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Transcript of 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
Lefthand Creek distance (km)
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
Lefthand Creek distance (km)
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
total Zndissolved Zntotal Zn, tributaries
0 2 4 6 8 10Zn
conc
entr
atio
n (
g L-1
)
050
100150200250300
total Zndissolved Zntotal Zn, tributaries
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
James Creek distance (km)
0 2 4 6 8 10
Cu
load
ing
(g d
-1)
0100200300400500600700800
total Cudissolved Cutotal Cu, tributaries
0 2 4 6 8 10Cu
conc
entr
atio
n (
g L-1
)
0
5
10
15
20total Cudissolved Cutotal Cu, tributaries
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
James Creek distance (km)
0 2 4 6 8 10
Pb
load
ing
(g d
-1)
0100200300400500600700800
total Cudissolved Cutotal Cu, tributaries
0 2 4 6 8 10Pb
conc
entr
atio
n (
g L-1
)
0
1
2
3
4total Cudissolved Cutotal Cu, tributaries
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
total Zndissolved Zntotal Zn, tributaries
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
Little Jim Creek distance (km)
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
total Cudissolved Cutotal Cu, tributaries
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
Little Jim Creek distance (km)
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
total Cudissolved Cutotal Cu, tributaries
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
80total 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
Zinc – Little James Creek Low 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
100
200
300
total Zndissolved Zntotal Zn, tributaries
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
Little Jim Creek distance (km)
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
total Cudissolved Cutotal Cu, tributaries
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
Little Jim Creek distance (km)
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
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total Cudissolved Cutotal Cu, tributaries
0.0 0.5 1.0 1.5 2.0 2.5 3.0Pb
conc
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total Cudissolved Cutotal Cu, tributaries
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flow
rat
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3 s-1
)
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0.001
0.002
0.003
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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.
Questions?