnel

12.3 JRT

12 7.14 JRT 7.04 JRT 10.3 Big Five (grey portion)

13 4.92 Corning Tunnel

6.33 Lower Slide Pile

8.7 Dew Drop

14 3.29 Upper Slide Pile

1.77 Lefthand Reference

5.65 Lick Skillet

15 3.06 Lefthand Reference

1.63 Lick Skillet 2.38 Upper Slide Pile

16 2.92 Lick Skillet 1.03 Upper Slide Pile

0.86 Lefthand Reference

89

We hypothesized that benthic macroinvertebrates and sediments, which have

proved to be good monitors of metal loading over time (Hare et al. 1991;

Woodward et al. 1994), would provide evidence of metal inputs in to the

streams by intermittent tributaries and snow melt. We expect that the

elutriated metal concentrations (total and dissolved) from waste rock piles will

correlate with downstream benthic macroinvertebrate and streambed

sediment concentrations. To test this hypothesis we conducted a correlation

analysis between total elutriated metal concentrations from the waste rock

piles and the downstream metal concentrations in benthic macroinvertebrate

metal and streambed sediments (Figure 45) for zinc, copper, and lead. We

conducted the same correlation analysis substituting dissolved elutriated

metals for total elutriated metals (Figure 46). The waste rock piles included in

this analysis are those in Table 12 above minus Corning Tunnel (due to the

close proximity of the White Raven site. For sites in which more than one

waste rock pile was analyzed (i.e., Argo Mine and Slide Mine), we summed

the concentrations assuming that metals from both piles leached metals

during precipitation events. We did not find correlations between downstream

benthic macroinvertebrate metal concentrations (copper and zinc) and total or

dissolved elutriated metal concentrations (copper and zinc) from waste rock

piles as indicated by the r2 values in Table 13. There was a week correlation

between lead in benthic macroinvertebrates and both total and dissolved lead

elutriated from waste rock piles. This came as a surprise because lead is the

least mobile of the three investigated metals and would not be expected to

90

enter the stream in similar concentrations as was mobilized by a storm event.

In addition, we did not find correlations for any of the investigated metals

between sediments and elutriated metal concentrations (total and dissolved)

from waste rock piles as indicated by the r2 values in Table 13 below.

Table 13 The r2 values observed from correlation analysis which tested the hypothesis that elutriated metals from waste rock piles correlated with downstream benthic macroinvertebrates and sediments. r2 values for lead in benthic macroinvertebrates a weak correlation in for both total and dissolved portions. benthic

macroinvertebrate vs. total elutriated

sediment vs. total

elutriated

benthic macroinvertebrate vs. dissolved elutriated

sediment vs. dissolved elutriated

zinc 0.018 0.003 0.003 0.07

copper 0.003 0.21 0.03 0.08

lead 0.24 0.02 0.32 0.009

These non-correlations can be attributed to the differences between waste

rock pile flow paths (length from waste pile to stream, slope of path from

waste rock pile to stream), the area of exposed waste rock, and the

mineralogy of the waste rocks along with their ability to leach metals. Lastly,

some of the waste rock piles are known to be constantly draining groundwater

discharge from under the waste rock piles or near the site area (i.e. Big Five

Tunnel, Argo Mine, Burlington Mine, and Bueno Mountain). These flows add

metal concentrations to the streams which can not be identified using results

from the elutriation tests.

91

Benthic macroinvertebrate metal concentrations downstream of waste rock pile vs. total elutriated metals

Total elutriated zinc (mg kg-1)

0 20 40 60 80 100 120

Mac

roin

verte

brat

e zi

nc (m

g kg

-1)

0

500

1000

1500

2000

2500

3000

3500

Streambed sediment metal concentrations downstream of waste rock pile vs. total elutriated metals

0 20 40 60 80 100 120

Sed

imen

t zin

c, (m

g kg

-1)

0

1000

2000

3000

4000

5000

6000r ² = 0r ² = 0.02

Total elutriated copper (mg kg-1)

0 10 20 30 40 50

Mac

roin

verte

brat

e co

pper

(mg

kg-1

)

0

200

400

600

800r ² = 0

0 10 20 30 40 50

Sed

imen

t cop

per (

mg

kg-1

)

0

1000

2000

3000

4000

5000

6000r ² = 0.21

Total elutriated lead (mg kg-1)

0 100 200 300 400 500

Mac

roin

verte

brat

e le

ad (m

g kg

-1)

0

50

100

150

200

250

300

350

0 100 200 300 400 500

Sed

imen

t lea

d (m

g kg

-1)

0

500

1000

1500

2000

2500

3000r ² = 0.02r ² = 0.24

Total elutriated zinc (mg kg-1)

Total elutriated copper (mg kg-1)

Total elutriated lead (mg kg-1)

Figure 45. A correlation analysis between macroinvertebrate (plots on the left) and sediment (plots on the right) metal concentrations downstream of waste rock piles and total elutriated metals (zinc – squares, copper – triangles, and lead – circles). Dashed lines are the 95% confidence intervals.

92

Benthic macroinvertebrate metal concentrations downstream of waste rock pile vs. dissolved elutriated metals

0 20 40 60 80 100 1200

1000

2000

3000

4000

Streambed sediment metal concentrations downstream of waste rock pile vs. dissolved elutriated metals

0 20 40 60 80 100 1200

1000

2000

3000

4000

5000

6000r ² = 0.07r ² = 0.003

0 5 10 15 20 250

200

400

600

800r ² = 0.03

0 5 10 15 20 25 300

1000

2000

3000

4000

5000

6000r ² = 0.08

0 5 10 15 20 25 300

50

100

150

200

250

300

350

0 5 10 15 20 25 30 350

500

1000

1500

2000

2500

3000r ² = 0.009r ² = 0.32

Dissolved elutriated zinc (mg kg-1)

Mac

roin

verte

brat

e zi

nc (m

g kg

-1)

Sed

imen

t zin

c, (m

g kg

-1)

Dissolved elutriated copper (mg kg-1)

Mac

roin

verte

brat

e co

pper

(mg

kg-1

)

Sed

imen

t cop

per (

mg

kg-1

)

Dissolved elutriated lead (mg kg-1)

Mac

roin

verte

brat

e le

ad (m

g kg

-1)

Sed

imen

t lea

d (m

g kg

-1)

Dissolved elutriated zinc (mg kg-1)

Dissolved elutriated copper (mg kg-1)

Dissolved elutriated lead (mg kg-1)

Figure 46. A correlation analysis between macroinvertebrate (plots on the left) and sediment (plots on the right) metal concentrations downstream of waste rock piles and dissolved elutriated metals (zinc – squares, copper – triangles, and lead – circles). Dashed lines are the 95% confidence intervals.

We can analyze the data for spatial correlations between elutriated

metal from waste rock piles and abandoned mills and mines and

93

macroinvertebrates and sediments if the sites did not contain constant

groundwater discharge to the stream. This would allow us to more

confidently state that the metal concentrations elutriated from the waste rock

pile were representative of the amount mobilized during a storm event and

flowing into the stream.

Of the sixteen waste rock pile sites, the Slide Mine and the White

Raven Mine waste rock piles were chosen for this analysis because flows

from intermittent streams near these sites are only observed during

precipitation events or snowmelt. The identification of metals into the stream

via drainage and precipitation events is difficult to distinguish between without

fingerprinting analysis of the sediments and stream water. This was beyond

the scope of this project and so for this analysis (correlating in-stream metal

concentrations with waste rock piles) we have chosen sites the White Raven

and Slide Mine sites on Lefthand Creek and the Evening Star Mine on Little

James Creek, all of which do not have groundwater discharge.

White Raven waste rock pile

Copper was the dominant metal elutriated from the White Raven Mine

waste rock pile. This can be attributed to the high copper content in the

minerals that were prevalent in the Ward mining district, including azurite

(Cu3(OH)2(CO3)2), chalcopyrite (CuFeS2), and bornite (Cu5FeS4) (Eckel

1961). Among all waste rock piles analyzed via the elutriation method, White

Raven waste rock pile contained the highest concentrations of copper and

lead concentrations and contained the third highest concentration of zinc

94

concentrations (Table 12 above). We also see high concentrations of copper,

zinc, and, lead in the stream water, macroinvertebrate and sediments

downstream of the White Raven site (Table 14). The high lead levels in the

waste rock of the White Raven mine (total elutriated = 417 mg kg-1) are

attributed to the prevalence of galena (PbS) in the White Raven vein. The

silver-lead ore produced at this site ranged from 10-15% lead (Cobb 1988).

High zinc levels in macroinvertebrates and sediments downstream of

the White Raven Mine (Table 14) reflect the presence of sphalerite (ZnS) in

the White Raven Mine vein (Eckel 1961). Zinc concentrations in

macroinvertebrates increase downstream of the White Raven Mine by 75%

(Figure 23, Table 14).

The next sampling point after the California Gulch reach is

approximately 8 km downstream. It would be helpful in the future to sample

this area for benthic macroinvertebrates and sediments to look for metal

accumulation from the White Raven site further downstream.

Table 14 Percent increases in benthic macroinvertebrate and sediment metal concentrations from above to downstream of the White Raven Mine and waste rock pile. A negative increase represents a decrease in concentration.

