Assessment of metal loads by tracer injection and synoptic sampling in the Lefthand Creek watershed,...

Assessment of metal loads by tracer injection and synoptic

sampling in the Lefthand Creek watershed, Boulder County,

ColoradoAlice Wood, Roshan Cholas, Laura Harrington,

Lily Isenhart, Ned Turner, and Joe Ryan

Overview

Background Methods Results

Background

Study area

Mountainous watershed Drains 220 km2

Elevation range from 4,200 m at the glacial headwaters near the Continental Divide to 1,400 m at the confluence with the St. Vrain Creek in Longmont, CO

Located at the northern tip of the Colorado Mineral Belt

Lefthand Watershed Task Force Report, 2002

Site History Hundreds of mines and

mills operated in the mid-1800s—late 1900s Brought settlers to the

area Traditional mining

practices involved abandoning sites when they were no longer profitable, and moving on to a new area.

Site History

Today’s legacy: acid mine drainage and metal contamination from mines and waste rock

AMD Chemistry The interaction of sulfide minerals, generally

pyrite, with oxygen and water generates sulfuric acid

2FeS2(s) + 7O2(aq) + 2H2O → 2Fe2+ + 4SO42- + 4H+

2Fe2+ + ½O2 + 2H+ → 2Fe3+ + H2O2Fe3+ + 6H2O ↔ 2Fe(OH)3(s) + 6H+

14Fe3+ + FeS2(s) + 8H2O → 2SO42- + 15Fe2+ + 16H+

Modern Concerns

Primary water supply to 14,000 customers of the Left Hand Water District Threat of toxic release to

drinking and agricultural water supply

Aquatic life toxicity Fish kills, impaired habitat

TMDL listings

Remedial actions

Current remedial activities: the Captain Jack Mine and Mill Superfund Site Honeywell voluntary cleanup of the Burlington Mine the development of a watershed-scale remediation plan by

a local stakeholder group

In the Lefthand Creek watershed, an understanding of toxic metal sources, transport, and fate is necessary to prioritize contaminated sites and develop efficient cleanup strategies.

Research Goal and Hypothesis Goal: Identify and quantify sources of metal

loading to Lefthand, James, and Little James Creeks.

Hypothesis: Metal loading tracer tests and synoptic sampling (Kimball, 1997; Kimball et al, 2001) can be applied in series to analyze changes in stream flow and metal concentrations with high spatial resolution throughout the Lefthand Creek watershed.

Methods

Tracer Tests

Conservative tracer (LiCl, NaCl) of a known concentrations is pumped into the stream at a known, constant rate

According to mass balances, dilution by inflowing stream water reduces the tracer concentration at downstream sites.

Stream discharge is calculated according to:

Kimball, 1997

Tracer solution

Injection pump

Stream

Sampling and

monitoring

Tracer tests

Monitored [Li] and conductivity at four sites Tracer injection tank

Monitor [Li] changes, obtain average tracer [Li] Upstream of injection

Monitor [Li] changes, obtain background [Li] Downstream of injection

Observe leading edge of tracer injection solution Downstream end of study reach

Observe arrival of tracer at most downstream sampling site

Tracer tests The tracer is pumped into the stream

continuously throughout the test. Sampling does not begin until the

tracer reaches a “steady state” through the entire stream reach.

Added a pulse of NaCl to the stream before beginning the LiCl injection NaCl spikes the downstream conductivity Provides measurable indication of the arrival of LiCl at

the most downstream sampling site

Synoptic Sampling Collection of stream water

samples at spatially frequent locations during the tracer injection period Collected both in-stream and

tributary samples

These samples provide a “snapshot in time” of tracer and metal concentrations in the stream Allows for stream discharge calculations for each

sample site Discharge and concentration data allow for load

calculations for each sample site

Synoptic Sampling

Lefthand Creek

JamesCreek

Little James Creek

Jamestown

Ward

Rowena

Hw

y 36Hwy

72

5/27/03

5/29/03

6/05/03

6/10/03

6/12/03

7/02/02

7/18/02

4/22/03

5/21/03

N

I kmI kmI km

Synoptic SamplingDate Location

Stream reach length

(m)

