Applied Geochemistry 17 (2002) 421430

www.elsevier.com/locate/apgeochem

Sorption of trace metals to an aluminum precipitate in a

stream receiving acid rock-drainage; Snake River,
Summit County, Colorado
LeeAnn Munka,*, Gunter Faurea, Douglas E. Pridea, Jerry M. Bighamb
a

Department of Geological Sciences,The Ohio State University, 125 South Oval Mall, Columbus, Ohio 43210, USA
b
School of Natural Resources, The Ohio State University, 2021 Coey Road, Columbus, Ohio 43210, USA
Received 6 July 2000; accepted 15 April 2001
Editorial handling by R. Fuge

Abstract
The quality of water in streams that are contaminated by acid drainage from mines and from the weathering of mineralized rocks improves as the water ows downstream. The purpose of this study was to investigate the geochemical processes that occur in one such stream and to determine the fate of the trace metals that are removed from the water. The
stream chosen for this purpose was the Snake River, Summit County, Colorado, which is aected by natural acid rockdrainage (ARD) containing SO4, Al, Fe, and various trace elements such as Zn, Cu, Pb, Ni, and others. Most of the Fe in
the Snake River is removed from solution by the oxidation of Fe2+ to Fe3+ and the subsequent precipitation of Fe-oxyhydroxides that form a massive ferricrete deposit near the springs that feed the river. Further downstream, the Snake River
(pH=3.0) mixes with water from Deer Creek (pH= 7.0) thereby increasing its pH to 6.3 and causing SO4-rich precipitates
of Al-oxyhydroxide to form. The precipitates and associated organic C complexes sorb trace metals from the water and
thus have high concentrations of certain elements, including Zn (54011,400 ppm), Cu (34221 ppm), Pb (90340 ppm),
and Ni (11197 ppm). The concentrations of these elements in the precipitates that coat the streambed rise steeply in the
zone of mixing and then decline downstream. The trace element concentrations of the water in the mixing zone at the
conuence with Deer Creek decrease by 75% or more and are up to 3 orders of magnitude lower than those of the
precipitates. Sorption curves for Zn, Cu, Pb, Ni, and SO4 were derived by stepwise neutralization of a sample of Snake
River water (collected above the conuence with Deer Creek) and indicate that the trace metals are sorbed preferentially with increasing pH in the general order Pb, Cu, Zn, and Ni. Sulfate is removed between pH 4 and 5 to form
an Al-hydroxysulfate and/or by sorption to microcrystalline gibbsite. The sorption data determined from the neutralization experiment were used to account for the downstream decrease of trace-metal concentrations in the precipitates. The results of this study demonstrate that the partitioning of trace metals in the Snake River is not only a
function of pH, but also depends on the progressive removal of trace metals as the water of the Snake River ows
through its conuence with Deer Creek. The chemical composition of the water also determines what compounds
precipitate with increasing pH. # 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction
When sulde minerals such as pyrite are oxidized at
or near the surface of the earth, ground and surface
* Corresponding author at present address: University of
Alaska, Anchorage Geology Department 3211 Providence Dr.
Anchorage Alaska 99508 USA. Tel.: +1-907-786-6840; fax:
+1-907-786-6850.

waters typically become acidic and are enriched in SO4,

Fe, Al, and trace elements (Wentz, 1974). Some of the
mobilized trace elements associated with acid drainage
pose a potential threat to the health of plants, animals,
and humans (Adriano, 1986; McBride, 1994). As acidic
Fe- and Al-rich streams are neutralized, amorphous to
semi-crystalline oxyhydroxides and hydroxysulfates of
Fe or Al can form (Stumm and Morgan, 1996). These
precipitates have surface sites that sorb cations and

0883-2927/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0883-2927(01)00098-1

