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D. W. Clow

Publications and source records attributed to D. W. Clow.

14 recordsLinked to original sources

Concentration-discharge relationships reflect chemostatic characteristics of US catchments

Concentration-discharge relationships have been widely used as clues to the hydrochemical processes that control runoff chemistry. Here we examine concentration-discharge relationships for solutes produced primarily by mineral weathering in 59 geochemically diverse US catchments. We show that these catchments exhibit nearly chemostatic behaviour; their stream concentrations of weathering products such as Ca, Mg, Na, and Si typically vary by factors of only 3 to 20 while discharge varies by several orders of magnitude. Similar patterns are observed at the inter-annual time scale. This behaviour implies that solute concentrations in stream water are not determined by simple dilution of a fixed solute flux by a variable flux of water, and that rates of solute production and/or mobilization must be nearly proportional to water fluxes, both on storm and inter-annual timescales. We compared these catchments' concentration-discharge relationships to the predictions of several simple hydrological and geochemical models. Most of these models can be forced to approximately fit the observed concentration-discharge relationships, but often only by assuming unrealistic or internally inconsistent parameter values. We propose a new model that also fits the data and may be more robust. We suggest possible tests of the new model for future studies. The relative stability of concentration under widely varying discharge may help make aquatic environments habitable. It also implies that fluxes of weathering solutes in streams, and thus fluxes of alkalinity to the oceans, are determined primarily by water fluxes. Thus, hydrology may be a major driver of the ocean-alkalinity feedback regulating climate change. Copyright ?? 2009 John Wiley & Sons, Ltd.

Hydrological Processes

Assessment of lake sensitivity to acidic deposition in national parks of the Rocky Mountains

The sensitivity of high-elevation lakes to acidic deposition was evaluated in five national parks of the Rocky Mountains based on statistical relations between lake acid-neutralizing capacity concentrations and basin characteristics. Acid-neutralizing capacity (ANC) of 151 lakes sampled during synoptic surveys and basin-characteristic information derived from geographic information system (GIS) data sets were used to calibrate the statistical models. The explanatory basin variables that were considered included topographic parameters, bedrock type, and vegetation type. A logistic regression model was developed, and modeling results were cross-validated through lake sampling during fall 2004 at 58 lakes. The model was applied to lake basins greater than 1 ha in area in Glacier National Park ( n = 244 lakes), Grand Teton National Park ( n = 106 lakes), Great Sand Dunes National Park and Preserve ( n = 11 lakes), Rocky Mountain National Park ( n = 114 lakes), and Yellowstone National Park ( n = 294 lakes). Lakes that had a high probability of having an ANC concentration <100 μeq/L, and therefore sensitive to acidic deposition, are located in basins with elevations >3000 m, with <30% of the catchment having northeast aspect and with >80% of the catchment bedrock having low buffering capacity. The modeling results indicate that the most sensitive lakes are located in Rocky Mountain National Park and Grand Teton National Park. This technique for evaluating the lake sensitivity to acidic deposition is useful for designing long-term monitoring plans and is potentially transferable to other remote mountain areas of the United States and the world.

Colorado;Idaho;Montana;Wyoming

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993-2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993-2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites. Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999-2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.

Atmospheric Environment

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1 ng L −1 and MeHg was less than 0.2 ng L −1 . THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56) ng L −1 at Sleepers River, Vermont; 112 (0.75) ng L −1 at Rio Icacos, Puerto Rico; and 55 (0.80) ng L −1 at Panola Mt., Georgia. Filtered (<0.7 μm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5 ng L −1 at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

Environmental Pollution

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (??? 30??), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year -1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris-probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley and Sons, Ltd.

