Aquatic Geochemistry 5: 207223, 1999.

1999 Kluwer Academic Publishers. Printed in the Netherlands.

207

The Interaction of Natural Organic Matter with Iron

in a Wetland (Tennessee Park, Colorado) Receiving
Acid Mine Drainage
STEFAN PEIFFER1, KATHERINE WALTON-DAY2 and DONALD L.
MACALADY3
1 Limnological Station, Department of Hydrology, University of Bayreuth, D-95440 Bayreuth;
2 United States Geological Survey, Denver Federal Center, Box 25046, M5415, CO 80225, USA;
3 Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, 80315, USA

(Received November 1998)

Abstract. Pore water from a wetland receiving acid mine drainage was studied for its iron and natural
organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples
were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow
for vertical pore-water sampling. The iron concentration increased with time (through the summer)
and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the
surface, significant amounts of ferric iron (up to 40% of 2 mmol L1 total iron concentration) were
observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory
experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass
a 0.45-m dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM
concentrations (>100 mg C L1 ) allow formation of such colloids at the redoxcline close to the
surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow
paths and resultant export of ferric iron from the wetland into ground water might be possible.
Key words: natural organic matter, ferrous iron, ferric iron, wetland, colloidal iron, acid mine
drainage, pore water

1. Introduction
Iron is one of the main products of the weathering of pyrite (Theobald et al.,
1963). Together with high acidity, elevated iron concentrations characterize the
water chemistry of surface water that receives acid mine drainage. Such waters
also frequently contain elevated concentrations of trace metals (Chapman et al.,
1983; Karlsson et al., 1988; Nordstrom and Alpers, in press).
On entering a wetland, some metal ions are immobilized by sorption to or
precipitation as metal oxides or sulfides (Machemer and Wildeman, 1991; WaltonDay, 1991). Such processes are mainly linked to the redox chemistry of iron in the
wetland:

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STEFAN PEIFFER ET AL.

The precipitation of ferric iron as amorphous ferric oxides results in adsorption of trace metals (Tessier et al., 1985).
The reduction of ferric iron to ferrous iron and the subsequent formation
of pyrite may result in incorporation of trace metals into the mineral phase
(Huerta-Diaz and Morse, 1992). This process is the reverse of the metal release that occurs during weathering of pyrite.
A previous field study about the effect of a natural wetland receiving acid mine
drainage (Tennessee Park, Colorado) on ground-water chemistry, however, indicated a possible net export of filterable (<0.1 m) iron from the wetland sediments
into the deep ground water (Walton-Day, 1996). This conclusion was based on
measurements of filterable iron in the subsurface. Elevated concentrations of filterable iron may be due to the formation of ferrous iron under reducing conditions.
Alternatively, solubilization of ferric iron composing 20% of total iron concentration by the high concentrations of natural organic matter (NOM) in the ground
water of the wetland (up to 40 mg L1 ) needs to be considered. Natural organic
matter is known to favour stabilization of ferric oxides as colloids (Tipping and
Cooke, 1982; Liang and Morgan, 1990; Amirbahman and Olson, 1995).
The objective of this study is to describe interactions between filterable NOM
and iron in a wetland and assess whether and how NOM increases the solubility of
iron. The dynamics of these components were studied in a pore-water depth profile
in the wetland at three different times, using a novel sampling technique. Additionally, the NOM from these samples was fractionated according to its hydrophobicity,
and the effect of flocculation of filterable iron on the NOM fractionation was
studied.
2. Study Site
The wetland is in the western part of Tennessee Park, an intermontane valley at
the northwestern headwaters region of the Arkansas River about 7 km northwest
of Leadville, Colorado (Figure 1). The wetland is about 26 hectares in size and is
located at about 2990 m elevation.
Geology in the vicinity of the wetland has been described in detail elsewhere
(Walton-Day, 1991). The St. Kevin Gulch area, in the foothills west of the wetland, consists of Precambrian schists, gneiss, and the St. Kevin Granite. Faults of
Tertiary Laramide age contain silver-bearing veins and were mined for silver, lead,
and zinc beginning in 1883 and continuing intermittently to the late 1980s. The
weathering of pyrite and other sulfide minerals in the mineral deposits causes acid
mine drainage in the area.
The wetland is mapped as lake flats (Capps, 1909) and as Quaternary alluvium
(Tweto et al., 1978) and probably contains a mixture of alluvium and deposits
from shallow lakes, which may have existed after glaciation. The wetland receives
surface water from at least five sources. A principal source of acid mine drainage

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

Figure 1. Location of the wetland and the monitoring wells.