Stream water (ug L-1) Macroinvertebrate (mg kg-1) Streambed sediments (mg kg-1)

Metal UP DOWN %

Increase UP DOWN%

Increase UP DOWN %

Increase White Raven

Copper 18.8 24 27.7% 474 668 40.9% 2460 4910 99.6% Lead 0.43 0.88 104.7% 18.9 27.4 45.0% 1220 2620 114.8% Zinc 71.7 95.3 32.9% 1118 1958 75.1% 2361 4870 106.3%

95

Slide Mine waste rock pile

Due to anecdotal evidence of metal inputs at the Slide Mine, we

expected sediments and benthic macroinvertebrate metals (those found to be

present in the waste rock piles) to increase from above to downstream of the

Slide Mine. The lower Slide Mine elutriated 53.7 mg kg-1 of lead as compared

to the White Raven site which elutriated 417 mg kg-1. Lead concentrations

increased by 944% from above to downstream of the Slide Mine in benthic

macroinvertebrates (1642 to 2922 mg kg-1). Zinc concentrations inputs from

Slide mine are the most likely source of the highest zinc concentrations in

macroinvertebrates found throughout the 10 km reach downstream of the

Slide Mine. In this case, elutriated metals from waste rock piles did not aid in

determining the extent of metal accumulation in macroinvertebrates

downstream. Once again, the size of the waste rock piles and the flow paths

during precipitation events are needed to further asses the impacts of the

individual waste rock piles.

Table 15 Percent increases in benthic macroinvertebrate and sediment metal concentrations from above to downstream of the Slide Mine site. A negative increase represents a decrease in concentration.

Stream water (ug L-1) Macroinvertebrate (mg kg-1) Streambed sediments (mg kg-1)

Metal UP DOWN %

Increase UP DOWN%

Increase UP DOWN %

Increase Slide Mine

Copper 15 7.7 -48.7% 122 202 65.6% 127 107 -15.7%

Lead 0.45 4.7 944.4% 4.54 10.5 131.3% 118 144 22.0%

Zinc 33 44.5 34.8% 1642 2922 78.0% 301 408 35.5%

96

Metal distribution between water, colloids, and sediments

We expected the behavior of copper, lead, and zinc to follow

speciation patterns that have been well documented in streams (Axtmann et

al. 1990; Hare et al. 1991; Kimball et al. 1995; Church et al. 1997; Farag et al.

1998; Munk et al. 2002). Water quality parameters have a direct effect on the

interactions of colloids with metals in stream systems by influencing the

mobility, transport, and attenuation of metals in streams and stream bed

sediments (Stumm 1992; Kimball et al. 1995). Chemical processes in the

stream depend on pH, which influences metal solubility, adsorption of metals

onto mineral and organic surfaces, and precipitation-dissolution reactions.

Calcium and magnesium (measured as hardness) compete with metals for

binding sites.

The distribution of metals in the colloidal phase is dominated by lead,

next copper and the least by zinc(Kimball et al. 1995; Schemel et al. 2000).

Evidence of these patterns are supported by observed distribution coefficients

(Kdobs, L kg-1), which can be used to describe the distribution between the

dissolved and colloidal phase. The observed distribution coefficient for each

metal requires measured colloidal concentrations from filtered samples.

1

11

(( )

( )observed sd

w

C mgkgK Lkg

C mgL

−−

−=)

(3)

where Cs in the solid phase (in this case colloidal) and Cw is the dissolved

concentration in the water (mg L-1). The concentrations of colloids in the

water were not measured, so as a substitute for.the Kd values, colloidal

97

fractions will be used. The colloidal fractions (fcolloid) of zinc, copper, and lead

can be expressed as

( )total dissolved

colloidtotal

C Cf

C−

= (4)

where Ctotal is the total (unfiltered) concentration of a metal and Cdissolved is the

dissolved (filtered) concentration of a metal. In agreement with the patterns

of metal colloidal partitioning, The colloidal fraction were calculated for all

water samples taken along the Lefthand Creek, James Creek, and Little

James Creek and averaged (Figure 47). These averages indicate that lead is

the most abundant in the colloidal phase, copper shows intermediate

behavior, and zinc is the least expected to adsorb to the colloidal phases

removed by 0.45 μm filtration. The observed colloidal fractions are

dependent upon pH (Stumm and Morgan 1996); however, this was not

proved with the steam data (Figure 47).

98

Little James Creek

Zn Cu Pb

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

James Creek

Zn Cu Pb

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

Lefthand Creek

Zn Cu Pb

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0 Lefthand Creek

pH6.4 6.6 6.8 7.0 7.2 7.4

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

Little James Creek

pH5.2 5.6 6.0 6.4 6.8

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

James Creek

pH6.0 6.2 6.4 6.6 6.8 7.0

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

Figure 47. The colloidal fraction (fcolloid) of zinc, copper, and lead in the three creeks of the Lefthand watershed (left column, mean and one standard deviation shown by error bar), and the dependence of the colloidal fraction on the pH of the water samples (right column - zinc (circles), copper (triangles), and lead (squares)).

Colloidal metals and Kint

General trends of copper, lead and zinc partitioning into the colloidal

phase also reflect the surface complexation constants, Kint, of these metals as

reported by Dzombak and Morel (1990) and represented logarithmically in

Table 16. The average colloidal fractions in Little James, James, and

Lefthand Creeks correspond well with these intrinsic surface complexation

constants (Figure 48 below). These trends give further evidence of the

99

characteristic binding sequence of Pb > Cu > Zn for acid mine drainage

streams.

Table 16 Intrinsic surface complexation constants (Kint ) reported by Dzombak and Morel (1990).

Metal Intrinsic surface complexation constant (Kint) Lead 4.65

Copper 2.89 Zinc 0.99

Little James Creek

log Kint

0 1 2 3 4 5

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

James Creek

0 1 2 3 4 50.0

0.2

0.4

0.6

0.8

1.0

Lefthand Creek

0 1 2 3 4 50.0

0.2

0.4

0.6

0.8

1.0

log Kint log Kint

Figure 48. Colloidal fractions of zinc (circles), copper (triangles), and lead (squares) compared to the logarithms of the intrinsic surface complexation constants (log Kint) reported by Dzombak and Morel (1990).

Colloidal metals and hardness

Hardness (Ca and Mg) plays a major role in the toxicity of metals to

aquatic life. The toxic metals compete with calcium and magnesium compete

with for binding sites on the gills of fish and gilled aquatic insects(Kiffney and

Clements 1992; Giddings et al. 2001; Paquin et al. 2002; Markich et al. 2005).

Toxic metals also compete with hardness for binding sites on iron hydroxide

complexes and organic matter in the stream water and therefore remain in the

dissolved phase. Therefore, we expect the colloidal fraction of metals to

100

increase and hardness decreases. Figure 49 displays the testing of this

hypothesis and shows that the fraction of colloidal zinc increases, copper

increases, and lead stays about the same as hardness increases. The

hardness in Little James Creek is extremely high (53 – 470 mg L-1 CaCO3) in

comparison to Lefthand Creek (14 – 38 mg L-1 CaCO3) and James Creek (7.3

– 11 mg L-1 CaCO3). The large differences in hardness coupled with the fact

that lead has the highest and zinc the lowest affinities for binding with

surfaces show that the colloidal fractions of all investigated metals are lower

in Little James and James Creeks than Lefthand Creek with zinc being

affected the most, lead the least and copper somewhere in between (Figure

49). It is important to note that there is a fair amount of variability amongst

these trends which suggests that hardness is not the only factor driving these

speciation patterns.

101

copp

er, f

collo

id

0.0

0.2

0.4

0.6

0.8

1.0

zinc

, fco

lloid

0.0

0.2

0.4

0.6

0.8

1.0

Hardness (mg CaCO3 L-1)

0 50 100 150 200 250 300 350 400 450 500

lead

, fco

lloid

0.0

0.2

0.4

0.6

0.8

1.0

Figure 49. Fractions of colloidal metal versus hardness in James (closed circles), Lefthand (open circles) and Little James (closed triangles creeks.

Colloidal metals and iron hydroxide surfaces

We expected the behavior of copper, lead, and zinc to follow

speciation patterns that have been well documented in streams (Axtmann et

al. 1990; Hare et al. 1991; Kimball et al. 1995; Church et al. 1997; Farag et al.

1998; Munk et al. 2002). We have shown that pH and hardness have a direct

effect on the interactions of colloids with metals in stream systems by

influencing the mobility, transport, and attenuation of metals in stream water.

102

When acid mine drainage tributaries mix with neutral pH streams, amorphous

and semi-crystalline oxyhroxides and hydroxysulfates of iron form (Stumm

and Morgan 1996). These precipitates have surface sites that sorb cations

which also depend upon pH. Figure 50 below shows the colloidal fraction of

iron as a function of pH. Although the correlation is not strong, we observe a

general increase in the fraction of colloidal iron as pH increases.

pH

5.25 5.50 5.75 6.00 6.25 6.50 6.75 7.00 7.25 7.50

Iron,

f collo

id

0.0

0.2

0.4

0.6

0.8

1.0

Figure 50. The influence of pH on colloidal fractions of iron (fcolloid) throughout the watershed.

The iron hydroxide surfaces play a major role in removing zinc, copper,

and lead from the dissolved fraction of the stream water (Stumm and Morgan

1996). To show the relationship between colloidal iron and the removal of

investigated metals, we plotted the colloidal fractions of investigated metals

as a function of the concentration of colloidal iron (μmol L-1) (Figure 51).