Hydrological Processes

Use of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks

Stable sulfur isotope ratios and major ions in bulk snowpack samples were monitored at a network of 52 high-elevation sites along and near the Continental Divide from 1993 to 1999. This information was collected to better define atmospheric deposition to remote areas of the Rocky Mountains and to help identify the major source regions of sulfate in winter deposition. Average annual ??34S values at individual sites ranged from + 4.0 to + 8.2??? and standard deviations ranged from 0.4 to 1.6???. The chemical composition of all samples was extremely dilute and slightly acidic; average sulfate concentrations ranged from 2.4 to 12.2 ??eql-1 and pH ranged from 4.82 to 5.70. The range of ??34S values measured in this study indicated that snowpack sulfur in the Rocky Mountains is primarily derived from anthropogenic sources. A nearly linear relation between ??34S and latitude was observed for sites in New Mexico, Colorado, and southern Wyoming, which indicates that snowpack sulfate in the southern part of the network was derived from two isotopically distinct source regions. Because the major point sources of SO2 in the region are coal-fired powerplants, this pattern may reflect variations in the isotopic composition of coals burned by the plants. The geographic pattern in ??34S for sites farther to the north in Wyoming and Montana was much less distinct, perhaps rflecting the paucity of major point sources of SO2 in the northern part of the network.

Atmospheric Environment

Major-ion chemistry of the Rocky Mountain snowpack, USA

During 1993-97, samples of the full depth of the Rocky Mountain snowpack were collected at 52 sites from northern New Mexico to Montana and analyzed for major-ion concentrations. Concentrations of acidity, sulfate, nitrate, and calcium increased from north to south along the mountain range. In the northern part of the study area, acidity was most correlated (negatively) with calcium. Acidity was strongly correlated (positively) with nitrate and sulfate in the southern part and for the entire network. Acidity in the south exceeded the maximum acidity measured in snowpack of the Sierra Nevada and Cascade Mountains. Principal component analysis indicates three solute associations we characterize as: (1) acid (acidity, sulfate, and nitrate), (2) soil (calcium, magnesium, and potassium), and (3) salt (sodium, chloride, and ammonium). Concentrations of acid solutes in the snowpack are similar to concentrations in nearby wetfall collectors, whereas, concentrations of soil solutes are much higher in the snowpack than in wetfall. Thus, dryfall of acid solutes during the snow season is negligible, as is gypsum from soils. Snowpack sampling offers a cost-effective complement to sampling of wetfall in areas where wetfall is difficult to sample and where the snowpack accumulates throughout the winter. Copyright ?? 2001 .

Atmospheric Environment

Carbon gas exchange at a southern Rocky Mountain wetland, 1996-1998

Carbon dioxide (CO2) and methane (CH4) exchange between the atmosphere and a subalpine wetland located in Rocky Mountain National Park, Colorado, at 3200 m elevation were measured during 1996-1998. Respiration, net CO2 flux, and CH4 flux were measured using the closed chamber method during snow-free periods and using gas diffusion calculations during snow-covered periods. The ranges of measured flux were 1.2-526 mmol CO2 m-2 d-1 (respiration), -1056-100 mmol CO2 m-2 d-1 (net CO2 exchange), and 0.1-36.8 mmol CH4 m-2 d-1 (a positive value represents efflux to the atmosphere). Respiration and CH4 emission were significantly correlated with 5 cm soil temperature. Annual respiration and CH4 emission were modeled by applying the flux-temperature relationships to a continuous soil temperature record during 1996-1998. Gross photosynthesis was modeled using a hyperbolic equation relating gross photosynthesis, photon flux density, and soil temperature. Modeled annual flux estimates indicate that the wetland was a net source of carbon gas to the atmosphere each of the three years: 8.9 mol C m-2 yr-1 in 1996, 9.5 mol C m-2 yr-1 in 1997, and 9.6 mol C m-2 yr-1 in 1998. This contrasts with the long-term carbon accumulation of ???0.7 mol m-2 yr-1 determined from 14C analyses of a peat core collected from the wetland.