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L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

anions depending on their charge, which is primarily

controlled by the pH of the surrounding solution. The
suspended particles and precipitates on the bottom of
stream channels are transported downstream during
periods of high ow and may be deposited in lakes and
reservoirs.
The Snake River in the Dillon watershed, Summit
County, Colorado, provides an opportunity to study the
distribution of trace elements between water and precipitates that are composed predominantly of an Alhydroxysulfate. This watershed lies within the Colorado
mineral belt, which has been mined for Au, Ag, and various sulde minerals since the 1860s (Lovering and Goddard, 1950). Although mining was discontinued in the
1930s, some of the streams are still contaminated by acid
mine-drainage (AMD) as well as by acid rock-drainage
(ARD). The drainage basins of the Snake River and Deer
Creek are underlain by granitic gneisses (Idaho Springs
Formation and Swandyke Hornblende Gneiss, respectively) of Precambrian age that were intruded by Tertiary
quartz monzonite plutons (Lovering, 1935). The bedrock
contains disseminated pyrite as well as quartz veins with
pyrite and other metallic suldes (Lovering and Goddard, 1950). Whole-rock chemical analyses indicate that
the Idaho Springs Formation is Al- and Si-rich, whereas
the Swandyke Hornblende Gneiss has relatively high
concentrations of Ca, Mg, and Fe.
Theobald et al. (1963) reported the presence of
brown, tan, and black precipitates on the streambed at
the conuence of the Snake River and Deer Creek and
determined that some of these precipitates contained Fe,
Al, Mn, and the trace metals Pb, Cu, and Zn. McKnight
and Bencala (1988, 1989) subsequently showed that Fe
concentrations in the Snake River vary hourly due to
photoreduction of Fe3+ to Fe2+. In addition, McKnight
et al. (1992a) correlated the concentrations of Fe and
organic C in the precipitates with decreasing metal concentrations and suggested that this relationship implies
that some metal cations are sorbed onto humic substances in the precipitates.
Numerous laboratory investigations of trace element
sorption to Fe-hydroxides have provided a basis for
understanding the partitioning of trace elements
between solution and sorbent (Ballistrieri and Murray,
1982; Dzombak and Morel, 1990; Stumm, 1992). In
addition, eld studies addressing various aspects of the
transport and fate of metals in waters receiving AMD
by Rampe and Runnells (1989), Broshears et al. (1996),
Schemel et al. (2000), and others have provided information about the interaction of multiple variables such
as pH, sorbent composition, downstream transport, etc.
that control the distribution of trace metals in natural
aquatic environments.
The objective of this paper is to test the hypothesis
that the partitioning of trace metals in the Snake River
at and just below its conuence with Deer Creek is

controlled predominantly by an increase of pH and the

resulting precipitation of an Al-hydroxysulfate. This
study is part of a larger research project of which the
objective is to investigate the weathering of mineralized
rocks in the drainage basin of the Snake River and to
study the geochemical processes that control the concentrations of trace elements in the Dillon Reservoir,
which is one of the principal sources of drinking water
for the city of Denver.

2. Methodology
2.1. Water and precipitate samples
Water and samples of tan to white occulant precipitates were collected from the streambed over a 60 m
interval at the conuence of the Snake River and Deer
Creek (Fig. 1). Precipitates were collected using a 60-ml
polypropylene syringe with attached plastic TMTygon
tubing. The precipitates and associated water were transferred to high-density polyethylene bottles that were

Fig. 1. Location of sample collecting sites. The Snake River

and Deer Creek are located in the southern part of Summit
County, Colorado, within the Colorado Mineral Belt. Collecting sites for water and precipitates are indicated with open circles (o) and are numbered. The water sample used for the
neutralization experiment is marked by the star.