209

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STEFAN PEIFFER ET AL.

emanates from tailings piles located about 2 km upstream from the discharge of
St. Kevin Gulch into the wetland. This acid mine drainage has a pH of 2.7 and
contains elevated concentrations of many constituents (Smith, 1991). The acid
mine drainage is diluted by the water of St. Kevin Gulch to a pH ranging from
3.5 to 4.5 before entering the wetland.
The ground-water system of Tennessee Park consists of a sand and gravel aquifer
overlain by the wetland (Paschke and Harrison, 1995). The hydrology of the wetland is characterised by a rise in the water table between October and June (WaltonDay, 1991) caused by accumulation of in-situ snow melt, and by excess surfacewater runoff. During the runoff period (May and June), slight upward gradients
cause minor ground-water flow into the base of the wetland sediments from the
underlying aquifer. As runoff wanes during the summer (July and August), the
water table in the wetland gradually lowers and the ground-water gradients reverse:
Water from the wetland sediments recharges the underlying aquifer.
3. Material and Methods
3.1.

SAMPLING DESIGN

3.1.1. Shallow ground-water sampling

Samples were collected from the shallow ground-water monitoring wells MW-10
and MW-13 and from St. Kevin Gulch near MW-13 (cf. Figure 1) at four times
during the period of decreasing water table in the wetland (June 13, July 6, July
28 and Aug. 22, 1994). Additional ground water was sampled from wells MW-8
and MW-6 on June 13. Ground-water samples were collected after at least three
casing volumes of water had been pumped from each well or after stabilization of
conductivity. All monitoring wells are screened over a 60-cm interval at a depth
greater than 1 meter below the ground surface. For a detailed description of the
well construction, see Walton-Day (1991). The samples were analyzed for pH,
conductivity, alkalinity, dissolved sulfide, NOM, and total and ferrous iron (cf.
Section 3.3 for the details).
3.1.2. Pore-water sampling
To gain information about the redox transformations close to the water table in the
wetland, dialysis pipes were constructed that allowed the sampling of pore water
at different depths close to well MW-13 (Figure 2). Screened polyvinylchloride
(PVC) pipes, with a diameter of 3.75 cm and of different length (6, 12, 18 and
30 cm) were threaded on both ends (Figure 3). Into one end, a solid PVC tap was
glued, to which a second PVC pipe could be screwed. A series of such pipes thus
forms a longer pipe with the individual segments sealed against each other. In the
field, a single pipe segment was pushed into predrilled holes until the segment
was covered with water, and a glassy serum bottle (height 3.5 cm,  1.5 cm)
was placed into the segment. Then, a second pipe segment was screwed onto the

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

211

Figure 2. Location of the pore-water well. The inset shows the decreasing water level in the
well.

first one and pushed deeper into the hole and so on. Like dialysis chambers (e.g.,
Hpner, 1981) the serum bottles were filled with deionized and deaerated water in
the laboratory. Instead of the rubber septum, the vials were covered with a cellulose
acetate membrane (0.45 m), which allowed diffusive transport of ions from the
pore water entering the PVC pipe.
After a period of equilibration, on three dates during the summer of 1994 (July
6, July 28 and August 22), the pipes were removed and the membranes of the
serum bottles were opened. The samples were either analyzed directly in the field
using field kits (cf. Section 3.3 for the details) or filled into glass vials for TOC
analysis in the laboratory. No conservation of the TOC samples was performed.
The equilibration times were 22, 22, and 25 days.

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STEFAN PEIFFER ET AL.

Figure 3. Scheme of two segments of the dialysis pipes for pore-water sampling. More
segments can be added to the top. See text for a detailed description of the device.

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

213

The great advantage of this construction is its flexibility with respect to the
variable water table. Unlike dialysis chambers, which usually cover only a short
vertical distance (40 cm), this system permits one to follow the declining water
table and to sample with a higher resolution (here 6 cm) at this depth, whereas at
deeper levels, larger PVC segments can be used.
3.2.