Correlations for zinc, copper, and lead were not found as expressed by r2

values of zero for all metals. A better correlation may be seen between the

concentrations of iron in the sediments and the concentrations of investigated

metals in the sediments. As iron precipitates form and bind with zinc, copper,

and lead at neutral pH, they drop out of the stream water column onto the

103

streambed. Iron concentrations were not measured in the streambed

sediments for this study but should be included in future investigations.

Zinc

, fco

lloid

0.0

0.2

0.4

0.6

0.8

1.0

Cop

per,

f col

loid

0.0

0.2

0.4

0.6

0.8

1.0

Colloidal iron (μmol/L)

0 2 4 6 8 10 12 14

Lead

, fco

lloid

0.0

0.2

0.4

0.6

0.8

1.0

Figure 51. Colloidal fraction of copper, zinc, and lead as a function of colloidal iron concentration (μmol L-1). Regression analysis determined r2 values of zero for all metals.

Streambed sediment metal partitioning

We hypothesized that the concentration of metals in sediments as a

fraction of the total amount of metals in the streams would be dominated lead,

followed by copper, and then zinc. The distribution of metals between the

stream water and sediments was calculated for each metal at all sites using a

distribution coefficient, Kd (equation 3 above). The average log-distribution

coefficients of all sampling sites in the watershed were calculated for zinc

(4.37 ± 0.94), copper (4.81 ± 0.71), and lead (5.8 ± 0.83) and support the

104

hypothesis. The large standard deviations of the average Kd values for

copper, zinc, and lead (Table 17) suggest the pH dependence of these

coefficients which has also been described by Stumm and Morgan (1996).

As pH increases, metals show greater affinity for the sediments and less

affinity for the dissolved phase (Figure 52). Once again, the affinity for metals

to bind to surfaces is dominated by lead, less by copper and the least by zinc.

Table 17 Average observed distribution coefficients between the dissolved phase and on the streambed

Metal log Kd (± 1 s.d.) Zinc 4.37 ± 0.94

Copper 4.81 ± 0.71 Lead 5.70 ± 0.83

Distribution coefficients (streamwater and sediments) vs. pH

pH

5.25 5.50 5.75 6.00 6.25 6.50 6.75 7.00 7.25 7.50

log

Kd

1

2

3

4

5

6

7copper lead zinc

Figure 52. Logarithms of the distribution coefficients (Kd, L kg-1) for sediment-water distribution of zinc, copper, and lead for all sampling sites in the watershed as a function of pH.

Benthic macroinvertebrates as biomonitors

Benthic macroinvertebrates have been used extensively to assess

water quality impairment in Rocky Mountain streams (Hare et al. 1991; Cain

et al. 1992; Hare 1992; Clements and Kiffney 1994; Maret et al. 2003; Meyer

105

et al. 2006). Even with the large variability among benthic macroinvertebrates

in their uptake and accumulation of metals, we are still able to observe

elevated metal concentrations in benthic macroinvertebrates in areas

downstream of abandoned mine and mill sites. For example, in James Creek

downstream of Bueno Mountain, zinc and lead concentrations were low in

water and sediments and continued to decline in concentration downstream;

however, metal concentrations in benthic macroinvertebrates remained high

and increased with stream distance until the confluence with Little James

Creek. In this case, as well as others, bioaccumulation of metals in benthic

macroinvertebrates aided in the determination of metal sources in areas

where metal concentrations in the stream water did not. As a note to future

investigators, we advise that samples for sediments and benthic

macroinvertebrates should be taken along the 8 km length of stream from

Sawmill Road to Lickskillet Road. Results from such a study will enable

future researchers to determine the extent of metal loading from California

Gulch.

In many instances where stream water concentrations indicated

decreases or no change in metal loading, metal concentrations in benthic

macroinvertebrates (along with metal concentrations in sediments) increased

by more than 100%. For example, copper and zinc concentrations in the

stream water decreased from above (LH4) to downstream of (LH5) the Big

Five tunnel drainage while lead remained below detection limits at both sites

(Table 18). These samples were both taken on July 8, 2005 when there was

106

not observable flow from the tunnel. However, zinc concentrations in

macroinvertebrates increased by 139%, copper concentrations in

macroinvertebrates increased by 1569%, and lead concentrations in

macroinvertebrates increased by 3050%. We observed similar increases in

sediments. Zinc concentrations in sediments increased by 1200%, the

concentration of copper in sediments increased by 2100%, and the

concentration of lead in sediments increased by 609%. This finding supports

the hypothesis that stream water concentrations would not be indicative of

metal sources while intermittent streams are not flowing.

Better correlations were observed between zinc and copper

concentrations in stream water and benthic macroinvertebrates than with lead

concentrations in stream water and benthic macroinvertebrates. This

correlation was more common for copper and zinc than it was for lead

because of the affinity for lead to adsorb to colloidal materials compared to

copper and zinc, which could make lead less bioavailable to aquatic

organisms. Zinc adsorbs the least to colloidal surfaces and is thus found in

the highest concentrations in the dissolved phase. Dissolved metals are

assimilated into the bodies of benthic macroinvertebrates, which explains why

zinc occurs in the highest concentrations in benthic macroinvertebrates

downstream of abandoned mine and mill sites relative to copper and lead.

High concentrations of zinc in all media, including waste rock piles is due to

its abundance in minerals throughout the watershed.

107

Table 18 Increases in concentrations of copper, zinc and lead in stream water, benthic macroinvertebrates, and sediments from above to downstream of the Big Five tunnel drainage. These sites were sampled on July 8, 2005, when the drainage was not flowing into Lefthand Creek. Negative values indicate decreases in concentrations.

Stream water (ug L-1) Macroinvertebrate

(mg kg-1) Streambed sediments

(mg kg-1)

Metal UP DOW

N %

Increase UP DOWN%

Increase UP DOWN %

Increase Zinc 6.1 3.5 -42.6% 467 1118 139.4% 194 2361 1117.0%

Copper 3.6 1.5 -58.3% 28.4 474 1569.0% 112 2460 2096.4% Lead 0.05 0.05 0.0% 0.6 18.9 3050.0% 172 1220 609.3%

Dissolved organic carbon and metal speciation

Metals are known to bind to organic matter and their total

concentrations in many waters have been correlated with the concentration of

dissolved organic carbon (DOC) (McKnight et al. 1992; Church et al. 1997;

Prusha and Clements 2004). Metals that bind to DOC are less bioavailable

and because of this we expected to see a decrease in metal accumulation in

macroinvertebrates as DOC increased. High DOC levels can inhibit metals

from bioaccumulating in benthic macroinvertebrates (Prusha and Clements

2004). This process is most effective for metals with a high affinity to bind to

organic matter.

Figure 53 shows the concentration of DOC compared to the metal

concentrations in benthic macroinvertebrates for all of the sampling sites. A

negative correlation between macroinvertebrate metal concentrations and

DOC was expected for all metals and in the order Pb > Cu > Zn due to their

affinity to adsorb to organic matter. However, we did not see such correlation

among the pooled data (Figure 53). Negative correlations were found

108

between benthic macroinvertebrates and DOC for all investigated metals in

James Creek and for zinc and lead in Little James Creek, however these

correlations were not significant (r2 values < 0.15). DOC becomes less

effective at controlling metal bioaccumulation in benthic macroinvertebrates at

higher metal concentrations. When available sites on organic matter become

saturated with metals, leaving no available sites, free metals have a greater

chance to bioaccumulate in the bodies of benthic macroinvertebrates.

We further investigated the role of DOC in metal speciation and plotted

the colloidal fractions of metals vs. DOC (Figure 54). If the colloidal fractions

are dominated by organic matter rather than iron hydroxide particulates, then

we should see a positive relationship between colloidal fractions and DOC.

As with the previous regression, r2 values were low for all metals indicating

weak correlations (zinc (0.14), copper (0.06), and lead (0.065) and inverse

relationships. The non-correlations observed may indicate the dependence of

metal speciation on the fractionation of DOC throughout the watershed.

McKnight et al. (1992) observed that the fractionation of DOC (%fulvic,

%humic, and %hydrophilic acids) can be a significant aspect of metal sorption

to DOC in a stream system. Future studies should include determination of

DOC fractions to investigate this hypothesis.

109

DOC (mg/L)1.25 1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50

Cu

in ti

ssue

( μg

g-1)

0

200

400

600

800Cu

Pb in

tiss

ue ( μ

g g-1

)

0

5

10

15

20

25

30

Pb

Zn in

tiss

ue ( μ

g g-1

)

0

500

1000

1500

2000

2500

3000

3500

Zn

r ² = 0.134

r ² = 0.303

r ² = 5.57e-3

Figure 53. Concentration of metals in benthic macroinvertebrates as a function of concentration of dissolved organic carbon (DOC) for all sampling sites.

110

DOC

1.5 2.0 2.5 3.0 3.5 4.0 4.5

f collo

id

0.0

0.2

0.4

0.6

0.8

1.0

copperleadzinc

Figure 54. The colloidal fraction of metals (fcolloid) as a function of DOC show weak correlations (zinc (0.14), copper (0.06), and lead (0.065).

In the future, benthic macroinvertebrate collections should include the

collection of two species from separate feeding guilds in order to decrease

variability among samples. This is possible if further investigations into the

abundance of metal tolerant species can be conducted to find a target

species. Future methods of collection could possibly include harvesting a

single species from background sites and placing them in encasements

throughout the study area. The amount of time the target species should

remain in the encasements shall rely on the lifespan and time of molting of

the species chosen. Researchers indicate that care must be taken when

using pooled communities to assess metal inputs to streams (Clements and

Kiffney 1994). The feeding guild of the benthic macroinvertebrates determines

their sensitivity to metals in the stream water column and the sediments. The

benthic macroinvertebrates used at each site varied in community diversity.