TracerTracer

concentration (M)

Tracer injection rate

(L/min)

Tracer injection duration

(min)

7/18/2002 Upper James Creek 4940 NaCl 6.2 0.82 260

7/2/2002 Lower James Creek 5212 NaCl 3 1.26 195

4/22/2003 Little James Creek 2872 LiCl 0.04 1.0 255

5/21/2003 Lefthand Creek – California Gulch 2514 LiCl 0.60 0.5 310

5/27/2003Lefthand Creek – Sawmill Rd. to

park4928 LiCl 0.06 1.1 195

5/29/2003 Lefthand Creek - park to Rowena 7072 LiCl 0.06 1.0 225

6/5/2003Lefthand Creek – Rowena to James

Creek confluence7088 LiCl 0.06 0.97 280

6/10/2003Lefthand Creek – James Creek

confluence to Buckingham Park5207 LiCl 0.06 1.3 226

6/12/2003Lefthand Creek – Buckingham Park

to Haldi intake5950 LiCl 0.05 1.0 320

6/17/2003 Little James Creek 2232 LiCl 0.02 0.35 390

11/15/2003 Lefthand Creek – California Gulch 1583 LiCl ** 1.0 185

Laboratory Procedures and Analysis

All synoptic samples were analyzed for pH in the lab within 24 hours of collection

~ 30 mL of each synoptic sample was filtered through hydrophilic nylon syringe filters 0.45 μm or 0.2 μm diameter pore size

All samples were acidified to a pH < 2 with trace-metal grade nitric acid for preservation

Metal analysis was performed with ICP-AES and ICP-MS

Definitions

We apply the following definitions for our study: Total metals – The metal concentrations

measured in the unfiltered synoptic samples Dissolved metals – The metal concentrations

measured in the filtered synoptic samples Colloidal metals – The metal concentrations

calculated by taking the difference of total and dissolved metal concentrations [MeC] = [MeT] – [MeD]

Load calculations Metal loads in a stream are the product of the

stream discharge and metal concentrations. Reported in g/day or mol/day

Loads were calculated for each synoptic sample site Fe, Al, Mn, Zn, Cu, Pb, Ca Total, dissolved, colloidal

Downstream load increases indicate an increase in stream discharge, an increase in metal concentrations, or both

Hardness and Standards

CDPHE Table Values Standards (TVS) were compared to the measured dissolved metal concentrations. TVS are based on water hardness

Hardness = the sum of calcium (Ca) and magnesium (Mg) concentrations expressed as mg/L CaCO3 Calculated for 4—5 sites along each stream reach

Results

Discharge – Lefthand CreekP

ea

k to

Pe

ak

Hw

yu

nn

am

ed

tri

bu

tary

(m

ine

)B

ig F

ive

Tu

nn

el t

rib

uta

ry

Ind

ian

a G

ulc

hP

uzz

ler

Gu

lch

Tu

sca

rora

Gu

lch

Sp

rin

g G

ulc

h (

Go

ld L

ake

)L

ick

Ski

llet

Gu

lch

Slid

e M

ine

Dra

ina

ge

Ro

we

na

Gle

nd

ale

Gu

lch

Nu

gg

et

Gu

lch

"Le

e H

ill"

Gu

lch

Jam

es

Cre

ek

un

na

me

d t

rib

uta

ry,

sou

th

un

na

me

d t

rib

uta

ry,

no

rth

Six

mile

Cre

ek

un

na

me

d t

rib

uta

ry,

sou

th

Ha

ldi D

itch

In

take

(L

HW

D)

un

na

me

d t

rib

uta

ry,

sou

th

un

na

me

d t

rib

uta

ry,

sou

th0 5 10 15 20 25 30

flow

rat

e (m

3 s-1

)