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L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

rinsed with stream water at each collection site. In

addition, the pH was measured twice at every sampling
location. The water and precipitate samples were refrigerated immediately upon returning to the laboratory,
and within 2 days the samples were centrifuged and the
supernatant water was decanted, ltered through 0.45
mm lters, and acidied by adding 12 drops of concentrated reagent-grade HNO3. The laboratory results
showed that 0.45 mm lters removed 98.4% by weight of
suspended solids from the water samples used in this
study. Other workers such as Schemel et al. (2000) and
McKnight et al. (1992b) have also used 0.45 mm lters
to separate suspended particles from natural waters. A
blank was prepared with the deionized water that was
used for all laboratory procedures in this study. The
water used as a blank was exposed to the same type of
sample bottle, ltered using the same ltering apparatus,
and acidied with HNO3 in the same way as the water
samples. The concentrations of trace metals detected in
this blank are reported in Table 1. The only elements
that were above detection limits were: Mn (0.2 mg/l), Sr
(0.2 mg/l), Cu (0.3 mg/l), Pb (0.02 mg/l), Zn (2.0 mg/l), Ni
(0.1 mg/l), and Cd (0.02 mg/l). Therefore, no blank corrections were necessary for any of the elements included
in this study.
The precipitates were dialyzed in order to remove any
soluble salts by using Spectra/Por dialysis tubing with a
wet tube diameter of 48 mm and a molecular weight cut
o of 12,00014,000 Daltons. The deionized water surrounding the dialysis tubing was changed every 48 h for

one week (Winland et al., 1991). The precipitates were

subsequently freeze-dried and X-ray diraction patterns
were obtained using top-ll powder mounts and CuKa
radiation on a vertical, wide-range goniometer (Philips
DW 1316/90) equipped with a theta-compensating slit, a
0.2 mm receiving slit and a diracted-beam monochrometer. Specimens were scanned from 10 to 70
2

with a 4 s step time and a 0.05
2
step interval. Peak
positions were determined by using the Jade 3.0 software by Materials Data Inc. Approximately 50 mg of
the precipitates were dissolved in 75 ml of reagent-grade
2 M HCl, centrifuged, decanted, and diluted to 100 ml
with additional 2 M HCl in volumetric asks. The precipitates were found to be between 96.2 and 99.9% acid
soluble with quartz as the primary mineral residue. The
precipitates were analyzed for total organic C by Human Laboratories, Golden, Colorado, using standard
methods.
The concentrations of trace elements in the water and
in the dissolved precipitates were determined by XRAL
Laboratories in Toronto,Canada by ICPMS, whereas
concentrations of major elements were measured by
ICPOES. Detection limits for both methods are presented in Tables 1 and 2.
The SO4 concentrations of the water and precipitates
were determined by precipitation of BaSO4 after adding
5.0 ml of saturated BaCl2 solution to known volumes of
sample solution. After a period of 5 days, the BaSO4
solids were recovered with 0.45 mm lters, air-dried, and
weighed.

Table 1
Major and trace element concentrations for water samples in the Snake River below the conuence with Deer Creek reported in mg/l
Sample

Det. limita

1W

2W

3W

4W

5W

6W

7W

Blank

pH
Distance (m)
Al
Fe
SO4 (ppm)
Mn
Na
K
Ca
Mg
Rb
Sr
Cu
Pb
Zn
Ni
Cd
Co
Cr

50
50

0.1
50
100
50
50
0.1
0.01
0.1
0.01
0.1
0.1
0.01
0.1
0.1

3.6
7
4380
124
49.2
1700.0
2740
1230
11,370
6210
8.0
70.70
20.6
2.71
614.0
21.3
2.81
14.1
0.7

5.9
15
BDb
BD
31.1
226.0
1780
690
13,090
3260
1.6
46.10
8.4
0.37
186.0
8.1
0.73
2.2
0.7

6.3
17
BD
BD
32.8
116.0
1620
540
13,150
2780
1.3
50.80
5.2
0.61
136.0
5.8
0.47
1.3
0.5

5.2
37
2040
238
10.7
714.0
2240
850
12,550
4590
2.4
71.20
24.3
2.13
487.0
17.3
1.86
6.5
1.0

5.2
41
2030
272
42.1
714.0
2250
790
12,600
4490
2.1
69.00
19.1
1.43
426.0
14.4
1.49
5.5
0.5

5.3
48
4690
514
46.8
508.0
2220
790
12,510
4530
2.3
67.10
22.2
2.22
467.0
15.0
1.69
5.6
0.6

5.2
54
1130
130
29.4
516.0
2280
830
12,500
4520
2.5
57.40
16.3
1.10
429.0
15.7
1.38
6.0
0.6

BD
BD

0.2
BD
BD
BD
BD
BD
0.2
0.3
0.02
2.0
0.1
0.02
BD
BD

a
b

Detection limits in mg/l.