111

Whole communities were digested to get a representative sample at each

site. The nature of this type of collection leads to various questions pertaining

to the accumulation of metals by individuals. Some individual fly larvae filter

feed through the sediments and detritus on rocks while others spin webs and

capture food moving downstream in the form of organic matter and,

sometimes, other larvae. We can also pose questions as to the extent of

metal resistance among individuals. The tolerance of these individuals

depends on their success in passing metals through the body.

Recommendations for remediation

We expected sediment and macroinvertebrate metal concentrations to

lead us to new sources of metal inputs to the streams that flow only

intermittently. We did not find any new sources of metal loading within the

watershed, but we were able to confirm previous recommendations and

reprioritize a few sites. Along Lefthand Creek, Wood et al. (2004) rated the

Dew Drop mine as medium priority because of copper and zinc

concentrations and pH. This ranking is supported by the elutriation test

results and the increases in metals in benthic macroinvertebrates and

sediments downstream of the site. The Big Five tunnel received a high

priority ranking from Wood et al. (2004) based on pH, zinc, copper and lead.

This study supports the ranking with the high concentrations of copper,

lead and zinc downstream of the Big Five tunnel in benthic

macroinvertebrates, sediments, and stream water. However, the leaching

capacity of the sediments from the two waste rock piles at Big Five was low

112

as shown by elutriation tests. The Slide Mine was given a medium priority

ranking by Wood et al. due to pH, zinc and copper. Based upon increases in

concentrations of zinc and lead downstream of this site in benthic

macroinvertebrates (also the highest concentrations in the creek among

benthic macroinvertebrates), we would change the prioritization of this site to

high. Current efforts are underway to remediate the Slide Mine as a voluntary

cleanup program (VCUP) site.

Along James Creek, the Bueno Mountain Mine was given a high

priority ranking based upon Al, Mn, Zn, Cu and Pb by Wood et al. (2004).

Concentrations in benthic macroinvertebrates and sediments support this

ranking with escalating increases of Copper, Zn and Pb for 8 km downstream

of known metal inputs. It is possible that these sources may also emanate

from upstream sources, such as the Fairday Mine or John Jay Mine.

The Bueno Mountain gully along Little James Creek also received a high

priority ranking based upon the same metals and pH. This area, including the

“streamside tailings,” was ranked as high priority by Wood et al. (2004).

These are supported by the lack of aquatic life, low pH, and high

concentrations of copper, zinc and, lead in the sediments. The most

problematic metal to aquatic life in this area is attributed to lead. The

Evening Star Mine, which was referred to as the “un-named” mine between

0.37 – 0.64 km by Wood et al. (2004), was assigned a medium priority

ranking due to Al, Cu, and Pb loading. Streambed sediment and benthic

macroinvertebrate metal concentrations did not confirm lead loadings within

113

the vicinity of the Evening Star Mine inflows, but we did detect elevated

copper and zinc concentrations in benthic macroinvertebrates in this area.

Additionally, the sediments from the Evening Star Mine’s waste rock elutriated

the highest levels of zinc of all tailings piles in the watershed. Copper and

lead concentrations in the Evening Star waste rock pile were ranked in the top

three of all waste rock piles. We advise maintaining the medium priority

ranking of Wood et al. (2004), but we recommend further investigations into

the transport of metals from this site. The Argo Mine gully was given a

medium priority ranking by Wood et al. (2004) due to Al and Cu, but this was

found to be inappropriate from the findings within this study. Concentrations

of copper and zinc in sediments just downstream of the gully were highest

among all samples taken in the creek and benthic macroinvertebrates

exhibited the highest lead and copper concentrations. The Argo Mine waste

rock pile exhibited the second highest elutriations of copper and lead and the

sixth-highest zinc concentration. We would recommend raising the priority of

the Argo Mine gully from medium to high. These rating changes were

changed without regards for size of waste rock piles or their flow paths.

However, the concentrations measured within the streambed sediments and

macroinvertebrates (which represent long term accumulation) and their

proximity to the waste rock piles, give evidence that these changes should be

considered.

114

Summary and Conclusions

Comparisons of stream water metal concentrations to the Colorado

Department of Public Health and the Environments aquatic life standards

provided a basis for the effects on the stream water ecosystem and provided

insight into the relationship between metal bioavailability and stream water

hardness. We were able to show correlations between benthic

macroinvertebrates and sediments in a majority of the samples taken in the

watershed. Besides the correlation between lead in stream water and

sediments, we did not find correlations between stream water and benthic

macroinvertebrates or between stream water and sediments for any of the

metals. Analysis of copper, zinc and lead concentrations in sediments and

benthic macroinvertebrates in relation to waste rock pile locations reconfirmed

known sources of metal inputs. Well documented metal speciation trends for

zinc, copper, and, lead were supported between stream water and sediments

and between dissolved and colloidal metals. They supported the binding

sequence; lead > copper > zinc. Correlations between colloidal metal

fractions and concentrations of iron were not supported with the available field

data. Finally, with the available dataset, the hypothesis which stated that

dissolved organic carbon plays a role in the metal distributions between

water, sediments and benthic macroinvertebrates was not supported.

115

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121

APPENDIX A

Sampling Dates

Table A. 1 Lefthand Creek water, benthic macroinvertebrate and sediment field sampling dates.

sample name GPS site name

water & macroinvertebrate

sampling date sediment sampling

date

LH1 5560A-1 7/6/2005 10/3/2005

LH2 5560A-6 7/22/2005 10/3/2005

LH3 5560A-8 7/22/2005 10/3/2005

LH4 5560A-13 7/8/2005 10/3/2005

LH5 5560A-14 7/8/2005 10/3/2005

LH6 5560A-17 7/8/2005 10/17/2005

LH7 5560A-21 7/8/2005 10/17/2005

LH-PU 5560A-PU 7/8/2005* 10/17/2005

LH-IN 5560A-IN 7/6/2005* 10/10/2005

LH8 5560A-56 7/6/2005 10/10/2005

LH9 5560A-95-1 6/20/2005 10/1/2005

LH10 5560A-96 7/6/2005 10/1/2005

LH11 5560A-101 7/2/2005 10/1/2005

LH-SL 5560A-SL1 7/2/2005* 10/1/2005

LH12 5560A-103 7/2/2005 10/1/2005

LH13 5560A-113 6/20/2005 10/1/2005

LH14 5560A-123 6/29/2005 10/1/2005

LH15 5560A-129 6/18/2005 10/1/2005

LH16 5560A-136-2 6/29/2005 10/1/2005

LH17 5560A-127 6/15/2005 10/1/2005

LH18 5560A-171 6/29/2005 10/1/2005

LH19 5560A-184 6/29/2005 10/27/2005 * Creek/tributary was dry upon sampling.

122

Table A. 2 James Creek water, benthic macroinvertebrate and sediment sampling dates

sample name GPS site name

water & macroinvertebrate

sampling date sediment

sampling date

J1 5561A-T1 7/25/2005 10/3/2005

J2 5561A-T2 7/23/2005 10/4/2005

J3 5561A-T3 8/1/2005 10/8/2005

J4 5561A-T4 8/1/2005 10/8/2005

J-FD 5561A-FD 8/1/2005 10/8/2005

J5 5561A-JOHN 8/1/2005 10/8/2005

J6 5561A-10 8/1/2005 10/8/2005

J7 5561A-16 7/23/2005 10/8/2005

J8 5561A-28 7/13/2005 10/17/2005

J9 5561A-30-582 7/13/2005 10/4/2005

J10 5561A-55 7/1/2005 10/4/2005

J-CU 5561A-CU 7/2/2005 10/4/2005

J11 5561A-52 7/1/2005 10/4/2005

J12 5561A-53 7/1/2005 10/4/2005

J-CG 5561A-CG 7/1/05* 10/4/2005

J13 5561A-61 7/1/2005 10/4/2005

J14 5561A-62 6/30/2005 10/1/2005

* Creek/tributary was dry upon sampling.

123

Table A. 3 Little James Creek water, benthic macroinvertebrate and sediment sampling dates.

sample name GPS site name

water-macroinvertebrate

sampling date sediment

sampling date

LJ1 5562A-0 7/18/2005 9/24/2005*

LJ2 5562A-1 7/18/2005 9/24/2005*

LJ3 5562A-6 7/18/2005 9/24/2005

LJ4 5562A-8 7/18/2005 9/24/2005

LJ5 5562A-10 7/18/2005 9/24/2005

LJ6 5562A-14 7/18/2005 9/24/2005

LJ7 5562A-16 7/18/2005 9/24/2005*

LJ8 5562A-18-1 7/13/2005 9/24/2005*

LJ9 5562A-21 6/30/2005 9/24/2005

LJ10 5562A-28 7/13/2005 9/24/2005*

LJ11 5562A-32 7/13/2005 9/24/2005*

LJ12 5562A-35 7/13/2005 9/24/2005

LJ13 5562A-38 6/22/2005 9/24/2005

*Creek/tributary was dry upon sampling.