FRACTIONATION OF NATURAL ORGANIC MATTER

Fractionation of NOM was studied in a sample from pore water close to well MW13 and from ground water from well MW-6. In this sample, which had been stored
in the refrigerator for approximately 1.5 years, all dissolved iron was in the ferric
form (see Section 4.1). To study the effect of colloid stabilization by NOM, the
fractionation was performed before and after ferric iron in solution was flocculated
using 0.1 mol L1 MgCl2 .
The XAD-fractionation technique as described by Thurman (1984) was used.
In brief, an acidified sample is pumped at a constant flow rate of 1 mL min1 into
a column that is packed with a nonionic acrylic ester (XAD-8). In a first step, the
humic substances of the NOM adsorb to XAD-8, whereas the hydrophilic effluent is collected and analyzed for its organic matter content. In a second step, the
column is back-eluted with NaOH, and the eluate with the humic substances also
is collected and analyzed for its organic matter content. In this article we present
results from the first step only.
3.3.

ANALYTICAL TECHNIQUES

Field kits (HACH) were used to measure alkalinity, dissolved sulfide, total iron
and ferrous iron in the field directly after sampling. The time span between the
opening of the vials and the fixation of a sample aliquot in the field kits never
exceeded 1 minute so that interferences by degassing of hydrogen sulfide or oxidation of ferrous iron can be excluded. Except for alkalinity, all concentrations
were determined colorimetrically, and all concentrations are mean values (SD =
<4%) of comparisons of the sample color to the color of standards made by at
least three people. Alkalinity was determined using the colorimetric endpoint of
Bromcresol blue. For ferrous and total iron analysis, a laboratory check, using the
phenanthroline method (Marczenko, 1976), indicated a bias of the field kit method
and nonlinearity of the readings, perhaps due to the high concentration of NOM.
Therefore, all field measurements had to be corrected according to:
1.379
c(Fe(II)) = 0.682 c(Fe(II))field

(1)

1.325
c(Fetot ) = 0.578 c(Fetot)field

(2)

where c(Fe(II))field , c(Fetot )field is the concentration of Fe(II) and total iron, respectively, as measured by use of a field kit.

214

STEFAN PEIFFER ET AL.

Table I. Natural organic matter (NOM) concentration and percentage of humic substances
retained after XAD-8 fractionation of NOM from ground water samples from well MW-6
before and after flocculation of ferric iron with 0.1 mol L1 MgCl2 and from pore waters of
two different depths sampled close to well MW-13 (cf. Figure 2). All NOM concentrations
given are in mg Carbon L1 . The well MW-6 sample was stored in the refrigerator for 1.5
years.
Sample

Untreated

Hydrophilic
effluent from the
XAD column

Percentage of humic
substances retained

Well MW-6 with iron

Well MW-6 after flocculation
Pore water 53 cm below
surface (Aug. 22, 1994)
Pore water 60 cm below
surface (Aug. 22, 1994)

22.4 0.9
14.6 0.1
64.1 0.1

12.0 0.7
16.6 0.5
25.6 0.9

46 3

60 2

28.5 0.6

20.3 1.6

29 2

The bias due to reduction of the colorless ferric iron phenanthroline complex in the presence of NOM and subsequent color formation was negligible (<
1 mol L1 ) within the one minute reaction time before reading. Natural Organic
Matter was measured using a TOC-analyzer after addition of 1 volume percent
concentrated HCl. The deionized water had relatively high blank values of 2.5 mg
C L1 . Detection limits were 0.03 mmol L1 for iron, 5 mol L1 for S(-II),
0.1 mmol L1 for alkalinity and 0.5 mg L1 for NOM.

4. Results
4.1.

FRACTIONATION OF NATURAL ORGANIC MATTER

Table I shows the results from the XAD-8 fractionation procedure. The data indicate that 40 to 60% of the NOM in the pore water close to well MW-13 and
in the ground water from well MW-6 was of hydrophilic nature. The initial iron
concentration in the well MW-6 sample we used was 442 mol L1 in the ferric
form and was filterable through an 0.45-m cellulose acetate filter. It could be
almost completely flocculated on addition of 0.1 mol L1 MgCl2 . This procedure
resulted in a decrease of the total iron content to 14 mol L1 and the NOM content
to 65% of the initial value. Flocculation of iron also resulted in a complete removal
of the NOM fraction containing the humic substances from the solution, which
then contained only hydrophilic compounds of the NOM.

