Tracing Sources of Streamwater Sulfate during Snowmelt Using S and O Isotope Ratios

of Sulfate and ${}^{35}\text{S}$ Activity

Author(s): James B. Shanley, Bernhard Mayer, Myron J. Mitchell, Robert L. Michel,
Scott W. Bailey and Carol Kendall
Source: Biogeochemistry , Oct., 2005, Vol. 76, No. 1 (Oct., 2005), pp. 161-185
Published by: Springer

Stable URL: https://www.jstor.org/stable/20055295

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Biogeochemistry

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Biogeochemistry (2005) 76: 161-185 ? Springer 2005
DOI 10.1007/sl0533-005-2856-9

Tracing sources of streamwater sulfate during

snowmelt using S and O isotope ratios of sulfate
and 35S activity

JAMES B. SHANLEY1'*, BERNHARD MAYER2, MYRON

J. MITCHELL3, ROBERT L. MICHEL4, SCOTT W. BAILEY5
and CAROL KENDALL4
!U.S. Geological Survey, P.O. Box 628, Montpelier, VT 05602, USA; 2Department of Geology and
Geophysics, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N IN4;
3State University of New York, College of Environmental Science and Forestry, 1 Forestry Drive,
Syracuse, NY 13210, USA; 4U.S. Geological Survey, 345 Middlefield Road, MS 434, Menlo Park,
CA 94025, USA; 5USDA Forest Service, Northeastern Research Station, Hubbard Brook Experi
mental Forest, 234 Mirror Lake Road, Campton, NH 03223, USA; *Author for correspondence
(e-mail: [email protected]; Phone: +1-802-828-4466; fax: +1-802-828-4465)

Received 28 April 2004; accepted in revised form 28 February 2005

Key words: Isotopic tracers, Oxygen-18, Sulfate, Sulfur-34, Sulfur-35, Vermont, Sleepers River

Abstract. The biogeochemical cycling of sulfur (S) was studied during the 2000 snowmelt at
Sleepers River Research Watershed in northeastern Vermont, USA using a hydrochemical and
multi-isotope approach. The snowpack and 10 streams of varying size and land use were sampled
for analysis of anions, dissolved organic carbon (DOC), 35S activity, and ?34S and <5180 values of
sulfate. At one of the streams, ?l80 values of water also were measured. Apportionment of sulfur
derived from atmospheric and mineral sources based on their distinct ?>34S values was possible for 7
of the 10 streams. Although mineral S generally dominated, atmospheric-derived S contributions
exceeded 50% in several of the streams at peak snowmelt and averaged 41% overall. However,
most of this atmospheric sulfur was not from the melting snowpack; the direct contribution of
atmospheric sulfate to streamwater sulfate was constrained by 35S mass balance to a maximum of
7%. Rather, the main source of atmospheric sulfur in streamwater was atmospheric sulfate
deposited months to years earlier that had microbially cycled through the soil organic sulfur pool.
This atmospheric/pedospheric sulfate (pedogenic sulfate formed from atmospheric sulfate) source is
revealed by ?l80 values of streamwater sulfate that remained constant and significantly lower than
those of atmospheric sulfate throughout the melt period, as well as streamwater 35S ages of
hundreds of days. Our results indicate that the response of streamwater sulfate to changes in
atmospheric deposition will be mediated by sulfate retention in the soil.

Introduction

Trends and patterns of sulfate concentrations in streamwater have received

much attention for several decades because sulfate plays a dominant role in the
anthropogenic acidification of surface waters (Reuss and Johnson 1986; Likens
and Bormann 1995; Driscoll et al. 2001; Likens et al. 2002). In recent years
attention in the USA and Europe has focused on how stream sulfate responds
to decreases in atmospheric deposition of sulfate (Stoddard et al. 1999; Clow

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 162

and Mast 1999). Trend detection in surface waters may be confounded by the
presence of sulfate produced by weathering of sulfur-containing minerals in the
watershed bedrock (Turk et al. 1993; Mayer et al. 1995a; Alewell et al. 1999;
Bailey et al. 2004). Rochelle et al. (1987) concluded that sulfate was in
approximate balance in many ecosystems in glaciated areas of eastern North
America, but more recent studies have found that the amount of sulfate
exported in drainage waters exceeds atmospheric inputs, suggesting the
importance of an internal sulfur source (Driscoll et al. 1998; Alewell et al. 1999;
Mitchell et al. 2001a, b; Likens et al. 2002). Accounting for geologic sulfate
sources is essential in analyzing the response of sulfate in streamwater to
changes in atmospheric deposition.
Sulfur may be retained in a catchment by adsorption, mineral precipitation,
uptake, and assimilatory or dissimilatory bacterial sulfate reduction (BSR).
These abiotic and biotic processes can result in a substantial residence time of
sulfur in soils (Mayer et al. 1995b; Alewell 2001; Novak et al. 2001), causing a
lag in streamwater response to changes in atmospheric sulfate inputs.
Stable isotope ratios of sulfur (34S/32S) have been used to assess the relative
contributions of atmospheric, pedospheric, and lithospheric sulfur to streamflow
(e.g. Krouse and Grinenko 1991; Mitchell et al. 1998). The ?34S values of mineral
sulfur vary widely (Nielsen et al. 1991), sometimes even within a small geographic
area (Bailey et al. 2004). In some areas, the ?34S values of atmospheric S also vary
and this variation has been used to apportion S sources (Alewell et al. 2000; Mast
et al. 2001). In the northeastern USA, however, <534S values of sulfate in atmo
spheric precipitation are often quite consistent, and average near 5%0 (Mitchell et
al. 1998). If <534S values of precipitation and bedrock are uniform within each
source but distinct from one another, and isotope fractionation effects during
sulfur transformations are minimal, then ?>34S values of sulfate in streamwater
may be used to quantify atmospheric and weathering sources of S. Isotopic
approaches provide constraints on the pools, cycling, and residence time of
sulfate that may be applied in models that predict ecosystem response to changes
in atmospheric input (Gbondo-Tugbawa et al. 2002).
Atmospheric sulfur contains a small quantity of the cosmogenic radioactive
isotope 35S (half-life 87 days). Detectable 35S in streamwater indicates the pres
ence of S deposited from the atmosphere within the last 1-2 years (Michel and
Naftz 1995; Sueker et al. 1999; Michel et al. 2000). If the decrease in specific
activity of 35S (mBq per mg S04) from precipitation to streamflow is due solely
to radioactive decay, it may be used to estimate an average age of streamwater
sulfate, and thus to assess how rapidly S cycles through a catchment (Michel et al.
2000). However, specific 35S activity may be diluted by 35S-free sulfate generated
from mineral weathering, resulting in an older apparent age of atmospheric S
unless the non-atmospheric component is subtracted before the calculation.
Much of the atmospheric sulfate entering a watershed is retained in the soil
and vegetation. Although <534S values and 35S activity help to distinguish
atmospheric and geologic S sources and to estimate ecosystem residence time
of S, they usually provide only limited information on S cycling in the soil