0.00

0.04

0.08

0.12

0.16

5/215/275/296/56/106/12tribs

Zinc – Lefthand Creek

Lefthand Creek distance (km)

0 5 10 15 20 25 30

Zn

load

ing

(g d

-1)

0

500

1000

1500

2000

2500

total Zndissolved Zntotal Zn, tributaries

0 5 10 15 20 25 30Zn

conc

entr

atio

n (

g L-1

)

0

100

200

300

800900 total Zn

dissolved Zntotal Zn, tributaries

Pe

ak to

Pea

k H

wy

unna

med

trib

utar

y (m

ine

)B

ig F

ive

Tun

nel t

ribu

tary

Indi

ana

Gul

chP

uzz

ler

Gul

ch

Tus

caro

ra G

ulch

Sp

ring

Gul

ch (

Go

ld L

ake)

Lick

Ski

llet G

ulch

Slid

e M

ine

Dra

inag

e

Ro

wen

a

Gle

ndal

e G

ulch

Nu

gget

Gul

ch

"Lee

Hill

" G

ulch

Jam

es C

ree

kun

nam

ed tr

ibut

ary,

so

uth

unna

med

trib

utar

y, n

orth

Six

mile

Cre

ek

unna

med

trib

utar

y, s

out

h

Ha

ldi D

itch

Inta

ke (

LHW

D)

unna

med

trib

utar

y, s

out

h

unna

med

trib

utar

y, s

out

h

0 5 10 15 20 25 30

flow

rat

e (m

3 s-1

)

0.00

0.04

0.08

0.12

0.16

5/215/275/296/56/106/12tribs

Copper – Lefthand Creek

0 5 10 15 20 25 30Cu

conc

entr

atio

n (

g L-1

)

0

40

80

120

160total Cudissolved Cutotal Cu, tributaries


0 5 10 15 20 25 30

Cu

load

ing

(g d

-1)

0200400600800

1000

total Cudissolved Cutotal Cu, tributaries

Pea

k to

Pea

k H

wy

unna

med

trib

uta

ry (

min

e)B

ig F

ive

Tun

nel t

ribu

tary

Indi

ana

Gul

chP

uzzl

er G

ulch

Tus

caro

ra G

ulch

Spr

ing

Gul

ch (

Gol

d La

ke)

Lick

Ski

llet G

ulch

Slid

e M

ine

Dra

inag

e

Row

ena

Gle

ndal

e G

ulch

Nug

get G

ulch

"Lee

Hill

" G

ulch

Jam

es C

reek

unna

med

trib

uta

ry, s

outh

unna

med

trib

uta

ry, n

orth

Six

mile

Cre

ek

unna

med

trib

uta

ry, s

outh

Hal

di D

itch

Inta

ke (

LHW

D)

unna

med

trib

uta

ry, s

outh

unna

med

trib

uta

ry, s

outh

0 5 10 15 20 25 30

flow

rat

e (m

3 s-1

)

0.00

0.04

0.08

0.12

0.16

5/215/275/296/56/106/12tribs

Lead – Lefthand Creek

0 5 10 15 20 25 30Pb

conc

entr

atio

n (

g L-1

)

0

5

10

15

20total Pbdissolved Pbtotal Pb, tributaries


0 5 10 15 20 25 30

Pb

load

ing

(g d

-1)

0

100

200

300

400total Pbdissolved Pbtotal Pb, tributaries

Pe

ak

to P

ea

k H

wy

un

na

me

d t

rib

uta

ry (

min

e)

Big

Fiv

e T

un

ne

l tri

bu

tary

Ind

ian

a G

ulc

hP

uzz

ler

Gu

lch

Tu

sca

rora

Gu

lch

Sp

rin

g G

ulc

h (

Go

ld L

ake

)L

ick

Ski

llet

Gu

lch

Slid

e M

ine

Dra

ina

ge

Ro

we

na

Gle

nd

ale

Gu

lch

Nu

gg

et

Gu

lch

"Le

e H

ill"