BD=below detection limit.

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L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

Table 2
Major and trace element concentrations of precipitates in the Snake River channel below the conuence with Deer Creek reported in
mg/g or wt.% of acid soluble precipitate
Sample

Det. limita

1P

2P

3P

4P

5P

6P

7P

pH
Distance (m)
Al%
Fe%
OC%
SO4%
Mn
Na
K
Ca
Mg
Rb
Sr
Cu
Pb
Zn
Ni
Cd
Co
Mo
Cr
W

50
50

0.1
50
100
50
50
0.1
0.01
0.1
0.01
0.1
0.1
0.01
0.1
1
0.1
0.01

3.6
7
12.7
7.1
13.5
12.9
180.8
543
410
1862
556
3.4
19.78
181.2
220.15
807.8
19.4
2.11
1.5
11
168.7
4.78

5.9
15
19.4
2.9
10.2
8.5
231.5
491
728
724
356
1.3
7.74
322.0
268.29
11,414.6
106.6
2.32
1.5
2
165.9
89.18

6.3
17
19.9
2.4
9.8
2.4
86.2
410
373
591
289
0.7
5.69
402.6
336.98
6593.8
196.7
3.92
1.1
4
132.4
339.55

5.2
37
20.5
2.8
6.5
9.7
41.9
465
429
608
326
0.9
4.44
150.2
89.24
542.7
19.9
2.71
0.6
8
89.4
235.07

5.2
41
22.5
3.6
5.3
13.6
54.1
569
616
3060
401
1.3
4.35
96.1
120.64
660.9
14.3
0.79
0.5
10
159.7
62.50

5.3
48
27.9
2.6
5.4
11.2
40.4
517
709
752
425
1.5
4.63
142.9
123.82
765.7
11.2
0.69
0.4
6
96.1
53.36

5.2
54
20.5
3.1
5.8
10.7
135.8
927
1399
701
431
3.0
4.85
89.2
105.79
718.4
22.4
1.55
1.1
11
138.7
21.46

Detection limits in mg/l.

2.2. Neutralization experiment

In order to determine the fraction of trace metals
sorbed as a function of pH, a sample of Snake River
water was progressively neutralized. Water collected
from just above the conuence with Deer Creek was ltered through a 0.45 mm lter, and 150 ml aliquots were
placed into 7 separate 200 ml Pyrex beakers. The initial
pH of this water was 3.1 when measured in the laboratory. One sample served as a reference for the remaining
6 subsamples, which were neutralized by adding a saturated solution of NaOH dropwise to obtain nal pH
values of 4.2, 4.8, 5.7, 6.0, 6.4 and 6.7. The solutions
were stirred once a day for one week and the pH of each
beaker was measured daily until it stabilized. The
increase in pH caused white precipitates to form, which
were similar in appearance to those collected in the eld.
After recovering the precipitates by ltering through
0.45 mm lters, the ltered solutions were acidied with
reagent-grade HNO3 and were analyzed for major elements by ICPOES and for trace elements by ICPMS.
Sulfate concentrations were determined by BaSO4 precipitation as described above. The fraction sorbed of
each element was calculated from the observed decrease
in the concentrations of the ltered solutions as compared to the control solution in the rst beaker. All ion

activities were calculated using the PHREEQC Interactive computer speciation model (Parkhurst, 1995).