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 163

(Mitchell et al. 2001a; Novak et al. 2001). For estimating the contributions of
these soil S sources, <5180 values of sulfate (Mayer et al. 1995b; Kester et al.
2003) and more recently <S170 values of sulfate (Bao et al. 2001; Lee et al. 2001;
Johnson et al. 2001) have proved especially useful. Atmospheric sulfate is
enriched in 180 because it derives some of its oxygen atoms from atmospheric
02, which has a <5180 value of +23%0 (Kroopnick and Craig 1972). When
atmospheric sulfate undergoes assimilatory bacterial sulfate reduction and re
oxidation in the soil, the distinctive high ?180 value is lost and reset to a lower
(5180 value (e.g. Mayer et al. 1995b) because some oxygen atoms in the sulfate
are replaced by oxygen from soil water with negative ?lsO values (Krouse and
Mayer 2000). These processes typically have only a small effect on the ?34S
values of sulfate unless dissimilatory bacterial sulfate reduction occurs
(Mitchell et al. 1998). The various processes affecting the isotopic composition
of sulfate are depicted in Figure 1.
At Sleepers River in northern Vermont, USA, Hornbeck et al. (1997)
reported that sulfate export in streamwater was greater than two times
atmospheric inputs during 1992-1994, suggesting a geologic S source. From a
regional survey, Bailey et al. (2004) reported that Sleepers River had an ele
vated S content in bedrock (7.9 mg S kg-1) with a relatively high <534S value
( + 8.5%0, significantly higher than the average <534S value of precipitation,
+ 5.6%0). Three base-flow stream samples had sulfate ?34S values of +7.3,
+ 9.1, and + 10.5%o, closely bracketing the value of the bedrock sample. These
initial analyses suggested that isotopic source apportionment of sulfate would
be possible at Sleepers River, leading to the current study.
The objective of this study was to provide new information on catchment S
cycling and dynamic variations of S sources during a hydrologie event using a
hydrochemical and multi-isotope approach. We chose to study snowmelt
because it is a hydrologically active time when 50% of the annual streamflow
typically occurs in a 6-week period. Our approach was to analyze the S34S and
c>180 values of sulfate and cosmogenic 35S activities in the snowpack, ground
waters, and surface waters to evaluate the relative contribution of different S
sources and the residence time of atmospherically derived S in the catchment. We
also applied hydrograph separation using ?lsO values of water to evaluate the
relative contributions of "new" and "old" water to discharge and the relation
between new water and sulfate concentrations and isotopic composition.

Methods

Site description

Sleepers River Research Watershed (Figure 2) in northeastern Vermont, USA,

was established in 1958 by the U.S. Department of Agriculture, Agricultural
Research Service, and is now operated by the U.S. Geological Survey (USGS).
Sleepers River was the site where the saturation-excess overland flow theory of

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 164

Precipitation and dry deposition

634S = 5.6; 5180= 12, high 35S activity

Throughfall
Little change Litterfall
Little change

Mineralization Assimilatory Bacterial O-horizon

S -Little change; Sulfate Reduction (C-S bond)
O of water/02 S -Little change; O reset A-horizon
Desorption Adsorption B-horizon
No change No change
Reoxidation Dissimilatory BSR
S -Large change; Water table
S -Large change; O of water/02
O -Moderate change

Weathering
Till/bedrock
S of source, no 35S,
O of source or water

Figure 1. Sulfur cycling in a forested ecosystem and resultant changes (in italics) in S and O
isotope ratios of sulfate. BSR means bacterial sulfate reduction. The isotope ratio values are given
for typical precipitation in northeastern USA. Processes within the regolith are paired horizontally
at the approximate depth in the system where they are most prominent. In general the process on
the right immobilizes aqueous sulfate and the process on the left makes it available for aqueous
transport, though in the case of dissimilatory BSR the sulfide may remain mobile, either in gas or
aqueous phase. Also, this latter process often occurs near the surface in saturated areas. Activity of
cosmogenic 35S (half-life 87 days) is highest in deposition, zero in weathering sources, and any
where in between within the soil zone depending on S residence time.

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 165

o.
E

8.

cd

S,

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 166

streamflow generation was developed by Dunne and Black (1970a, b; 1971).

Their work formed the basis for recent research on streamflow generation
processes using chemical and isotopic approaches (Kendall et al. 1999; Shanley
et al. 2002a). The 11,125-ha basin contains several gaged watersheds of various
size and land cover (Shanley et al. 2002a). This study was conducted primarily
within the 41-ha forested W-9 catchment and its tributary subcatchments, but
samples were also taken from the 59-ha agricultural W-2, and the larger mixed
land use watersheds W-3 (836 ha) and W-5 (11,125 ha).
The Sleepers River watershed is underlain primarily by the Waits River
Formation, a calcareous granulite interbedded with sulfidic micaceous phyllites
and biotite schists (Hall 1959; Bailey et al. 2004). The bedrock is mantled with
one to several meters of silty basal till derived mostly from the Waits River
Formation. The calcareous lithology generates high-pH calcium bicarbonate
sulfate waters throughout the Sleepers River watershed.