Gu

lch

Jam

es

Cre

ek

un

na

me

d t

rib

uta

ry,

sou

th

un

na

me

d t

rib

uta

ry,

no

rth

Six

mile

Cre

ek

un

na

me

d t

rib

uta

ry,

sou

th

Ha

ldi D

itch

In

take

(L

HW

D)

un

na

me

d t

rib

uta

ry,

sou

th

un

na

me

d t

rib

uta

ry,

sou

th

0 5 10 15 20 25 30

flow

rat

e (m

3 s-1

)

0.00

0.04

0.08

0.12

0.16

5/215/275/296/56/106/12tribs

Discharge – Upper James Creek

0 1 2 3 4 5

flow

rat

e (m

3 s-1

)

0.00.51.01.52.02.53.0

un

na

me

d g

ully

, S

ou

th

LIt

tle J

am

es

Cre

ek

Jam

est

ow

n

Mo

orh

ea

d G

ulc

h

Joh

n J

ay

MIn

e

Fa

ird

ay

MIn

e

Zinc – James Creek

James Creek distance (km)

0 2 4 6 8 10

Zn

load

ing

(g d

-1)

05000

10000150002000025000300003500040000


0 2 4 6 8 10Zn

conc

entr

atio

n (

g L-1

)

050

100150200250300


0 2 4 6 8 10

flow

rat

e (m

3 s-1

)

0.00.51.01.52.02.53.0

un

na

me

d g

ully

, S

ou

th

LIt

tle J

am

es

Cre

ek

Jam

est

ow

n

Mo

orh

ea

d G

ulc

h

Joh

n J

ay

MIn

e

Fa

ird

ay

MIn

e

Le

fth

an

d C

ree

k C

on

flue

nce

Copper – James Creek


0 2 4 6 8 10

Cu

load

ing

(g d

-1)

0100200300400500600700800


0 2 4 6 8 10Cu

conc

entr

atio

n (

g L-1

)

0

5

10

15


0 2 4 6 8 10

flow

rat

e (m

3 s-1

)

0.00.51.01.52.02.53.0

un

na

me

d g

ully

, S

ou

th

LIt

tle J

am

es

Cre

ek

Jam

est

ow

n

Mo

orh

ea

d G

ulc

h

Joh

n J

ay

MIn

e

Fa

ird

ay

MIn

e

Le

fth

an

d C

ree

k C

on

flue

nce

Lead – James Creek


0 2 4 6 8 10

Pb

load

ing

(g d

-1)

0100200300400500600700800


0 2 4 6 8 10Pb

conc

entr

atio

n (

g L-1

)

0

1

2

3


0 2 4 6 8 10

flow

rat

e (m

3 s-1

)

0.00.51.01.52.02.53.0

un

na

me

d g

ully

, S

ou

th

LIt

tle J

am

es

Cre

ek

Jam

est

ow

n

Mo

orh

ea

d G

ulc

h

Joh

n J

ay

MIn

e

Fa

ird

ay

MIn

e

Le

fth

an

d C

ree

k C

on

flue

nce

Discharge – Little James Creek

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (

m3 s

-1)

0.0000.0050.0100.0150.0200.0250.030

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

ra

te (

m3 s

-1)

0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

4/22/03 – High Flow

6/17/03 – Low Flow

Zinc – Little James Creek High Flow

Little Jim Creek distance (km)

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Zn

load

ing

(g d

-1)

0

200

400

600

800


0.0 0.5 1.0 1.5 2.0 2.5 3.0Zn

conc

entr

atio

n (

g L-1

)

0

200

400

600

10000

20000total Zndissolved Zntotal Zn, tributaries

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.0000.0050.0100.0150.0200.0250.030

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

Copper – Little James Creek High Flow


0.0 0.5 1.0 1.5 2.0 2.5 3.0

Cu

load

ing

(g d

-1)