3. Results and discussion

3.1. Precipitate mineralogy and metal sorption at the
Snake River/Deer Creek conuence
The pH of the Snake River increases from 3.0 above
the conuence to 6.3 just below the conuence with
Deer Creek and then stabilizes at 5.25.3 further downstream where the water is more completely mixed
(Fig. 2a). A occulent tan to white precipitate occurs on
the streambed in the mixing zone and further downstream. Chemical analyses indicate that the precipitates
collected from the Snake River streambed are composed
predominantly of Al-hydroxysulfate with signicant
quantities of associated Fe and organic C (Table 2). Xray diraction analyses of the tan to white precipitates
yield broad diraction bands centered at about 4.4, 2.2
and 1.5 A that are indicative of a material with very
short-range structural order. No further renements of
the precipitate mineralogy were attempted. The most
abundant trace metals in the precipitates include: Zn,
Cu, Pb, Ni, Cr, and W (Table 2). Concentrations of Zn,

L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

Fig. 2. (a) Changes in pH as a function of distance downstream

at the Snake River/Deer Creek conuence. (bf) Concentrations of Zn, Cu, Pb, Ni, and SO4 (ppm) in the precipitates
formed at the Snake River/Deer Creek conuence as a function
of distance downstream.

Cu, Pb, and Ni in the streambed precipitates as shown

in Fig. 2be increase with rising pH and then decrease
again farther downstream as the pH decreases.
In order to describe the distribution of cations between
water and precipitates forming at the conuence, the concentration ratio (CR) is introduced, which is dened as:
CR

Xs
:
Xl

Where (X)s is the concentration of an element in the

precipitate and (X)l is the concentration of the element in
the associated water. This parameter is not necessarily
identical to Kd because it is not certain that equilibrium
existed between the owing water and the precipitates

425

that accumulated on the streambed. In addition, an

unknown fraction of the precipitate collected at each
site may have been transported from locations
upstream. The concentration ratio (CR) should, therefore, be thought of as an enrichment factor, because the
concentrations of metals in the accumulated precipitates
are up to 3 orders of magnitude higher than those measured in the water (Tables 1 and 2). Nevertheless, the
numerical values of log CR for the metals included in
this study increase with rising pH as expected for log Kd
with log CR Pb > log CR Cu > log CR Zn > log CR
Ni. At pH 5.3 in the stream, log CR Pb is 5.3, log CR
Cu is 4.8, log CR Zn is 2.4, and log CR Ni is 1.9. This
sorption sequence is in agreement with laboratory
experiments reported by Dzombak and Morel (1990) for
the Kd values of these trace metals sorbed on fresh precipitates of hydrous ferric oxide.
Trace elements are concentrated in the precipitates
that form along the Snake River channel, whereas the
water in the mixing zone at the conuence is depleted in
these elements. The mixing zone is dened by samples
13 in Fig. 1. The data in Table 1 indicate that 75% or
more of the dissolved Zn, Cu, Pb, Ni, and Co are
removed from the water over a distance of only 12 m.
As a result, the quality of the water that ows through
this geochemical mixing zone is signicantly improved.
The concentrations of trace-metals in water samples 47
are slightly increased (Table 1), probably due to the
decrease in pH downstream. In addition, the interaction
of acid water with two galvanized metal culverts under
the road in Fig. 1 may contribute some Zn and Fe to the
Snake River water.
According to single-element batch experimental data,
cations should sorb least at low pH due to the net positive
charge of oxyhydroxide surfaces (Dzombak and Morel,
1990; Langmuir, 1997). However, the precipitates formed
at the conuence of the Snake River and Deer Creek have
high concentrations of Cu (180 ppm) and Pb (220 ppm)
even though the water is distinctly acidic (pH=3.6). Zinc
and Ni are also sorbed at pH=3.6, but their concentration ratios (CR) are lower than those of Pb and Cu. The
most likely explanation for this phenomenon is that
sorption of cations at low pH is facilitated by the presence of SO2
anions that form bridging complexes
4
between positively charged sites on the sorbent and the
sorbate cation. Webster et al. (1998) showed that SO2
4
ions enhance the sorption of Pb, Cu, and Zn onto natural mine-drainage precipitates and synthetic specimens
of schwertmannite and ferrihydrite.
The presence of humic substances may also enhance
the sorption of some trace metals (McKnight et al.,
1992b); however, Smith et al. (1999) reported that the
presence of natural organic matter (NOM) in acid sulfate waters containing high concentrations of Fe and Al
did not enhance the sorption of cations. Similarly,
Webster et al. (1998) reported that the presence of