Field sampling

The study period encompassed the late winter and spring snowmelt of 2000,
from late February to late April. We collected 3-12 samples from each of 10
streams draining watersheds with areas from 2 to 11,125 ha, at the same times
and sites as samples collected for another study (Shanley et al. 2002b). We also
sampled 3 groundwater seeps and 4 shallow wells screened within the till (1.5-m
screens, maximum depth 3 m) within one day of peak snowmelt (4 to 5 April).
Stream sampling included a premelt sample before the hydrograph rise, and
then focused on high flows from both radiational melt and rain-on-snow
events. Samples were taken from the centroid of flow in 10-L collapsible
polyethylene (PE) containers for determination of 35S activity and in 1-L PE
bottles for determinations of the <534S and <5lsO values of sulfate. A 500-ml PE
bottle was filled for major anion and DOC analysis. Samples for analysis of
<5180 of water were collected in 16-ml glass vials with conical polyseal caps.
Meltwater was collected from snowmelt lysimeters to use as the atmospheric
end member in isotopic hydrograph separation (Shanley et al. 2002a). Depth
integrated snowpack samples were collected by removing an approximately
0.2 x 0.2 m column from the wall of an excavated pit with a lexan shovel into a
large PE container. Four open-field snowpack samples were taken near the
W-9 catchment on 23 February (just prior to a minor thaw) and two additional
samples were taken on 22 March (just prior to the onset of the main melt
sequence) for determination of sulfate concentrations, ?34S and ?lsO values of
sulfate, and 35S activity (22 March only).

Isotopic and chemical analyses

Samples for 35S activity determination were dripped through ion exchange
resin columns in the field. The 35S columns and water samples for <5180 analysis

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 167

were shipped to the USGS isotope lab in Menlo Park, CA. Sulfate was eluted
from the columns and analyzed for 35S as described in Michel et al. (2000).
Replicate precision averaged 0.71 mBq l-1 or 0.12 mBq/mg S04 (C.V. 33%).
The (5180 of water was determined with a precision of ?0.05%o. Samples for
anion analysis were filtered (0.45 /im) and chilled, and shipped to the USGS in
Boulder, CO, where they were analyzed by ion chromatography. Samples for
DOC were filtered (0.7-/im glass fiber) to amber glass vials and analyzed by
ultraviolet persulfate oxidation with infrared detection at the USGS laboratory
in Troy, NY.
Samples for determining the stable isotope composition of sulfate were
dripped through separate ion exchange columns in the field laboratory, and
columns were sent to the Isotope Science Laboratory (ISL) at the University of
Calgary (Alberta, Canada). In Calgary the sulfate was eluted from the column
and precipitated as BaS04 by adding a BaCl2 solution. The filtered, washed
and dried BaS04 was converted to sulfur dioxide (S02) in an elemental ana
lyzer and swept with a He stream into an isotope ratio mass spectrometer (VG
Prism II) for isotope ratio determinations. For oxygen isotope analyses on
S042_, BaS04-oxygen was converted to CO at 1450?C in a pyrolysis reactor
(Finnigan TC/EA). The resultant gas was subsequently swept with a He stream
into a mass spectrometer (Finnigan MAT delta plus XL) for isotope ratio
determinations in continuous-flow mode (CF-IRMS). Stable isotope ratios are
reported in the usual ? notation in permil with respect to the international
standards V-CDT for sulfur isotope measurements and V-SMOW for oxygen
isotope measurements. Precision (standard deviation on replicate analyses)
averaged 0.26%o for ?34S values and 0.53%o for <5180 values of sulfate.

Mixing models

?180 of water
Snowmelt is an ideal time for isotopic separation of streamflow into event and
pre-event water and the method has been successfully applied at Sleepers River
(Shanley et al. 2002a). As in past studies, streamwater was separated into old
and new water with a standard two-component <S180 mixing model using the
varying composition of meltwater from the lysimeters for the new water signal
and a constant pre-melt base flow for the old water signal.

S34S of sulfate
We applied a two-component sulfate-S source separation to differentiate
atmospheric from mineral-derived sulfate. This separation requires three
conditions: (1) a constant known <S34S value for atmospheric sulfate; (2) a
constant known <534S value for sulfate from mineral weathering that is
different from that of the atmospheric source; and (3) processes that frac
tionate sulfur isotopes such as dissimilatory bacterial sulfate reduction do
not occur.

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 168

We used snowpack ?>34S for the atmospheric end member and stream base
flow (534S for the mineral end member, giving a 2-3%0 difference between
atmospheric and stream base flow <534S values of sulfate that was small but
sufficiently distinct to satisfy condition (2). The fraction of atmospheric S in
streamwater was given by:

Satm = (S SBF - S Ssw)/(<53 SBf - ?34SSp) (1)

where subscripts ATM = atmosphere, SW = streamwater, BF = stream
water at base flow, and SP = snowpack.

?180 of sulfate
The <5180 of sulfate was treated identically to the <534S of sulfate, assuming two
component mixing and using an equation analogous to equation 1.

35S activity
The specific activity of 35S (mBq per mg S04) data were analyzed in two ways.
In the first approach, we attributed all of the 35S activity in streamwater to the
melting snowpack (and subsequent rainfall). This would yield a maximum
contribution from the snowpack as any remaining 35S activity from aged
atmospheric sulfur would be attributed to the snowpack. Mixing fractions were
calculated as for ?34S above, with the simplification that the 35S activity at
baseflow is zero so the analagous equation reduces to:

Snew = (a SSw/# Ssp) (2)

where SNEW is the fraction of new atmospheric S in streamwater and a refers
to the specific 35S activity. The second approach was to calculate the
apparent age of stream sulfate assuming simple radioactive decay of 35S in
precipitation:

A = r1/2ln(a35SSp/a35Ssw) (3)

where A is mean streamwater sulfate age in days and T\? is the half-life of
35S (87 days). After the atmospheric fraction of streamwater sulfate was
determined by Equation (1), its specific 35S activity was recomputed and
Equation (3) was re-applied to compute the age of the atmospheric fraction
of stream sulfate.