0

20

40

60

80


0.0 0.5 1.0 1.5 2.0 2.5 3.0Cu

conc

entr

atio

n (

g L-1

)

0

10

20

30

200 total Cudissolved Cutotal Cu, tributaries

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.0000.0050.0100.0150.0200.0250.030

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

Lead – Little James Creek High Flow


0.0 0.5 1.0 1.5 2.0 2.5 3.0

Pb

load

ing

(g d

-1)

0

20

40

60

80

100


0.0 0.5 1.0 1.5 2.0 2.5 3.0Pb

conc

entr

atio

n (

g L-1

)

0

20

40

60


0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.0000.0050.0100.0150.0200.0250.030

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

Zinc – Little James Creek Low Flow


0.0 0.5 1.0 1.5 2.0 2.5 3.0

Zn

load

ing

(g d

-1)

0

100

200

300


0.0 0.5 1.0 1.5 2.0 2.5 3.0Zn

conc

entr

atio

n (

g L-1

)

0200400600800

10000

20000total Zndissolved Zntotal Zn, tributaries

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.0000

0.0005

0.0010

0.0015

0.0020

0.0025

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

Copper – Little James Creek Low Flow


0.0 0.5 1.0 1.5 2.0 2.5 3.0

Cu

load

ing

(g d

-1)

0

2

4

6

8

10


0.0 0.5 1.0 1.5 2.0 2.5 3.0Cu

conc

entr

atio

n (

g L-1

)

020406080

100120 total Cu

dissolved Cutotal Cu, tributaries

0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.000

0.001

0.002

0.003

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

uta

ry,

sou

th

wa

terf

all

CR

10

2J

culv

ert

un

na

me

d t

rib

uta

ry,

sou

th

Lead – Little James Creek Low Flow


0.0 0.5 1.0 1.5 2.0 2.5 3.0

Pb

load

ing

(g d

-1)

0

2

4

6

8

10


0.0 0.5 1.0 1.5 2.0 2.5 3.0Pb

conc

entr

atio

n (

g L-1

)

020406080

100120


0.0 0.5 1.0 1.5 2.0 2.5 3.0

flow

rat

e (m

3 s-1

)

0.000

0.001

0.002

0.003

un

na

me

d t

rib

uta

ry,

sou

th

ne

ar

Arg

o M

ine

trib

uta

ry (

Em

mit

ad

it)B

ala

rat

Cre

ek

no

rth

min

e w

ast

e p

ile

un

na

me

d t

rib

uta

ry,

S

"str

ea

msi

de

ta

ilin

gs"

un

na

me

d t

rib

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Discussion of Results

Metal Sources – Lefthand Creek California Gulch

Big Five, Captain Jack, White Raven Sites

“Lee Hill” Gulch Ephemeral (?) tributary at

approximately 19.4 km downstream

Metal sources – James Creek

Most sources are in the Upper James Creek (upstream of Jamestown) John Jay Mine Fairday Mine Unknown sources: 2.5 km and 4.8 km

The Little James Creek brings is the largest contributor to the James Creek

The Golden Age Mine may be contributing lead upstream of the James-Lefthand Confluence

Metal sources – Little James Creek

Present during both high and low flow sampling events Balarat Creek Emmit Adit

Present only during high flow event Unnamed tributary near the

Streamside Tailings area

Acknowledgements Many thanks to all of the organizations who helped

to fund this research: CU Outreach Program Undergraduate Research Opportunity Program (UROP) Research Experience for Undergraduates (REU) University Government of Graduate Students

Thanks to the Geology L.E.G.S. lab for analysis And especially to the individuals who offered their

time and expertise: Dr. Joe Ryan, Lily Isenhart, Roshan Cholas, Marc Cittone,

Michael Costanzo, Nicole Denovio, Laura Harrington, Tracy Kirkland, Kim Raby, Emily Schneider, and Ned Turner.

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Assessment of metal loads by tracer injection and synoptic sampling in the Lefthand Creek watershed,...

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