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L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

humic acids had a negligible eect on the sorption of Cu

to ferric hydroxides. In addition, Ali and Dzombak
(1996a,b) demonstrated that at low pH SO2
4 ions compete extremely well with simple organic acids for sorption sites on goethite, and that the presence of SO2
4
ions enhances the sorption of Cu2+ by forming ternary
complexes. Recently, Zuyi et al. (2000) reported that, in

the pH range 48, variable concentrations of fulvic acid

do not increase the sorption of Zn to surfaces of Al2O3,
but that fulvic acid does compete for sorption sites with
univalent inorganic anions such as I . Therefore, humic
substances appear only to enhance cation sorption at
low pH in solutions that lack high concentrations of
divalent anions such as SO2
4 .

Fig. 3. Concentrations of Al, Fe, and OC (organic carbon) in the precipitates as a function of distance downstream.

Fig. 4. (a) Al3+ activity and (b) SO4 activity for the step-wise neutralization of Snake River water as a function of pH.

L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

427

In accordance with sorption theory, the concentrations of trace metals in the precipitate downstream of
the conuence should remain high because sorption of
cations is favored at elevated pH values of 56. The
reason for the comparatively lower observed concentrations of trace metals in the precipitate downstream of
the conuence is that signicant amounts of metals were
removed from the water upstream in the mixing zone.
Therefore, trace-metal concentrations of the precipitates
are not only pH dependent, but are also a function of
the distance downstream from the point of contamination due to the rapid depletion of trace metals by precipitation/sorption reactions.
3.2. Sulfate and organic carbon at the Snake River/Deer
Creek conuence
Many metallic and nonmetallic elements form oxyanions in well-oxygenated surface waters. These ions are
preferentially sorbed at low pH, but desorb as the pH rises.
Accordingly, the SO4 concentration of the precipitates
decreases from site 1 (pH=3.6) to site 3 (pH=6.3) and
then increases again downstream as the pH decreases to
5.25.3 (Fig. 2f). Organic C concentrations also decrease
as a function of distance downstream (Fig. 3) and
appear to be correlated with Fe, but not with Al, as
reported by McKnight et al. (1992b).
In the Snake River, SO4 is removed at pH=3.6 due to
the formation of an Al-hydroxysulfate precipitate and
because of sorption of SO4 to the surfaces of the Al(OH)3.
The concentration of SO4 in the precipitates at pH 6.3 is
lower than at pH 3.6, either because microcrystalline
gibbsite (Al(OH)3) formed or because of desorption of
some of the SO4, or due to a combination of both processes. Further downstream the concentration of SO4 in
the precipitate increases again because the pH decreases
from 6.3 to 5.2.
3.3. Neutralization experiment
In order to understand how trace elements are distributed between water and the precipitates that form in
the Snake River at its conuence with Deer Creek, a
sample of Snake River water, collected above the conuence, was progressively neutralized in the laboratory.
As the pH increased to 4.8 and above, the amount of
white precipitate increased (Fig. 5a). The activity of Al3+
in these solutions begins to decrease near pH 4.8 in Fig. 4a,
which also corresponds with the lowest SO4 activity in
Fig. 4b. These results indicate that at and above pH=4.8
the solutions were in equilibrium with Al-hydroxysulfate
and/or solid Al(OH)3, which is in agreement with results
reported by Nordstrom and Ball (1986) for Al-rich acidcontaminated waters. The concentrations of trace metals
in the ltered water prior to neutralization were: Pb=71
mg/l, Cu=96 mg/l, Zn=499 mg/l, and Ni=20 mg/l. The