Results

Hydrology

Water Year 2000 (October 1999 through September 2000) at Sleepers River
featured the typical autumn flow increase with some high flow events, followed
by recession to winter base flow as precipitation was stored in the snowpack

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 169

?2.5
CD

is 20
CO
JZ
?
CO
' ? 1.5
CO
O
g 1.0
S
c

to
c
0.5

wuONDJFMAMJJAS
1999 2000

Figure 3. Daily precipitation amount and continuous st

water year at the 41-ha W-9 catchment at Sleepers Riv

(Figure 3). Snowmelt in March and April cl

rograph. In 2000 the snowmelt recession las
above-average rainfall in April and May. Th
the lowest flow of any of the nine summer
there were occasional moderate peak flows f
September.
The winter of 2000 was relatively mild with below-average snowfall. The
peak snow water equivalent (SWE) ranked 33 among 43 years of record from
1960 to 2002 (Shanley et al. 2002c). The winter was also unusual in that it
lacked a major thaw, but several minor warm-ups periodically reduced the
snow water equivalent and produced moderate streamflow. The main melt
sequence began in late March (Figure 4). Flow progressively increased with a
series of diurnal melts, culminating in two rain-on-snow events, 22 mm on 28
March and 29 mm on 4 April. These two storms generated the highest flows of
the melt period (1.2 and 1.3 mm h_1, respectively, in W-9, the headwater
catchment), and isotope sampling focused on these and subsequent snowmelt
peaks. These snowmelt peaks were less than those of most previous years, e.g.,
a 2.0 mm h"1 peak in 1996 (Kendall et al. 1999).

Solute chemistry

The sulfate concentration in the snowpack was 12 /ieq l-1 at its maximum
SWE of 199 mm on 23 February, just before a late winter thaw. On 22
March SWE was 169 mm and the sulfate concentration had decreased to
6.2 ??eq 1_1. Sulfate concentration in streamwater varied inversely with

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 170

Li 30
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21 26 31 5 10 15 20 25
March April
Figure 4. Daily precipitation with continuous hydrograph and hydrograph
of water during the main 2000 snowmelt period, with sulfate, DOC, and n
Isotopic hydrograph separation was not possible after isotopically heavy rai

Table 1. Sulfate mass balance at w-9 for water years 1992-1994 and for wa
and 35S mass balance at w-9 for the 2000 snowmelt period.

Units Input Output Ratio

Water year 1992-1994 (Hornbeck et al. (1997)) meq m~2 year 45.1 106.9 2.37
Water year 2000 meq m~2 year 48.1 131.3 2.73
2000 snowmelt: 22 March-29 April meq m-2 9.1 41.4 4.55
35S, 2000 snowmelt, 25 March-4 April mBq m-2 473* 157 0.33
*363 mBq m from snowpack; 110 mBq m from rainfall during this period,
concentration as snowpack.

discharge (r2 = 0.52, p< 0.0001) during snowmelt, decr

170 ?ieq 1_1 at base flow to 90 /?eq 1_1 at peak melt (Figure 4
to sulfate, nitrate and DOC concentrations increased sharply

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 171
1 at 417 1 at 343

50
0
10
9 ?34S
8
7
Bf
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50 5
4
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v 10 ?180 of sulfate
3:oft
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Figure 5. Boxplot of sulfate concentrations, ?34S and c5180 of sulfate, and 35S activities for snow,
10 streams, and groundwater (seep) samples during the 2000 snowmelt.

episodes (Figure 4). Nitrate concentration increased from 12^eql_1 during

pre-melt to a maximum of 28 ?xeq 1_1 during the first major snowmelt peak
on 28 March, after which it gradually decreased to 10 ??eq 1_1 by the end
of the melt period, with progressively lower concentration peaks during
subsequent flow peaks. DOC concentration increased from 1.0 mg 1_1
during pre-melt to its maximum of 4.1 mg 1_1, also during the 28 March
peak. Unlike nitrate, DOC continued to increase significantly in response to
flow increases throughout the melt. For water year 2000, sulfate output in
streamwater was 2.7 times the input in wet (bulk) deposition (Table 1).
During the snowmelt period alone, sulfate export was more than four times
the input.

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 172

Isotopic compositions

Snowpack
Snowpack sulfate on 23 February had ?34S values near + 5.6%0 and ?lsO
values near +12%0. On 22 March, after minor thawing, the snowpack had
nearly identical (534S and <5180 values (Figure 5). Sulfate in two meltwater
samples collected near the end of snowmelt in late April had somewhat lower
<534S values of 4.2 and 5.0%o, and a slightly higher ?180 value (measured on one
sample only) of 13.5%0. The 35S activity of the Sleepers River snowpack on 22
March was 6.9 mBq/mg S04.

Groundwater
Sulfate at seven groundwater sites in the W-9 catchment sampled during peak
melt had a median ?34S value of 7.5%0 (range of 5.2-8.5%0). The median <5180
value of sulfate was 2.0%o (range of 1.2-3.0%o with one exception of 5.9%0)
(Figure 5). Groundwater was not sampled for 35S activity.