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

4.2.

215

PORE - AND GROUND - WATER COMPOSITION

Table II presents an overview of the water chemistry in the shallow ground-water

wells. All wells are reduced and contain dissolved sulfide; well MW-6 contained
the greatest concentrations. Ferric iron was present in all wells, except in well MW6 where sulfide concentrations were the greatest. The pH increases slightly towards
the outflow from the wetland. Although the water table fell during the summer, the
water chemistry in wells MW-13 and MW-10 was fairly stable. In contrast, St.
Kevin Gulch clearly reflects the seasonal variations. The pH, alkalinity, and NOM
concentration increase towards the end of summer. In addition, at St. Kevin Gulch
on July 28, one-third of the total iron was in the ferrous form, and on Aug. 22 40%
was in the ferrous form, which is due to photoreductive processes (McKnight et
al., 1988).
Seasonal variation was also observed in the pore waters. Figure 4 shows a plot of
the total iron concentration versus depth in the pore-water well. Although we could
not analyze the pore water in the upper few centimeters on July 6, it is clear that
the total iron concentration is highest on July 28, except at 50-cm depth. The iron
concentration peaks within 15 cm of the surface on July 28 and Aug. 22, which
coincides with the decreasing water level at these sampling dates (cf. Figure 2).
On July 6, the wetland was still flooded at this well. It seems that the decreasing
water level coincides with an increase in concentration of species in the pore water
relative to the well water by a factor of three for dissolved iron and even higher for
the NOM (cf. Figure 4 and Figure 5).
The decreasing water level also affects the redox conditions in the system with
the relative portion of ferric iron highest on July 28 comprising more than 40%
of the total iron content (Figure 6). It further seems that the iron concentration is
closely related to the high organic carbon content (>100 mg L1 , Figure 5), which
also is highest on July 28. A linear-regression analysis between these two variables
was calculated with data from the sampling dates July 28 and Aug. 22 and from all
depths, which yields (r 2 = 0.89, p > 0.999, c(NOM) and c(Fetot ) in mmol L1 ):
c(Fetot ) = 0.31 0.083 + (0.17 0.017) c(NOM)

(3)

5. Discussion
As was pointed out in Section 4.1, the ground-water sample from well MW-6 was
stored in the refrigerator for more than a year and still had an iron concentration of
442 mol L1 at a pH of 6.4, which was all in the ferric form. Such a concentration
distinctly exceeds the solubility of ferric oxides at this pH,
Fe(OH)3 Fe3+ + 3 OH

(4)

which would be 1015.2 mol L1 (Ksp(FeOH3) 1038 mol4 L4 , Stumm and Morgan, 1996). Iron could not be removed by filtration through a 0.45-m filter, which

216

Table II. Composition of ground water and water from St. Kevin Gulch close to well MW-13 at various sampling dates
during summer 1994 (n. d. = not detectable; blanks indicate that the parameter was not measured). AlK = alkalinity;
S-(II)t ot = total sulfide; el. cond. = electrical conductivity.
Date

MW-8
MW-6
MW-13

Jun 13
Jun 13
Jun 13
Jul 6
Jul 28
Aug 22
Jun 13
Jul 6
Jul 28
Aug 22
Jul 6
Jul 28
Aug 22

MW-10

SK Gulch

NOM
(mg C L1 )

20.0
10.0
8.2
26.6
16.2
11.8
6.1
4.3
35.3

Fe2+
(mmol L1 )

Fe3+
(mmol L1 )

Alk
(meq L1 )

S(-II)tot
(mol L1 )

pH

El. cond.
(S)

0.20
0.54
0.28
0.28
0.36
0.36
0.60
0.38
0.60
0.54
n. d.
n. d.
n. d.

n. d.
n. d.
0.09
0.06
0.04
0.06
n. d.
0.18
n. d.
0.09
n. d.
n. d.
n. d.

0.5
1.2
1.2
0.8
0.9
0.8
1.5
1.3
n. d.
1.3
n. d.
0.04
0.85

4.7
46.0
5.3
n. d.
n. d.
n. d.
6.2
n. d.
n. d.
15.6
n. d.
n. d.
n.d.

5.6
5.6
6.1
6.2
6.0
6.0
6.2
6.7
6.6
6.1
4.3
5.4
5.9

230
213
246
212
225
204
252
263
271
264
150
135
149

STEFAN PEIFFER ET AL.