Fig. 5. a. Amount of sorbent (mg/l) formed as a function of

pH. (b-f) Sorption edges for Pb, Cu, Zn, and Ni, and percentage removal of SO4 from neutralization of Snake River water.
Filled circles are data points from this experiment and the
dashed curves are interpolated from solid line sorption curves
reported by Dzombak and Morel (1990). The concentration of
Al in the water of the Snake River was 1.5  104 mol/l
whereas, Fe ranged from 1.00  104 to 1.00  103 mol/l in
the experiments reported by Dzombak and Morel (1990). The
concentrations of the trace metals in the Snake River and those
that were used in the experiments in Dzombak and Morel
(1990) were Pb=3.4  107 (this study) and Pb=5.00  107
mol/l (Dzombak and Morel, 1990); Cu=1.5  106 and 5.00 
107 mol/l; Zn=1.6  106 and 7.58  107 mol/l; and Ni=3.4
 107 and 5.00  107 mol/l; SO4=7.70  104 and was 1.00
 105 mol/l respectively.

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L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

fraction of Pb, Cu, Zn, and Ni sorbed increased with

increasing pH (Fig. 5be). At pH=4.8, Pb and Cu were
75% sorbed, whereas Zn was only 11% sorbed and Ni
was 18% sorbed. Lead was completely sorbed at
pH=5.7 and Cu at pH=6.4, whereas Zn and Ni were
not completely sorbed even at the highest pH (6.7)
reached in this experiment. Sulfate removal from solution began at pH=4.2 with the formation of the sorbent
and maximum removal was reached at pH=4.8, which
corresponds to the rst hydrolysis constant for Al.
Removal of SO4 from solution decreased with increasing pH. The activities of trace-metal ions indicate that
the solutions remained undersaturated with respect to
all possible trace-metal salts over the entire pH range.
Therefore, trace metals were removed from the water by
sorption on the surfaces of solid Al(OH)3 and/or Alhydroxysulfate that formed rather than by precipitation
of insoluble salts. The concentrations of Fe were below
the detection limit in all of the solutions utilized for this
experiment.
The sorption of Pb, Cu, Zn, and Ni in Figure 5b-e
increases with increasing pH in the same sequence as
previously reported from laboratory experiments with
simple solutions (Dzombak and Morel, 1990). Therefore, the results of the neutralization experiment indicate that sorption of ions from Snake River water was
inuenced by the composition and the amount of sorbent that formed, and by the pH which controlled the
solubility of the sorbent and the polarity of charged sites
on its surface. Sorption of the trace metals and removal
of SO4 did not begin until pH 4.2 in this experiment
because of the initial absence of sorbent in the ltered
water.
The sorption curves for the cations in Fig. 5be are
compared to data reported by Dzombak and Morel
(1990) for sorption on synthetic ferric hydroxide

(dashed curves). A corresponding data set for sorption

of trace metals to Al-hydroxysulfate or to microcrystalline Al(OH)3 has not been reported. Therefore, the data
from Dzombak and Morel (1990) were used for comparison even though in the neutralization experiment
the sorbent was mostly an Al-hydroxysulfate and/or
Al(OH)3, and the water contained a mixed suite of dissolved species. The sorption edges for Pb, Cu, Zn, and
Ni derived by laboratory neutralization of Snake River
water in Fig. 6be generally occur at lower pH than the
sorption curves reported by Dzombak and Morel (1990).
The variation is attributable to one or more of the following factors: dierences in the sorbate:sorbent ratio of
the aqueous phase and in the composition of the sorbent,
as well as the presence of SO4 and dissolved organic
material in the Snake River water. Sulfate removal
appears to be lower in the Snake River experiment
compared to experimental results reported by Dzombak
and Morel (1990), probably because the concentration
of SO4 in the Snake River is an order of magnitude
higher and complete removal/sorption of all the SO4
does not occur.
3.4. Sorption and transport processes at the Snake
River/Deer Creek conuence
The pattern of trace metal concentration in the Aloxyhydroxide precipitates in the channel of the Snake
River is reproduced for Cu in Fig. 6 by a simple calculation based on the results of the neutralization experiment described above. The calculation assumes that
water in the Snake River at pH=3.0 contains 100 ng/ml
of Cu as it ows into the mixing zone where the pH rises
to 6.3 due to dilution with water from Deer Creek.
According to the results of the neutralization experiment, 90% of the Cu sorbs at pH=6.0. Therefore, 90 ng