124

Water quality data

Table A. 4 Lefthand Creek water quality data - pH, specific conductance, and temperature

site name GPS Site

Name sample date pH

specific conductance

(μS cm-1) temperature

(ºC)

LH1 5560A-1 7/6/05 6.7 30.2 13.5

LH2 5560A-6 7/22/05 7.0 47.0 14.6

LH3 5560A-8 7/22/05 7.0 45.1 14.5

LH4 5560A-13 7/8/05 6.8 25.2 11.9

LH5 5560A-14 7/8/05 6.7 30.8 11.6

LH6 5560A-17 7/8/05 6.7 29.7 11.5

LH7 5560A-21 7/8/05 6.5 37.7 11.2

LH8 5560A-56 7/6/05 6.7 47.6 12.8

LH9 5560A-95-1 6/20/05 6.8 61.2 12.3

LH10 5560A-96 7/6/05 6.9 63.9 10.5

LH11 5560A-101 7/2/05 7.2 63.5 12.0

LH12 5560A-103 7/2/05 7.1 71.8 11.2

LH13 5560A-113 6/20/05 7.0 77.0 10.5

LH14 5560A-123 6/29/05 7.0 12.1 12.6

LH15 5560A-129 6/18/05 7.3 115 11.3

LH16 5560A-136-2 6/29/05 6.7 41.1 11.7

LH17 5560A-127 6/15/05 6.9 61.6 11.5

LH18 5560A-171 6/29/05 6.9 42.6 11.3

LH19 5560A-184 6/29/05 6.8 47.6 11.0

125

Table A. 5 Lefthand Creek water quality data - Dissolved Organic Carbon (DOC)

site name GPS site name

distance downstream

(km) DOC, ppm st dev (ppm) RSD %

LH1 5560A-1 0 2.81 0.031 1.1

LH2 5560A-6 0.539 2.81 0.00957 0.34

LH3 5560A-8 0.67 2.8 0.0707 0.25

LH4 5560A-13 1.302 3.25 0.126 0.39

LH5 5560A-14 1.311 3.23 0.005 0.15

LH6 5560A-17 1.5 3.18 0.00816 0.26

LH7 5560A-21 1.788 3.12 0.005 0.16

LH8 5560A-56 2.514 2.59 0.0171 0.66

LH9 5560A-95-1 11.429 2.88 0 0

LH10 5560A-96 11.47 2.85 0.005 0.18

LH11 5560A-101 12.435 2.8 0.00957 0.34

LH12 5560A-103 12.675 2.78 0.01 0.36

LH13 5560A-113 16 2.78 0.0171 0.61

LH14 5560A-123 18.317 2.7 0.015 0.56

LH15 5560A-129 19.482 2.71 0 0

LH16 5560A-136-2 21.702 1.97 0.005 0.25

LH17 5560A-127 22.493 1.94 0 0

LH18 5560A-171 26.391 2 0.00957 0.48

LH19 5560A-184 30.508 2.04 0.005 0.24

CONTROL - - 0.739 0.002 0.27

MQ - Blank - - 0.764 0.0416 5.45

Field Blank - - 1.06 0.0212 1.99

126

Table A. 6 James Creek water quality data - pH, specific conductance, and temperature

site name

GPS site name

sample date

specific conductance (μS cm-1)

temperature (ºC) pH

J1 5561A-T1 7/25/05 6.4 20.5 12.4

J2 5561A-T2 7/23/05 6.9 22.0 16.3

J3 5561A-T3 8/1/05 6.4 20.8 15.9

J4 5561A-T4 8/1/05 6.3 23.6 15.3

J5 5561A-JOHN 8/1/05 6.4 24.8 14.4

J6 5561A-10 8/1/05 6.4 24.5 14.4

J7 5561A-16 7/23/05 6.6 23.5 16.7

J8 5561A-28 7/13/05 6.4 23.0 15.3

J9 5561A-30-582 7/13/05 6.2 25.1 14.2

J10 5561A-55 7/1/05 6.6 27.9 13.0

J11 5561A-52 7/1/05 6.7 31.9 12.8

J12 5561A-53 7/1/05 6.4 30.5 11.9

J13 5561A-61 7/1/05 6.3 33.5 10.5

J14 5561A-62 6/30/05 6.1 33.6 10.0

127

Table A. 7 James Creek water quality data - Dissolved Organic Carbon (DOC) site name

GPS site name

distance downstream

(km) DOC, ppm st dev (ppm) RSD %

J1 5561A-T1 0.00 1.6 0 0

J2 5561A-T2 1.20 1.67 0 0

J3 5561A-T3 7.80 1.77 0 0

J4 5561A-T4 8.36 1.85 0.0141 0.76

J5 5561A-JOHN 9.00 2.2 0.0707 0.32

J6 5561A-10 10.18 2.08 0.0707 0.34

J7 5561A-16 10.18 2.82 0.00707 0.25

J8 5561A-28 14.00 1.99 0.00957 0.48

J9 5561A-30-582 14.42 1.78 0 0

J10 5561A-55 16.69 1.81 0.005 0.28

J11 5561A-52 18.21 1.82 0 0

J12 5561A-53 18.29

J13 5561A-61 19.04 1.76 0.0129 0.74

J14 5561A-62 20.42 1.87 0.005 0.27

CONTROL - - 0.739 0.002 0.27% MQ - Blank - - 0.764 0.0416 5.45% Field Blank - - 1.06 0.0212 1.99

128

Table A. 8 Little James Creek water quality data - pH, specific conductance, and temperature

site name GPS site name sample

date pH

specific conductance

(μS cm-1) temperature

(ºC)

LJ1 5562A-0 7/18/05 6.7 209 13.1

LJ2 5562A-1 7/18/05 6.2 200 16.5

LJ3 5562A-6 7/18/05 6.7 181 19.8

LJ4 5562A-8 7/18/05 6.5 201 17.3

LJ5 5562A-10 7/18/05 5.9 187 13.5

LJ6 5562A-14 7/18/05 5.4 1620 12.9

LJ7 5562A-16 7/18/05 5.6 1360 13.4

LJ8 5562A-18-1 7/13/05 5.7 1100 20.8

LJ9 5562A-21 6/30/05 6.1 481 16.8

LJ10 5562A-28 7/13/05 5.7 640 17.0

LJ11 5562A-32 7/13/05 6.1 824 20.5

LJ12 5562A-35 7/13/05 6.2 703 19.0

LJ13 5562A-38 6/22/05 6.3 507 16.8

129

Table A. 9 Little James Creek water quality data - Dissolved Organic Carbon (DOC)

sample name

GPS site name

distance downstream

(km) DOC, ppm st dev (ppm) RSD %

LJ1 5562A-0 0 3.36 0.006 0.15

LJ2 5562A-1 0.25 3.76 0.00707 0.19

LJ3 5562A-6 0.9 3.68 0.00957 0.26

LJ4 5562A-8 0.92 4.36 0.0141 0.32

LJ5 5562A-10 1.14 3.57 0 0

LJ6 5562A-14 1.43 2.28 0.0707 0.31

LJ7 5562A-16 1.59 2.78 0.041 0.51

LJ8 5562A-18-1 1.8 1.68 0.0212 1.27

LJ9 5562A-21 1.87 2.86 0.0707 0.25

LJ10 5562A-28 2.37 2.86 0.005 0.17

LJ11 5562A-32 2.49 3.04 0.0141 0.47

LJ12 5562A-35 2.6 3.16 0.007 0.22

LJ13 5562A-38 2.89 3.08 0.0212 0.69

CONTROL - - 0.739 0.002 0.27% MQ - Blank - - 0.764 0.0416 5.45% Field Blank - - 1.06 0.0212 1.99

NC, Not Collected due to lack of water at site

130

APPENDIX B

Metal concentrations in water

Table B. 1 Lefthand Creek Cu, Pb, and Zn concentrations in water

site name

GPS Site Name

total Cu

(μg L-1)

dissolved Cu

(μg L-1)

total Pb

(μg L-

1

dissolved Pb

(μg L-1)

total Zn

(μg L-

1

dissolved Zn

(μg L-1)

LH1 5560A-1 5* 5.8* BDL** 0.29** BDL 5.8

LH2 5560A-6 1* 2.4* BDL** 0.46** 2.9 2.9

LH3 5560A-8 0.86 1.2 BDL** BDL** 4.9 BDL

LH4 5560A-13 1 3.6 BDL** BDL** 5.4 6.1

LH5 5560A-14 1.2 1.5 0.41 BDL** 5.9 3.5

LH6 5560A-17 20.6* 18.8* 1.4 0.43** 74 71.7

LH7 5560A-21 28* 24* .65** 0.82** 106 95.3

LH8 5560A-56 21.7* 18* 0.61** 0.6** 80 69.3

LH9 5560A-95-1 7.7* 6.6* 0.88** 0.31** 30.4 25.8

LH10a 5560A-96a 8.1 5.3* 0.93 BDL** 31.4 23.3

LH10b 5560A-96b 23 24 BDL BDL 33 28

LH11 5560A-101 7.1* 15 BDL 0.45 32.2 35

LH12 5560A-103 7.5* 7.7* BDL 4.7 33 44.5

LH13 5560A-113 7.2* 6.3* 2.1 BDL 32.9 26.4

LH14 5560A-123 7 5.1 1.7 BDL 31.3 23.5

LH15 5560A-129 7.3* 5.2* 0.86 BDL 29.6 23.2

LH16 5560A-127 1.9* 1.9 1.6* BDL 8.1 7.2

LH17 5560A-136-2 1.6 2 1.4* 0.25** 7.6 5.4

LH18 5560A-171 3 2.9 1.3* BDL 9.1 5.4

LH19 5560A-184 2.7 2.1 0.61* BDL 8.1 5.3

FB FIELD_BLANK 2.7 2.1 BDL BDL BDL 2.8*

BDL, Below Detection Limit * Analyzed by ICP-MS, Detection Limit for Copper, 2 μg L-1