Streamwater
In eight of the ten streams, pre-melt base flow ?34S values were between 7.3 and
8.9%0. In seven of these eight streams, (534S values decreased (by 0.1 to 2.0%o),
toward the atmospheric value of 5.6%0, at peak snowmelt (Table 2). Stream C
was the exception in that its ?34S value shifted away from the atmospheric value
(increased) during the 28 March event, despite having at that time the highest
streamwater 35S activity measured in the entire study (Table 2). The stream
draining the 2-ha BXA catchment (Figure 2) maintained ?34S values similar to
the snowpack throughout the melt. The BXA stream is the outlet to a swamp and
flows only during snowmelt. At W-2, the small agricultural catchment, ?34S
values remained lower than atmospheric sulfate throughout the melt.
The ?180 values of streamwater sulfate were much lower than those of the
snowpack and varied little spatially or temporally (Figure 5). The median
sulfate <5180 values for the 10 streams ranged narrowly between 2.5 and 4.0%o,
and the absolute range for all stream samples was 1.5-5.5%0, compared to a
value of 12%0 for snowpack sulfate (Figure 5).
Except for some of the pre-melt samples, minor amounts of 35S were present
in all streamwater samples. The absolute range among the 26 stream samples
analyzed was 0.0-0.75 mBq/mg S04 with a median of 0.34 mBq/mg S04. The
35S activities were highest during the early snowmelt peaks.

Mixing models

Old and new water

Based on hydrograph separation using oxygen isotope ratios of water, old
water dominated the rising limb of the overall melt hydrograph (Figure 4),

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 173

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 174

consistent with past findings at Sleepers River (Shanley et al. 2002a). Coinci
dent with peak flow events, the new water fraction reached 40% on 28 March
and 50% on 4 April. The rainfall on 4 April had an unusually high <5180 value,
confounding any subsequent isotopic separation between groundwater and
atmospheric water during this snowmelt.

?34S
Because of concerns about spatial variability of sulfate sources in groundwater
and the limited groundwater sampling area, we used the isotopic composition
of sulfate in pre-melt base flow of each stream as an integrated signal repre
senting the geologic sulfate source. We illustrate the <534S source separation
approach for Stream B (Figure 2), for which we had the most sulfate isotope
analyses (12). The <534S value of Stream B streamwater was 7.5%0 at base flow in
February. On 25 March, early in the main melt sequence, the stream ?34S value
had increased to 8.0%o but 35S still was not detectable, indicating negligible

at12
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March April
2000
Figure 6. Snowmelt hydrograph with stream sulfate concentrations and temporal patterns of <534S
and <5180 values of streamwater sulfate at Stream B within the W-9 catchment. Horizontal stippled
bars represent end member values of atmospheric-derived and mineral-derived <$34S and atmo
spheric <5180 of sulfate used in the mixing models.

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 175

input of atmospheric S to the stream. Hence we assigned 8.0%o as the ? S end

member signal from weathering of S-containing minerals. The <534S value of the
snowpack, 5.6%0, was assumed to represent the sulfur isotope composition of
the atmospheric end member. These end member <534S values provide a
2.4?0.5%o separation for determining mixing ratios for sulfate in Stream B
based on this simple two-source mixing model.
Near the peak of the March 28 rain-on-snow event, ?34S values in Stream B
decreased from 8.0%o to 6.8%0 (Figure 6), a shift one-half of the way toward the
atmospheric composition. The mixing model (Equation 1) therefore suggests
that at peak discharge, 50% of the sulfur in streamwater originated from
mineral weathering and 50% originated from atmospheric sources. After
increasing to greater than 7.0%o during the subsequent recession, ?34S values
again shifted toward the atmospheric end member during a small diurnal melt
on 3 April and the 4 April rain-on-snow event. After a multi-day recession
following this event, the ?34S value increased to 7.7%0, nearly back to the base
flow value of 8.0%o. During a series of subsequent small diurnal and rain-on
snow peaks, <534S values fluctuated between 7.1 and 7.6%0, except for a late
diurnal peak on 24 April when streamwater ?34S matched its lowest value of
6.8%0.
The <534S values of streamwater sulfate tended to vary inversely with stream
discharge; as discharge increased, ?34S values decreased so the calculated
percentage of atmospheric sulfur in streamwater increased (Figure 6). Also, the
percentage of atmospheric sulfur in streamflow approximately tracked the
percentage of new water in streamflow. Although only five samples for ?34S
were collected during the interval before 4 April when hydrograph separation
was possible, they revealed a positive but weak relation (r2 = 0.54, p = 0.15)
between percentage of atmospheric sulfur and percentage of new water,
approximately along the 1:1 line.
For the 7 streams where source separation was possible during snowmelt, the
calculated maximum contribution of atmospheric S to streamwater sulfate
occurred at or near the early snowmelt peak during the rain-on snow events of
March 28 and April 4. The median peak atmospheric S contribution was 55%
and ranged from 3 to 91% (Table 2). With the exception of a single high and a
single low value, the range was 42-70%. For all streamwater samples for which
an atmospheric S contribution could be calculated using this isotope ratio
approach (n = 33), the grand flow-weighted mean atmospheric S contribution
was 41% (Table 2).

?180 of sulfate
In contrast to the relatively small 2-3%0 separation in end member <534S
values of sulfate, there was a large 9-10%o separation in end member <5180
values of sulfate. Also in contrast to <534S patterns, there was no discernable
shift of streamwater sulfate ?180 values toward the <5180 value of atmospheric
sulfate during the melt event (Figure 6). Therefore, the mixing model was not
applied.