Well #

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

217

Figure 4. Vertical pore-water profiles of total dissolved iron on three different dates. The
concentration increases during summer and shows maxima close to the water level and at
40-cm depth.

indicates that the ferric iron stays in solution either complexed by the NOM or as
very small colloids.
The NOM content of the well MW-6 sample is 24.6 mg C L1 . Therefore, the
molar Fe/C-ratio is 0.22, which is similar to the ratio described by Equation (3).
Such a ratio implies that extremely small organic ligands complex the ferric iron,
which seems unreasonable. McKnight et al. (1985) reported that the fulvic acids
isolated from a Sphagnum bog with similarly high NOM concentrations have a
molecular mass range from 1000 to 5000 g mol1 and a mean carbon content of
48.5%. Even with a molecular mass of 1000 g mol1 , the resulting total ligand concentration would not exceed (24.6 mg L1 /0.485/1000 g mol1 ) 50 mol L1 .
Given the dissolved-iron concentrations of 442 mol L1 , ferric iron in the stored
well MW-6 sample would be excessive compared to organic ligands, and therefore,
precipitation of iron as ferric hydroxides would be favoured. It seems, however,
that fulvic acids are associated with the ferric oxides. From Table I it becomes

218

STEFAN PEIFFER ET AL.

Figure 5. Vertical pore-water profiles of NOM at two different dates. The NOM concentration
correlates well with the total iron concentration (Figure 4).

clear that the addition of MgCl2 coprecipitates the humic substance fraction of the
NOM together with the iron. In addition, the concentration of carboxylic groups
of the NOM exceeds that of reactive surface sites at the ferric oxide surface as the
following rough estimate indicates:
c(COOH) = c(NOM) CSC 120 mol L1

(5)

where c(-COOH) is the concentration of carboxylic groups in solution; c(NOM) is

the concentration of NOM in solution, 0.0246 g C L1 ; CSC is the coordinating
site content, 4.54.9 mmol (g NOM)1 (Buffle, 1988)
c(sites) = c(Fe) MMFe SSA SCRS 20 mol L1

(6)

where c(Fe) is the concentration of iron, 442 mol L1 ; MMF e the molecular mass
of iron, 55.9 g mol1 ; SSA the specific surface area, 300 m2 g1 (Dzombak and
Morel, 1990); SCRS the surface concentration of reactive sites, 2.2 mol m2
(Dzombak and Morel, 1990)

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

219

One might envison a surface reaction between the carboxylic groups of the
fulvic acids and the ferric oxides (Tipping, 1981; Balistrieri and Murray, 1987)
that results in a negative surface charge of the particles (Tipping and Cooke, 1982).
We, therefore, hypothesize that the suspended ferric oxides are stabilized by the
adsorbed NOM.
Fulvic acids have a positive effect on the colloid stability of hematite, provided that the pH is close to neutral (between 6 and 7) and the concentration of
Ca2+ and Mg2+ is low (Liang and Morgan, 1990; Amirbahman and Olson, 1995).
Moreover, oxidation of ferrous iron in the presence of high amounts of organic
compounds seems to promote the formation of extremely small ferric oxide
particles (von Gunten and Schneider, 1991). At fulvic acid concentrations
>0.1 mg L1 , colloid stability may arise from repulsion between negatively
charged goethite particles to which humic substances are adsorbed (Liang and
Morgan, 1990). In hard water, the negative charge is balanced by Ca2+ and Mg2+
ions (Tipping and Cooke, 1982) resulting in reduction of colloid stability (Amirbahman and Olson, 1995). Therefore, conditions in the shallow ground
water of the Tennessee Park wetland are ideal for forming stable colloids with
its soft water (6c(Ca), c(Mg) < 1 mmol L1 , Walton-Day, 1991), circum-neutral
pH, high ferrous iron, and NOM concentrations (Table II).
The high percentage of dialysable ferric iron in the pore waters of the wetland
during summer (Figure 6) may be explained by the combined effect of oxidation of ferrous iron and colloid formation in the presence of high amounts of
NOM. Enhanced breakdown of organic matter and excretion of NOM from the
higher plants is concomitant with the increase of primary productivity of the biomass in the wetland during summer (Hemond, 1982; Wetzel, 1983) and results in
high surface concentrations of NOM in the wetland. McKnight et al. (1985) also
observed greater NOM concentrations at the surface of a Sphagnum bog with a
maximum of 62 mg L1 at late summer. Additionally, evapotranspiration affects
the concentration of dissolved compounds (Mulholland and Kuenzler, 1979) so
that a seasonal increase of NOM in the pore waters of wetlands with a maximum
during mid-summer is a common phenomenon in wetlands (Marin et al., 1990,
Yavitt, 1994). Also, the oxygen production is enhanced close to the surface. As
Wetzel (1983) states, higher plants in wetlands are colonized by epiphytic algae,
whose productivity and oxygen production often exceed that of the macrophytes.
The high redox potential then favours oxidation of ferrous iron. In the presence of
excess negative surface charge from the NOM, ferric oxide colloids then are able
to form. A time scale analysis according to Webster et al. (1998) demonstrated that
the equilibration time in the field is sufficient to allow diffusion of such colloids
into the serum bottles. The time necessary to establish 90% equilibrium of the iron
colloids (size of the iron colloids: 5 nm; diffusion coefficient: 4 107 cm2 s1 )
would be 27 days, which is somewhat longer than the equilibration time we used
(cf. Section 3.1).