** Analyzed by ICP-MS, Detection Limit for Lead, 1 μg L-1

131

Table B. 2 James Creek Cu, Pb, and Zn Concentrations in Water

site name

GPS site name

total Cu

(μg L-

1)

dissolved Cu

(μg L-1)

total Pb (μg

L-1)

dissolved Pb

(μg L-1)

total Zn

(μg L-

1)

dissolved Zn

(μg L-1()

J1 5561A-T1 0.91 BDL* BDL BDL** 2.9 2.8

J2 5561A-T2 3.1* 1.3 0.68** 38** BDL 4.9

J3 5561A-T3 3.8* 1.1 BDL** BDL** BDL 4.5

J4 5561A-T4 1.4* 1.2 1.4 BDL** BDL BDL

J5 5561A-J0HN 1.7* 1.4 BDL** BDL** 3.1 3.5

J6 5561A-10 2.6* 1.4 0.78** 0.6** 2.7 5.2

J7 5561A-16 5.9 1.5 BDL** 0.52** 3.7 8.8

J8a 5561A-28a 1.2 1.6 0.54** BDL** 3 6.3

J8b 5561A-28b 14 13 BDL BDL 3 4

J9 5561A-30-582 1.7* 2.1 0.73** BDL** 2.9 4.7

J10 5561A-55 1.4* 2.4* 0.56** BDL** 4.8 3.6

J11 5561A-52 5.6* 2.1* 0.66** BDL** 4.8 8.1

J12 5561A-53 1.5* 2* 0.36** BDL 4.7 4.2

J13a 5561A-61a 6* 1.7* 0.72** BDL** 5.3 7.4

J13b 5561A-61b 16 12 BDL BDL 17 7

J14 5561A-62 1.5* 1.9* 0.61** BDL** 5.9 4.7

FB FIELD_BLANK 5* 1.5* BDL BDL BDL 2.8* BDL, Below Detection Limit * Analyzed by ICP-MS, Detection Limit for Copper, 2 μg L-1

** Analyzed by ICP-MS, Detection Limit for Lead, 1 μg L-1

132

Table B. 3 Little James Creek Cu, Pb, and Zn Concentrations in Water

site name GPS Site Name

total Cu (μg L-1)

dissolved Cu

(μg L-1)

total Pb

(μg L-

1)

dissolved Pb

(μg L-1)

total Zn

(μg L-1)

dissolved Zn

(μg L-1)

LJ1 5562A-0 1.4* 1.7* BDL** BDL** BDL BDL

LJ2 5562A-1 48.1* 46.4* 1** BDL** 112 117

LJ3 5562A-6 164 53.3* 6.6 0.59** 322 278

LJ4 5562A-8 20* 17.6* 1.1** 0.84** 89.4 95.4

LJ5a 5562A-10a 41 39.8 61.3 51.6 215 219

LJ5b 5562A-10b 71 --- 106 --- 256 ---

LJ6 5562A-14 51.7 46.3 38.6 26.5 1100 1100

LJ7 5562A-16 68.9 38.8 77.7 24.1 1440 1040

LJ8 5562A-18-1 57.8 49.1 69.7 40.6 1260 1250

LJ9 5562A-21 29.2 29.8 5.3 5.8 717 737

LJ10 5562A-28 79 77.7 10.8 9.6 603 615

LJ11 5562A-32 28 24.9* 4.6 2.1** 543 567

LJ12 5562A-35 14.2* 7* 1.7** 0.35** 420 415

LJ13 5562A-38 8.8* 5* 0.88** 0.44** 360 353

FB FIELD BLANK 1.4* 1.7* BDL** BDL** BDL BDL

BDL, Below Detection Limit * Analyzed by ICP-MS, Detection Limit for Copper, 2 ug L-1

** Analyzed by ICP-MS, Detection Limit for Lead, 1 ug L-1

133

APPENDIX C

Metal concentrations in benthic macroinvertebrates

Table C. 1 Lefthand Creek concentrations of Cu, Zn, and Pb in Benthic macroinvertebrate Digest Solution as Reported by EPA Region VIII Laboratory

site name GPS site name

macroinvertebrate dry wt (g)

Cu (μg L-1)

Pb (ug L-1)

Zn (ug L-1)

LH1 5560A-1 0.602 54.1* 0.76* 466

LH2 5560A-6 0.567 70.6* 0.9* 770

LH3 5560A-8 0.432 56.6 1.5 756

LH4 5562A-13 0.92 52.2* 1.1* 859

LH5 5560A-14 0.678 813 18.1 1810

LH6 5560A-17 0.114 108 4.3 255

LH7 5560A-21 0.0475 63.5 2.6 186

LH8 5560A-56 0.842 483 9.9 3710

LH9 5560A-95-1 0.409 179 5.7 1950

LH10a 5560A-96a 0.531 164 4.2 2269

LH10b 5560A-96b 0.630 196 3.6 2861

LH11 5560A-101 1.62 394 14.7 5320

LH12 5560A-103 0.722 292 15.1 4220

LH13 5560A-113 0.162 55.4 5.2 748

LH14 5560A-123 0.798 322 14.2 4930

LH15 5560A-129 0.622 181 15 2480

LH16 5560A-136-2 0.914 206 15.1 3560

LH17 5560A-127 0.698 111 12.1 1890

LH18 5560A-171 1 136 16.4 2030

LH19 5560A-184 1.011 120 10.1 1670

LB LAB_BLANK - BDL BDL BDL BDL, Below Detection Limit *Analyzed by ICP-MS

134

Table C. 2 Lefthand Creek Cu, Zn, and Pb Concentrations in Benthic macroinvertebrates Calculated from values in Table C.1

site name

GPS site name

macroinvertebrate

dry wt (g) Cu

(ug g-1 dry wt) Pb

(ug g-1 dry wt)

Zn (ug g-1 dry

wt)

LH1 5560A-1 0.602 44.9* 0.6* 387

LH2 5560A-6 0.567 62.3* 0.8* 679

LH3 5560A-8 0.432 65.5 1.7 875

LH4 5562A-13 0.92 28.4* 0.6* 467

LH5 5560A-14 0.678 600 13.3 1335

LH6 5560A-17 0.114 474 18.9 1118

LH7 5560A-21 0.0475 668 27.4 1958

LH8 5560A-56 0.842 287 5.9 2203

LH9 5560A-95-1 0.409 219 7.0 2384

LH10a 5560A-96a 0.531 164 4.2 2269

LH10b 5560A-96b 0.630 156 2.90 2271

LH11 5560A-101 1.62 122 4.54 1642

LH12 5560A-103 0.722 202 10.5 2922

LH13 5560A-113 0.162 171 16.0 2309

LH14 5560A-123 0.798 202 8.90 3089

LH15 5560A-129 0.622 145 12 1994

LH16 5560A-136-2 0.914 113 8.26 1947

LH17 5560A-127 0.698 79.5 8.67 1354

LH18 5560A-171 1 68.0 8.20 1015

LH19 5560A-184 1.011 59.3 5.00 826

LB LAB_BLANK - BDL BDL BDL

BDL, Below Detection Limit *Analyzed by ICP-MS

135

Table C. 3 James Creek concentrations of Cu, Zn, and Pb in Benthic macroinvertebrate Digest Solution as Reported by EPA Region VIII Laboratory

site name GPS site name

macroinvertebrate dry weight (g)

Cu (ug L-1)

Pb (ug L-1)

Zn (ug L-

1)

J1 5561A-T1 0.646 43.4 BDL 324

J2 5561A-T2 0.695 48.4 BDL 477

J3 5561A-T3 0.281 47.2 2.2 252

J4 5561A-T4 0.56 72.9 1.5 482

J5 5561A-JOHN 0.466 58.1 BDL 301

J6 5561A-10 0.461 54.9 BDL 337

J7 5561A-16 0.798 ---* ---* ---*

J8a 5561A-28a 0.501 55.5 BDL 622

J8b 5561A-28b 0.336 39.6 BDL 455

J9 5561A-30-582 0.507 58.1 1.6 771

J10 5561A-55 0.637 83.2 6.1 1250

J11 5561A-52 0.745 93.1 7.4 1630

J12 5561A-53 0.735 126 6.7 2020

J13a 5561A-61a 0.522 72.6 6.1 1230

J13b 5561A-61b 0.544 79.0 8.0 1430

J14 5561A-62 0.561 83 9.9 1280

LB LAB_BLANK - BDL BDL BDL BDL, Below Detection Limits *Not determined due to laboratory digestion failure

136

Table C. 4 James Creek Cu, Zn, and Pb Concentrations in Benthic macroinvertebrates Calculated from values in Table C.3

site name

GPS site name

macroinvertebrate dry weight (g)

Cu (ug g-1 dry wt)

Pb (ug g-1 dry wt)

Zn (ug g-1 dry wt)