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 176

35S activity and sulfur age

If we assume that the sole source of 35S to streamwater was new atmospheric
sulfate (the melting snowpack plus new rain, which we assumed to have the
same 35S concentration as the snowpack), then the contribution of snowpack
sulfate to streamwater sulfate (Equation 2) was no more than 7% at any one
time, reaching this maximum during the 28 March event. Alternatively, we
could assume that 35S was contributed by both new and previously deposited
atmospheric sulfur and calculate a mean sulfur age (Equation 3). The 35S ages
during snowmelt had a rather narrow range from 280 to 385 days among the
10 streams. If the geologic sulfate, which contains no 35S, is subtracted from the
streamwater sulfate based on results from the source apportionment using ?34S
values, the range of minimum ages of the remaining atmospheric S decreased to
184?320 days. The grand mean of 35S ages (n = 23) for all streams was
372 days; for cases where an unambiguous atmospheric S component could be
calculated (n = 15), the mean 35S age of atmospheric S in streamwater was
287 days (Table 2). Note that computed ages are minimum mean ages, as any S
older than 1-2 years has lost most of its radioactive 35S and is indistinguishable
from ~one-year old S.
As snowmelt progressed, the activity of 35S tracked the ?>34S values of
sulfate in Stream B in an inverse manner, suggesting a shift to younger
sulfate as the atmospheric sulfate component in streamwater increased. Al
though only five samples for 35S were collected in Stream B, the relation
between <534S values and 35S activity in streamwater sulfate was strong and
highly significant (r2 = 0.81, p = 0.03). At the peak 35S activity during the
28 March event, the minimum mean age of the atmospheric sulfur compo
nent was 248 days.

Uncertainty in the ?34S mixing model

There are two sources of uncertainty in the mixing model results - analytical
uncertainty and uncertainty of end member values. For the <534S model, the
analytical uncertainty (standard deviation of replicate analyses) was 0.26%o.
For the atmospheric end member (snowpack), temporal variability was negli
gible and spatial variability (standard deviation of four replicates) was 0.15%0.
Assessing uncertainty in the geologic end member (base flow) was more
problematic, as usually only one sample was taken per site. However, one
could argue that all of the small streams draining a common lithology and till
within the forested headwater W-9 catchment should have a common geologic
end member. Using these base flow values (except that from the atmospheri
cally influenced BXA) as a measure of geologic <534S variability, we computed a
standard deviation of 0.55%o. Although this is a substitution of spatial vari
ability for the desired temporal variability, note that the two pre-melt samples
collected at stream B had a similar ?34S difference of 0.5%o. Applying the total
analytical and end member composition uncertainty using the method of
G?n?reux (1998), the uncertainty in the computed S source percentages
from the <534S separation at Stream B ranged from 20 to 28% over the melt

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 177

hydrograph. This high uncertainty stems principally from the narrow separa
tion of the end members.

Discussion

We used a combined hydrologie, chemical, and isotopic approach to assess

sources of sulfate during snowmelt. Collectively, four isotopic indicators that
each track a somewhat different aspect of sulfur cycling and/or hydrologie
behavior of the catchment build a framework for understanding sulfate dynamics
in Sleepers River streamwater. In the following sections we discuss solute
dynamics, atmospheric and geologic sulfur sources, evidence for pedogenic sul
fate, and finally we link the discussion together with a conceptual model of sulfur
cycling. Note that in the discussion of sources, sulfur and sulfate are purposely
distinguished, as sulfate from one source may be formed with sulfur from another
(e.g. pedogenic sulfate formed with atmospheric sulfur).

Solute dynamics

During snowmelt at Sleepers River, rain and meltwaters cause large increases
in streamflow. Past studies at Sleepers River have shown that DOC and nitrate
concentrations increase with increasing flow as surficial soil horizons are flu
shed during snowmelt (Titus et al. 1995; Shanley et al. 2002b). In contrast, Ca
and other solutes derived from weathering are diluted by meltwater. Sulfate has
a mineral weathering source as well as an atmospheric/pedogenic source, thus
could exhibit both dilution and flushing. Sulfate concentration in streamwater
did in fact dilute by nearly 50% during snowmelt (Figure 4). However, the
relative dilution was somewhat less for sulfate than it was for Ca and the other
base cations (Shanley et al. 2004). The potential sulfate dilution is partly
counteracted by a labile pool of pedogenic sulfate in the upper soil, which is
flushed by infiltrating meltwater and by rising water tables during snowmelt.

Atmospheric and geologic sulfur sources

Atmospheric component
In the source separation we assumed that the snowpack ?34S value of + 5.6%0
represents the atmospheric end member. Given our results showing that much of
the atmospheric sulfur in streamwater pre-dates the snowpack, the representa
tiveness of this end member becomes an important issue. Based on other regional
determinations (Stam et al. 1992; Zhang et al. 1998; Alewell et al. 2000) and also
on a USA compilation (Newman et al. 1991), a <534S value of 5.6%0 appears to be
broadly representative of atmospheric sulfate. In a European study, Novak et al.
(2001) cautioned that ?34S values in throughfall were on average 1%0 lower than

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 178

those of precipitation, but Zhang et al. (1998) found seasonal reversals of this
relation at Hubbard Brook, NH. Our snowpack samples were collected within
the forested W-9 watershed, but given that the forest is 85% deciduous, there
should be minimal alteration by the canopy during winter.
Cosmogenic 35S is an excellent tracer of young atmospheric sulfate. Glob
ally, the production of cosmogenic 35S is fairly uniform in space, whereas the
deposition of sulfate is highly variable. Thus 35S activities normalized to sulfate
mass tend to increase with decreasing sulfate deposition. The 35S activity of
6.9 mBq/mg S04 measured in the Sleepers River snowpack on 22 March was
intermediate between reported activities in snowpacks in a region of low S
deposition, the Rocky Mountains (21 mBq/mg S04 (Sueker et al. 1999) and
60 mBq/mg S04 (Michel et al. 2000)) and in precipitation at an area of high S
deposition in central Europe (2-6 mBq/mg S04 (Novak et al. 2004)). Although
the snowpack at the Vermont site is prone to sulfate elution during periodic
midwinter thaws, elution should not affect the 35S activity as expressed per unit
mass of sulfate. The snowpack develops over a 4?5 month period thus some of
its 35S decays, but its activity at the start of snowmelt is the effective initial
(zero-age) activity of atmospheric inputs during snowmelt.