220

STEFAN PEIFFER ET AL.

Figure 6. Vertical profile of the ratio: ferric to total iron in the pore water. The high ratio close
to the surface on July 28 reflects changing redox conditions during summer.

Liang et al. (1993) observed similar effects of NOM that was injected with
oxygen-containing water into a sandy aquifer containing Fe(II). Because of the
presence of NOM, small colloids (<3000 molecular mass) formed on oxidation of
the ferrous iron at low oxygen tensions, which then were transported along flow
paths in the ground water.
Accordingly, the decrease of NOM and iron (particularly ferric) concentration
in late August can be explained by a decrease of the photosynthetic activity towards
the end of summer. However, our data do not allow an explanation for the second
peak of both substances at about the 40-cm depth. Stability of the NOM-coated
ferric oxide colloids under reducing conditions has not yet been investigated. However, the occurrence of these species in the deeper monitoring wells even in the
presence of low concentrations of sulfide (Table II) indicates some degree of redox
stability.

THE INTERACTION OF NATURAL ORGANIC MATTER WITH IRON

221

6. Conclusion
The pore-water sampling device designed for this study was an important tool to
elucidate the dynamics of the interaction between iron and NOM in a wetland of
varying water levels. There is strong evidence from this study that the elevated
NOM concentrations in this wetland have a significant mobilizing effect on ferric
iron. Our data indicate that the following processes occur at the boundary between
oxic and anoxic pore water close to the surface of the wetland. During summer,
evapotranspiration results in a subsurface concentration of dissolved substances,
such as ferrous iron, in the pore water. This effect coincides with high photosynthetic activity that produces large amounts of organic carbon and also pumps
oxygen into the pore water; therefore, oxidation of ferrous iron can occur in the
presence of high NOM concentrations. Given the low hardness of the pore water,
conditions are ideal for the formation of small iron oxide colloids stabilized by
surficially bound organic matter. This effect is reflected by the high fraction of
ferric iron compared to the total dissolved iron concentration found in these pore
waters.
Because the wetland is underlain by an oxic deeper ground-water aquifer, we
hypothesize that similar processes occur at the bottom of the wetland. Because of
reducing conditions in the wetland, ferrous iron is transported during summer to
the redoxcline at the oxic aquifer. Oxidation to ferric iron occurs in the presence of
NOM and, therefore, part of the ferric oxide is stabilized as colloidal iron. These
small particles then can be transported with the ground water, which could explain
the net export of iron from the wetland hypothesized by Walton-Day (1991).

Acknowledgments
This study was performed as part of a grant given by the Deutsche Forschungsgemeinschaft (Pe 438/2-1) to the first author of this paper. We are grateful to Suzanne
Paschke, Marion Peiffer, Jim Ranville, and Ning Li Zu for their field assistance, to
Diane McKnight for her support in the XAD fractionation and to Silke Br for the
measurements of the NOM. We thank Aria Amirbahman and Diane McKnight and
two anonymous reviewers for their critical comments on an earlier version of this
manuscript. Vern Tate assisted in the design of the pore-water samplers.

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