J1 5561A-T1 0.646 33.6 BDL 250.8

J2 5561A-T2 0.695 34.8 BDL 343.2

J3 5561A-T3 0.281 84.0 3.9 448.4

J4 5561A-T4 0.56 65.1 1.3 430.4

J5 5561A-JOHN 0.466 62.3 BDL 323.0

J6 5561A-10 0.461 59.5 BDL 365.5

J7 5561A-16 0.589 36.8 -- --

J8a 5561A-28a 0.501 55.4 BDL 620.8

J8b 5561A-28b 0.336 58.9 BDL 677.1

J9 5561A-30-582 0.507 57.3 1.6 760.4

J10 5561A-55 0.637 65.3 4.8 981.2

J11 5561A-52 0.745 62.5 5.0 1094.0

J12 5561A-53 0.735 85.7 4.6 1374.1

J13a 5561A-61a 0.522 69.5 5.8 1178.2

J13b 5561A-61b 0.544 72.6 7.4 1314.3

J14 5561A-62 0.561 74.0 8.8 1140.8

LB LAB_BLANK - BDL BDL BDL

BDL, Below Detection Limits *Not determined due laboratory digestion failure

137

Table C. 5 Little James Creek concentrations of Cu, Zn, and Pb in Benthic macroinvertebrate Digest Solution as Reported by EPA Region VIII Laboratory

site name

GPS site name

macroinvertebrate

dry weight (g) Cu (ug L-1) Pb (ug L-1) Zn (ug L-1)

LJ1 5562A-0 0.973 27.5* 21.7* 267

LJ2 5562A-1 0.786 185 30.1 2540

LJ3 5562A-6 1.222 410 58 388

LJ4 5562A-8 0.869 168 30.6 288

LJ5a 5562A-10a 0.786 257 450 330

LJ5b 5562A-10b 1.103 316 402 359

LJ6 5562A-14 NMP NMP NMP NMP

LJ7 5562A-16 NMP NMP NMP NMP

LJ8 5562A-18-1 NMP NMP NMP NMP

LJ9 5562A-21 0.773 87.9 320 209

LJ10 5562A-28 NMP NMP NMP NMP

LJ11 5562A-32 NMP NMP NMP NMP

LJ12 5562A-35 NMP NMP NMP NMP

LJ13 5562A-38 NMP NMP NMP NMP

LB LAB_BLANK - BDL BDL BDL BDL, Below Detection Limit NMP, No Benthic macroinvertebrates Present * Analyzed by ICP-MS

138

Table C. 6 Little James Creek Cu, Zn, and Pb Concentrations in Benthic macroinvertebrates Calculated from values in Table C.5

site name

GPS site name

macroinvertebrate dry weight (g)

Cu (ug g-1 dry wt)

Pb (ug g-1 dry wt)

Zn (ug g-1

dry wt)

LJ1 5562A-0 0.973 14.1* 11.2* 137

LJ2 5562A-1 0.786 118 19.1 1616

LJ3 5562A-6 1.222 168 23.7 159

LJ4 5562A-8 0.869 96.7 17.6 166

LJ5a 5562A-10a 0.786 163 286 210

LJ5b 5562A-10b 1.103 143 182 163

LJ6 5562A-14 NMP NMP NMP NMP

LJ7 5562A-16 NMP NMP NMP NMP

LJ8 5562A-18-1 NMP NMP NMP NMP

LJ9 5562A-21 0.773 56.9 207 135

LJ10 5562A-28 NMP NMP NMP NMP

LJ11 5562A-32 NMP NMP NMP NMP

LJ12 5562A-35 NMP NMP NMP NMP

LJ13 5562A-38 NMP NMP NMP NMP

LB LAB_BLANK --- BDL BDL BDL

BDL, Below Detection Limit NMP, No Benthic macroinvertebrates Present *Analyzed by ICP-MS

139

APPENDIX D

Metal concentrations in bed sediments

Table D. 1 Lefthand Creek Metal Concentrations in Sediment Digest Solution Riverbed Sediments as Reported by University of Colorado – LEGS laboratory

site name GPS site name sediment dry wt.

(g) Cu

(mg L-1) Pb

(mg L-1) Zn

(mg L-1)

LH1 5560A-1 1.009 0.628 1.33 1.77

LH2 5560A-6 1.014 1.83 2.38 3.95

LH3 5560A-8 1 7.09 5.75 12.7

LH4 5562A-13 1.006 5.58 8.60 9.70

LH5 5560A-14 0.761 72.3 18.3 28.8

LH6 5560A-17 1.013 124 61.2 118

LH7 5560A-21 0.753 183 97.6 181

LH8 5560A-56 1.066 35.1 13.5 50.0

LH9 5560A-95-1 0.981 11.8 6.2 24.6

LH10 5560A-96 1.007 9.59 6.72 20.2

LH11 5560A-101 1.088 6.84 6.39 16.2

LHSL 5560A-SL 1.067 6.04 17.9 34.5

LH12 5560A-103 1.052 5.57 7.54 21.3

LH13 5560A-113 1.031 3.77 6.35 17.9

LH14 5560A-123 0.733 2.44 4.11 12.2

LH15 5560A-129 1.02 4.61 4.31 18.5

LH16 5560A-136-2 1.0132 2.70 4.84 11.8

LH17 5560A-127 1.005 3.35 7.03 10.6

LH18A 5560A-171A 0.985 3.01 5.50 10.1

LH18B 5560A-171B 1.073 3.18 5.85 10.3

LH18C 5560A-171C 1.13 3.34 6.25 11.1

LH19 5560A-184 1.051 3.61 6.97 10.7

SEDB1 LAB_BLANK 1 - 0.02 0.00 0.024

SEDB2 LAB_BLANK 2 - 0.00 0.00 0.011

SEDB3 LAB_BLANK 3 - 0.02 0.05 0.048

140

Table D. 2 Lefthand Creek Cu, Zn, and Pb Concentrations in Riverbed Sediments Calculated from Values in Table D.1

site name GPS site name sediment dry wt

(g) Cu

(mg kg-1) Pb

(mg kg-1) Zn

(mg kg-1)

LH1 5560A-1 1.009 12.3 26.3 35.0

LH2 5560A-6 1.014 36.2 47.0 78.1

LH3 5560A-8 1 143 116 256

LH4 5562A-13 1.006 112 172 194

LH5 5560A-14 0.761 1918 486 764

LH6 5560A-17 1.013 2460 1220 2361

LH7 5560A-21 0.753 4910 2620 4870

LH8 5560A-56 1.066 665 255 946

LH9 5560A-95-1 0.981 243 127 507

LH10 5560A-96 1.007 192 134 404

LH11 5560A-101 1.088 127 118 301

LHSL 5560A-SL 1.067 114 339 652

LH12 5560A-103 1.052 107 144 408

LH13 5560A-113 1.031 73.6 124 350

LH14 5560A-123 0.733 66.9 113 334

LH15 5560A-129 1.02 91.0 85.0 366

LH16 5560A-136-2 1.0132 53.6 96.1 234

LH17 5560A-127 1.005 67.0 141 213

LH18A 5560A-171A 0.985 61.4 112 206

LH18B 5560A-171B 1.073 59.7 110 193

LH18C 5560A-171C 1.13 59.6 111 197

LH19 5560A-184 1.051 69.1 134 205

141

Table D. 3 James Creek Metal Concentrations in Sediment Digest Solution Riverbed Sediments as Reported by University of Colorado – LEGS laboratory

site name GPS site name sediment dry

weight (g) Cu

(mg L-1) Pb

(mg L-1) Zn

(mg L-1)

J1 5561A-T1 1.011 2.10 3.00 3.67

J2 5561A-T2 1.02 6.74 5.36 4.18

J3D 5561A-T3D 1.134 1.67 3.72 2.85

J3E 5561A-T3E 1.123 1.69 3.64 2.85

J3F 5561A-T3F 0.981 1.43 3.14 2.59

J4 5561A-T4 1.183 1.36 8.97 3.12

J5 5561A-JOHN NC NC NC NC

JFD 5561A-FD 1.064 2.31 6.41 3.98

J6 5561A-10 0.991 6.07 8.82 7.71

J7 5561A-16 1.109 1.22 3.88 2.75

J8 5561A-28 1.105 1.17 4.71 3.36

J9 5561A-30-582 1.091 4.52 6.18 4.20

J10 5561A-55 1.012 3.27 9.43 8.09

J11 5561A-52 NC NC NC NC

J12 5561A-53 1.018 4.01 11.2 12.3

JCG 5561A-CG 0.972 1.81 2.50 2.06

J13 5561A-61 0.995 8.75 15.4 12.5

J14 5561A-62 0.385 6.60 6.10 5.47

SEDB1 LAB_BLANK 1 - 0.02 0.00 0.02

SEDB2 LAB_BLANK 2 - 0.00 0.00 0.01

SEDB3 LAB_BLANK 3 - 0.02 0.05 0.05

142

Table D. 4 James Creek Cu, Zn, and Pb Concentrations in Riverbed Sediments Calculated from Values in Table D.3

site name GPS site name sediment dry

weight (g) Cu

(mg kg-1) Pb

(mg kg-1) Zn

(mg kg-1)