Geologic component

The <534S separation hinges on the assumption that base flow represents the
geologic end member. Clearly geologic S is important, based on the 2.7 ratio of
S exports to inputs calculated for this study year, which agrees closely with an
earlier 3-year average of 2.4 reported by Hornbeck et al. (1997). Both ratios
used sulfate input in bulk deposition, which underestimates dry deposition.
Dry deposition of S was not measured at our site, but has been estimated at
21% of total S deposition for the Arbutus Watershed in the Adirondacks, New
York (Park et al. 2003) and 21% of bulk deposition at Hubbard Brook, New
Hampshire (Likens et al. 2002). The presence of primary sulfides (as opaque
minerals) is well-documented in the Waits River formation (Hall 1959), and
Bailey et al. (2004) also isolated secondary sulfate minerals.
The ?34S values of stream sulfate at base flow were generally within 1%0 of
the ?34S value of 8.5%0 measured in one sample of Waits River bedrock (Bailey
et al. 2004). Base flow at the small agricultural W-2 catchment had a much
lower base flow ?34S value of 4.1%0, possibly due to different <534S values of its
bedrock or to past fertilizer use. However, the narrow range of base flow ?34S
values of sulfate, at least among streams within the W-9 catchment, suggests
that a <534S value near 8.0%o (allowed to vary for individual stream base flows)
is a robust end member value for mineral-derived sulfate. On the other hand,
four of the seven streams within W-9 had detectable 35S in these base flow
samples, indicating that some atmospheric sulfur was present. Small amounts
of meltwater from the minor mid-winter thaws could have caused this 35S
signal without appreciably altering ?34S values of streamwater sulfate.

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 179

Evidence for pedogenic sulfate formation

Three lines of evidence support the importance of pedogenic sulfate formed

from atmospheric sulfur in this ecosystem. The first argument uses the <5180
values of sulfate. Despite an overall contribution of 41% atmospheric sulfur to
streamwater sulfur during snowmelt (Table 2), the ?180 values of streamwater
sulfate were consistently lower than, and did not shift toward, those of
atmospheric sulfate (Figures 5 and 6). This finding suggests that atmospheric
sulfate is assimilated by soil microbes, with the end result that the high
atmospheric ?lsO value of sulfate is reset to a lower value typical of pedogenic
sulfate (Mitchell et al. 1998) (Figure 1).
The shift of the atmospheric sulfate <5180 signal to lower values within the
soil has been previously noted (Mayer et al. 1995a, b). Even in areas where
soil is thin or absent, such as the alpine/subalpine zone of the Rocky
Mountains, only a limited atmospheric sulfate <5180 signal propagates
through the landscape Johnson et al. 2001; Kester et al. 2003). Mayer et al.
(1995a) showed a progressive decrease in the ?180 values of sulfate in soil
solution with depth, indicating that the immediate source of sulfate was
mineralization of C-bonded sulfur. The resetting of the atmospheric ?180
signal of sulfate is similar to the resetting of the atmospheric <5180 signal of
nitrate at the Sleepers River site (Kendall et al. 1995) and elsewhere
(Kendall 1998; Campbell et al. 2000; Mayer et al. 2001a; Burns and Ken
dall, 2002).
The second line of evidence for pedogenic sulfate formation is provided by
the 35S patterns. The low 35S activities in streamflow relative to the snowpack
suggest that most of the atmospheric sulfur appearing in streamflow was older
than the current year's snowpack. Regardless whether the 35S activity in
streamwater is attributed solely to new atmospheric sulfate inputs (Equation 2)
or to atmospheric/pedogenic sulfate with a range of ages (Equation 3), the 35S
patterns indicate that most of the incoming atmospheric S resides for a con
siderable time in the soil zone. The computed ages of 184-320 days probably
reflect a mixture of young sulfate in rain and snowmelt with atmospheric/
pedogenic sulfate of varying age. Much of the pedogenic sulfate in streamwater
likely formed from atmospheric sulfur deposited at an earlier time (Mayer et al.
2001b). As noted previously, based on 35S activities (Equation 2), the direct
contribution of snowpack sulfate to stream sulfate never exceeded 7%. This
result is consistent with the sulfate c>180 results, in that such a small contri
bution may not be enough to cause a detectable shift in ?180 values of
streamwater sulfate.
In the alpine/subalpine Loch Vale Colorado watershed, Michel et al.
(2000) used 35S to calculate that ~40% of stream sulfate was supplied by
the current year's snowmelt. This high direct atmospheric contribution rel
ative to that in the present study reflects greater throughput of atmospheric
sulfate in this zone of thin soils and sparse vegetation. In three larger Rocky
Mountain basins that extend to lower elevations, Sueker et al. (1999)

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 180

calculated S ages that were similar to those in our study. Field experi
ments using amendments of 35S likewise show soil retention of most of the
added S in the organic soil pool (Schindler et al. 1986; Dhamala and
Mitchell 1995).
The third line of evidence for pedogenic sulfate formation uses mass bal
ance considerations. The amount of sulfate in the snowpack and subsequent
rainfall was 22% of the mass of sulfate exported in streamflow during the
snowmelt period (Table 1). This amount is considerably less than the 41%
mean overall contribution of atmospheric S to streamwater sulfate calculated
from stable S isotope ratios. The additional source of atmospheric sulfur
must be S previously deposited and stored in the catchment, and may include
S eluted from the snowpack during thaws earlier in the winter. Soil retention
is supported by the 35S mass balance; only 33% of the 35S in the snowpack
and subsequent rainfall could be accounted for in stream export through the
peak melt period (Table 1). Collectively, the isotopic and mass balance evi
dence suggest that much of the atmospheric S input ultimately is exported in
streamwater as pedogenic sulfate, after the atmospheric sulfate has cycled
through the organic soil S pool.

Effect of soil processes on isotopic results

Sulfate adsorption
Pedogenic sulfate formed in the O and A horizons, as well as any atmospheric
sulfate that passes through the forest floor, may be adsorbed in the B-horizon.
This process would further increase sulfate retention times, with no change in
isotopic composition.