Fig. 6. Predicted sorption of Cu obtained from sorption data points for Cu in the Snake River and changes in pH measured as a
function of distance downstream. Numbers next to data points indicate the pH values used to interpolate percent sorbed from the
experimental sorption data.

L.-A. Munk et al. / Applied Geochemistry 17 (2002) 421430

of Cu are sorbed from each ml of water in the stream,

leaving only 10 ng/ml in the water. Farther downstream
at pH=5.5, 85% of the Cu is sorbed causing 8.5 ng of
Cu to be removed by the precipitate and leaving 1.5 ng/
ml in solution. Still farther downstream at pH=5.0,
80% of the remaining Cu is sorbed transferring 1.2 ng
of Cu to the precipitate for each ml of water such that
its concentration is reduced to 0.3 ng/ml. Similar calculations were performed for the other trace elements,
which produced curves having similar shapes as that in
Fig. 6. Therefore, this calculation adequately explains
why the concentrations of trace metals in the precipitate
decrease downstream even though the pH of the water
remains between 5.2 and 5.3. This calculation also
demonstrates why the concentrations of trace metals in
the Snake River decrease in the mixing zone at the conuence with Deer Creek, thereby improving the water
quality of the Snake River.

429

downstream and results in an improvement in the water

quality by natural processes.
Acknowledgements
This research was supported in part by funds from the
Friends of Orton Hall, Department of Geological Sciences, Ohio State University, and by a Graduate Student Alumni Research Award from the Graduate
School, Ohio State University. We thank Ken Bencala,
Jenny Webster-Brown, and Don Runnels for their
helpful reviews that improved this paper. In addition, I
(L. Munk) thank my collegues Giehyeon Lee, Nadine
Piatak, and Linda Centeno for their input that resulted
from numerous discussions about this research. Finally,
edits made by Erich Guy are greatly appreciated.

References
4. Conclusions
The Snake River is contaminated by acid rock-drainage, which results from the oxidation of pyrite and
other sulde minerals within the underlying bedrock of
the drainage basin. As the Snake River mixes with Deer
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form and sorb trace metals as the pH of the water
increases.
Experimental neutralization of Snake River water
shows that Pb, Cu, Zn, and Ni are sorbed with increasing pH, whereas SO4 is initially removed from the water
at low pH and is subsequently released as the pH
increases. In addition, the neutralization experiment
conrmed that there is a preferred sorption sequence
such that Pb is removed at the lowest pH followed by
Cu, Zn, and Ni. Sorption of trace metals at low pH is
enhanced by the presence of anions such as SO4, which
form ternary bridging complexes with the sorbent. The
results of the neutralization experiment demonstrate
that the sorption of trace elements can be eectively
investigated by neutralizing natural water samples in the
laboratory.
A sorption/transport calculation that combines the
results of the sorption experiment with observed changes in pH of the water reproduces the patterns of trace
metal distribution at the Snake River/Deer Creek conuence. In addition, the calculation accounts for the
progressive depletion of trace metals in the water and
for the resulting improvement in water quality.
The changes in pH of the environment control not
only the formation and the composition of the sorbent,
but also the partitioning of trace elements between
water and the precipitates. The progressive downstream
depletion of trace metals in the Snake River limits the
amount of trace metals available for sorption farther

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