J1 5561A-T1 1.011 41.8 59.6 72.7

J2 5561A-T2 1.02 133.2 105.8 82.2

J3D 5561A-T3D 1.134 29.5 66.0 50.2

J3E 5561A-T3E 1.123 30.1 65.1 50.7

J3F 5561A-T3F 0.981 29.3 64.4 52.7

J4 5561A-T4 1.183 23.0 152.9 52.9

J5 5561A-JOHN NC NC NC NC

JFD 5561A-FD 1.064 43.7 121.3 75.1

J6 5561A-10 0.991 123.5 179.5 156.7

J7 5561A-16 1.109 21.9 70.3 49.6

J8 5561A-28 1.105 21.1 85.8 61.0

J9 5561A-30-582 1.091 83.5 114.1 77.3

J10 5561A-55 1.012 65.1 188.0 161.0

J11 5561A-52 NC NC NC NC

J12 5561A-53 1.018 79.3 222.0 243.9

JCG 5561A-CG 0.972 37.3 51.6 42.3

J13 5561A-61 0.995 177.5 313.3 254.1

J14 5561A-62 0.385 345.4 319.1 285.7

143

Table D. 5 Little James Creek Metal Concentrations in Sediment Digest Solution Riverbed Sediments as Reported by University of Colorado – LEGS laboratory

site name

GPS site name sediment dry weight (g)

Cu (mg L-1)

Pb (mg L-1)

Zn (mg L-1)

LJ1A 5562A-0A 1.03 3.93 3.15 4.39

LJ1B 5562A-0B 1.01 1.03 3.44 3.54

LJ1C 5562A-0C 1.02 2.40 3.25 3.86

LJ2 5562A-1 1.03 1.08 3.15 2.37

LJ3 5562A-6 1.07 38.0 7.93 35.2

LJ4D 5562A-8D 0.93 69.5 11.9 66.9

LJ4E 5562A-8E 1.04 73.3 12.5 71.5

LJ4F 5562A-8F 1.05 78.4 13.4 75.9

LJ5D 5562A-10D 1.00 0.74 3.28 2.00

LJ5E 5562A-10E 0.97 0.69 3.19 1.89

LJ5F 5562A-10F 0.98 0.72 3.27 1.99

LJ6D 5562A-14D 0.99 1.51 6.55 3.61

LJ6E 5562A-14E 0.97 1.55 6.67 3.68

LJ6F 5562A-14F 1.00 1.58 6.85 3.72

LJ7i 5562A-16i 0.25 0.84 6.87 1.25

LJ7ii 5562A-16ii 0.51 1.62 12.6 2.34

LJ7iii 5562A-16iii 0.75 2.44 17.1 3.19

LJ7iv 5562A-16iv 1.01 3.18 21.7 4.07

LJ7v 5562A-16v 1.25 3.86 26.2 4.91

LJ8A 5562A-18-1A 0.98 10.2 12.4 15.4

LJ8B 5562A-18-1B 0.97 10.2 12.1 15.1

LJ8C 5562A-18-1C 1.01 10.3 12.3 15.4

LJ9A 5562A-21A 1.13 2.06 10.6 4.46

LJ9B 5562A-21B 1.19 2.11 11.1 4.38

LJ9C 5562A-21C 1.03 1.88 9.78 4.06

LJ10D 5562A-28D 1.01 12.3 38.0 14.8

LJ10E 5562A-28E 1.06 13.4 41.6 16.1

LJ10F 5562A-28F 1.01 11.5 32.8 13.2

LJ11A 5562A-32A 1.01 9.54 34.4 7.46

144

LJ11B 5562A-32B 1.03 10.1 40.1 8.17

LJ11C 5562A-32C 1.01 9.80 35.1 7.41

LJ12 5562A-35 1.00 4.73 16.5 4.81

LJ13i 5562A-38i 0.26 0.69 6.18 1.44

LJ13ii 5562A-38ii 0.50 1.29 10.3 2.35

LJ13iii 5562A-38iii 0.76 1.93 14.5 3.46

LJ13iv 5562A-38iv 1.00 2.53 18.5 4.21

LJ13v 5562A-38v 1.27 3.24 23.0 5.27

SEDB1 LAB_BLANK 1 - 0.02 0.00 0.02

SEDB2 LAB_BLANK 2 - 0.00 0.00 0.01

SEDB3 LAB_BLANK 3 - 0.02 0.05 0.05

145

Table D. 6 Little James Creek Cu, Zn, and Pb Concentrations in Riverbed Sediments Calculated from Values in Table D.5

site name gps site name sediments dry

weight (g) Cu

(mg kg-1) Pb

(mg kg-1) Zn

(mg kg-1)

LJ1A 5562A-0A 1.03 77.3 61.9 86.0

LJ1B 5562A-0B 1.01 20.3 68.3 70.2

LJ1C 5562A-0C 1.02 47.5 64.2 76.1

LJ2 5562A-1 1.03 20.9 61.6 46.0

LJ3 5562A-6 1.07 715 149 663

LJ4D 5562A-8D 0.93 1505 257 1447

LJ4E 5562A-8E 1.04 1420 243 1384

LJ4F 5562A-8F 1.05 1513 259 1464

LJ5D 5562A-10D 1.00 14.6 65.8 39.8

LJ5E 5562A-10E 0.97 14.1 66.2 38.8

LJ5F 5562A-10F 0.98 14.5 67.0 40.4

LJ6D 5562A-14D 0.99 30.5 133 72.9

LJ6E 5562A-14E 0.97 32.2 139 76.2

LJ6F 5562A-14F 1.00 31.9 139 74.9

LJ7i 5562A-16i 0.25 65.9 545 97.5

LJ7ii 5562A-16ii 0.51 63.8 502 91.9

LJ7iii 5562A-16iii 0.75 65.2 458 85.0

LJ7iv 5562A-16iv 1.01 63.3 433 80.9

LJ7v 5562A-16v 1.25 62.1 422 78.8

LJ8A 5562A-18-1A 0.98 209 254 316

LJ8B 5562A-18-1B 0.97 211 251 313

LJ8C 5562A-18-1C 1.01 206 246 307

LJ9A 5562A-21A 1.13 36.6 189 79.2

LJ9B 5562A-21B 1.19 35.7 188 73.9

LJ9C 5562A-21C 1.03 36.7 191 79.1

LJ10D 5562A-28D 1.01 246 764 297

LJ10E 5562A-28E 1.06 254 793 306

LJ10F 5562A-28F 1.01 230 658 264

LJ11A 5562A-32A 1.01 191 690 149

146

LJ11B 5562A-32B 1.03 197 783 159

LJ11C 5562A-32C 1.01 195 699 147

LJ12 5562A-35 1.00 95.0 333 96.4

LJ13i 5562A-38i 0.26 52.7 482 110.3

LJ13ii 5562A-38ii 0.50 51.5 413 93.5

LJ13iii 5562A-38iii 0.76 50.9 386 91.3

LJ13iv 5562A-38iv 1.00 50.8 373 84.6

LJ13v 5562A-38v 1.27 51.3 365 83.3

147

Percentage of fine grained sediments

Table D. 7 Lefthand Creek - percent of <63 um grain size in total sediment sample at each site.

GPS site name total weight (g) <63 μm sample wt (g) weight % of <63 μm

sediments

5560A-1 1484.1 13.414 0.904

5560A-6 1717.8 4.672 0.272

5560A-8 954 2.187 0.229

5560A-13 871.1 1.128 0.129

5560A-14 1203.4 0.898 0.075

5560A-17 1528.1 2.36 0.154

5560A-21 1541.9 0.831 0.054

5560A-56 1576.5 12.389 0.786

5560A-95-1 1699.3 2.985 0.176

5560A-96(1) 1582.7 0.782 0.049

5560A-96(2) 1483.9 0.634 0.043

5560A-101 1506.1 1.567 0.104

Slide Mine discharge 908.6 144.535 15.907

5560A-103 1604.6 6.972 0.435

5560A-113 1810.8 3.578 0.198

5560A-123 1635.8 0.887 0.054

5560A-129 1603.9 5.638 0.352

5560A-136-2 1575.4 9.378 0.595

5560A-127 1541.3 3.386 0.220

5560A-171 1601.1 8.562 0.535

5560A-184 1300.1 3.27 0.252

148

Table D. 8 James Creek - percent of <63 um grain size in total sediment sample at each site.

GPS site name total weight (g) <63 μm sample wt (g) weight % of <63 μm

sediments

5561A-T1 1455 9.34 0.642

5561A-T2 1664 2.64 0.159

5561A-T3 1610 10.38 0.645

5561A-T4 1527 1.59 0.104

5561A-FD 1570 2.43 0.154

5561A-10 1625 3.08 0.190

5561A-16 1427 5.74 0.402

5561A-28 1353 13.43 0.992

5561A-30-582 1446 8.08 0.559

5561A-55 1620 12.12 0.748

5561A-53 1573 3.55 0.225

5561A-CG 1577 12.53 0.795

5561A-61 1766 2.02 0.114

5561A-62 1449 0.54 0.037

149

Table D. 9 Little James Creek - percent of <63 um grain size in total sediment sample at each site.

GPS site name total weight (g) <63 μm sample wt (g) weight % of <63 μm

sediments

5562A-0(1) 1447 15.1 1.044

5562A-0(2) 1482 15.6 1.052

5562A-1 1196 9.59 0.802

5562A-6 1189 20.9 1.758

5562A-8 1332 32.9 2.470

5562A-10 1254 44.8 3.573

5562A-14 1300 10.8 0.833

5562A-15 1369 14.1 1.029

5562A-16 1329 9.30 0.700

5562A-18-1 1136 20.6 1.809

5562A-21 1148 39.3 3.424

5562A-28 1376 9.84 0.715

5562A-32 1536 30.0 1.955

5562A-38 1331 10.4 0.780

150