Assimilatory bacterial sulfate reduction

The low ?180 values of stream sulfate suggest assimilatory bacterial sulfate
reduction followed by mineralization of C-bonded S, which would decrease
the (5180 value while preserving the ?34S value of atmospheric sulfate. The
mean 35S age of greater than 200 days, dating back to the previous growing
season, allows sufficient time for these conversions. From stream base flow
values, it appears that a <5180 value for sulfate near 2%0 can be expected
from sulfur oxidation in this system (assuming sulfate minerals do not
contribute), with the sulfate-oxygen contributed primarily by soil water.
Despite seasonal variations in soil water ?180, the ?180 value of this
pedogenic sulfate is likely to remain constant as it is "buffered" by the
pool of adsorbed sulfate. The lack of change in the <S180 value of
streamwater sulfate even when atmospheric sulfur contributions reach 50%
(Figure 6) suggests that atmospheric S was reduced (by assimilatory bac
terial sulfate reduction) and re-oxidized within the catchment. Oxidation of
C-bonded sulfur is the likely source of the stream sulfate containing the
atmospheric S.

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 181

Dissimilatory bacterial sulfate reduction

Dissimilatory BSR is the lone soil process that could cause significant
fractionation of sulfur isotope ratios (Figure 1), which would violate the
assumptions of the mixing model. Dissimilatory BSR causes increases in the
?34S of sulfate in porewaters in hyporheic zones, riparian soils, and wetlands
during dry periods, potentially increasing stream ?34S values while
decreasing S04 concentrations (Alewell and Novak 2001; Eimers et al.
2004). The opposite pattern occurs when the 32S-enriched sulfide product is
reoxidized and flushed from soils during recharge periods, causing decreases
in streamwater <534S values (Eimers et al. 2004). This latter process could
operate during snowmelt flushing and thus could confound the signal of
atmospheric sulfate, which also causes a decrease in ?34S values of
streamwater sulfate in this system. We discount the importance of dissimi
latory BSR during snowmelt for two reasons: (1) this process can cause
large isotope fractionations that would void the mixing model results, but
the calculated atmospheric contributions from the model were reasonable
and consistent with mass balances, and (2) any reduced sulfur from this
process likely would have been already oxidized and flushed from the soil
during fall recharge.

Conceptual model

Weathering of sulfur-containing minerals in the bedrock and till dominates the

sulfate flux from Sleepers River watersheds. Based on two-component mixing
using stable sulfur isotope ratios, the snowmelt period flow-weighted mean
atmospheric S contribution to streamwater sulfate was 41%, consistent with
the annual sulfate input/output ratio of 0.42 (Hornbeck et al. 1997). The
atmospheric component consists of a small amount of atmospheric sulfate that
enters the stream unaltered, and a larger fraction that enters the soil organic S
pool, ultimately reaching the stream weeks, months, or years later as pedogenic
sulfate.
Our results suggest a scenario in which most atmospheric sulfate undergoes
assimilatory bacterial sulfate reduction and resides in the soil for months or
years as carbon-bonded S, then is subsequently mineralized to sulfate (pedo
genic sulfate) and flushed to the stream by meltwaters. During the initial
snowmelt period, the percentage of atmospheric S in streamwater, as computed
from ?34S, closely matched the percentage of new water as computed from the
?180 values of water. Despite the match, this is not a simple matter of new
(event) water conveying recently deposited atmospheric sulfate to the stream;
the low 35S activities indicate that most stream sulfur is several months old, and
the low <5180 values of streamwater sulfate show that the original atmospheric
sulfate has been reduced and re-oxidized in the soil. The new water is primarily
flushing this pedogenic sulfate.

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 182

Conclusions

Four isotopic indicators, hydrologie measurements, and solute chemistry were

combined to elucidate sulfur biogeochemistry during snowmelt in a Vermont
catchment. The two most significant findings were: (1) geologic sulfur dominates
stream sulfate except at peak snowmelt when atmospheric sulfur may dominate;
and (2) nearly all of the sulfate in streamwater formed from atmospheric sulfur is
pedogenic, i.e. the original S-O bonds in atmospheric sulfate were broken and
new sulfate was formed in the soil environment, most likely through assimilatory
bacterial sulfate reduction and subsequent re-mineralization. In seven of ten
watersheds of differing size and land use, distinctive <534S values of weathering
and atmospheric end members enabled source separation. The maximum
atmospheric/pedospheric contribution exceeded 50% for most streams during a
rain-on-snow event early in the melt period, and averaged (flow-weighted) 41%
for all samples (n = 33) during the active melt period. The pedogenic origin of
stream sulfate was identified by the shift in <5180 values from the distinctive high
values of atmospheric sulfate to constant values that were 9-10%o lower in stream
sulfate. The percentage of atmospheric/pedospheric sulfur in streamwater (as
calculated from ?34S) covaried with the percentage of "new water" in streamflow
(as determined by the ?180 of water), and covaried also with activity of the
radioactive cosmogenic 35S (half life 87 days), whose source is the atmosphere
and is an indicator of young sulfate. However, 35S ages of the atmospheric
component of stream sulfate ranged from 184 to 320 days, suggesting that most
of the atmospheric/pedospheric sulfur detected in streamflow was deposited well
before the study snowmelt period. During the snowmelt period, the new water in
snowmelt effectively flushes the pedogenic sulfate from the soil. The finding that
most sulfate is mediated in the soil, and may reside in the catchment for several
months to years, suggests that catchment response to changes in atmospheric S
emission and deposition may be delayed.

Acknowledgements

This work was supported by the U.S. Geological Survey Water, Energy, and
Biogeochemical Budgets (WEBB) program. We thank Paul Schuster and Doug
Halm for field asssistance. This paper benefitted from reviews by Cyndi Kester
and Dan Doctor of the USGS, and two anonymous reviewers.

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