Global Biogeochemical Cycles

The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

Geochimica et Cosmochimica Acta

Trends in precipitation and stream-water chemistry in the northeastern United States, water years 1984-96

Trends in precipitation and stream-water chemistry during water years 1984-96 were examined at eight precipitation monitoring sites and five nearby streams operated by the U.S. Geological Survey in the northeastern United States. The statistical analyses indicate the following: 1)Stream-water sulfate (SO4) concentrations decreased at seven of eight precipitation monitoring sites and in each of five streams. 2)Calcium plus magnesium (Ca + Mg) concentrations decreased at seven of eight precipitation monitoring sites and in three of five streams. 3)Precipitation acidity decreased at five of eight precipitation monitoring sites, but alkalinity increased in only one stream. These results indicate that decreases in atmospheric deposition of SO4 have resulted in decreased precipitation acidity. The chemical response of stream water to changes in precipitation chemistry was complex. Decreases in stream-water SO4 concentrations generally matched decreases of precipitation SO4. In stream water, increases in alkalinity were uncommon because decreases in SO4 concentrations often were accompanied by decreases in Ca + Mg concentrations. The decreases in Ca + Mg concentrations might be related to depletion of base cations from soil caused by long-term exposure to acidic deposition. Increases in streamwater alkalinity might not occur until rates of acidic deposition are reduced to substantially less than the rate of cation resupply by weathering and atmospheric deposition. In areas where forests are aggrading, recovery of stream-water alkalinity will be delayed further because of the acidifying effect of biomass accumulation.

Fact Sheet

Controls on surface water chemistry in the upper Merced River basin, Yosemite National Park, California

Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 μequiv. l −1 . Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 μequiv. l −1 . Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock. Chloride concentrations in surface water samples varied widely, ranging from <1 to 96 μequiv. l −1 . The annual volume-weighted mean chloride concentration in the Merced River at the Happy Isles gauge from 1968 to 1990 was 26 μequiv. l −1 , which was five times higher than in atmospheric deposition (4–5 μequiv. l −1 ), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 μequiv. l −1 . Concentrations of sulphate in quarterly samples collected at the watershed outlet also showed relatively little variation, suggesting that sulphate may be regulated to some extent by a within-watershed process, such as sulphate adsorption.

Hydrological Processes

Weathering rates as a function of flow through an alpine soil

The effect of flow on release rates of solutes from soil in a 39-m2 alpine catchment in the Colorado Rockies was measured during the summers of 1990-1994. Flow rates through the soil were varied by augmenting natural rainfall with deionized irrigation water. Daily water inputs averaged between 96 and 216 1 day-1 during the five field seasons, and mean discharge (inputs minus evapotranspiration) varied from 35 to 175 1 day-1. Volume-weighted mean concentrations of base cations and silica decreased only moderately in response to the increased water inputs. Input fluxes of solutes in precipitation were similar in each of the study seasons, but output fluxes of base cations and silica in surface outflow increased substantially in conjunction with the average water input rate for the season. Weathering rates calculated from the chemical fluxes increased substantially in response to increases in water input rates. The increases appear to be largely attributable to enhanced transport of solutes from the soil matrix under high flow conditions. At high flow, physical flushing of micropores presumably occurs to a greater extent than during low-flow periods because of greater soil wetness and higher hydrologic head. Increased flushing would also cause an increased rate of diffusion of solutes from microcracks in mineral surfaces and constricted pore spaces in response to an increased concentration gradient between those regions and adjacent areas in the soil matrix. Another consequence of the increased flushing that occurs during periods of high flow is that concentrations throughout the soil matrix tend to be lower, which might increase chemical weathering rates of some silicate minerals such as microcline, which are relatively close to saturation. Decreased Si concentrations under high-flow conditions appear to promote dissolution of amorphous aluminosilicates or desorption of Si from mineral surfaces, buffering Si concentrations in the soil solutions. Thus, both physical transport of solutes and subsequent chemical effects appear to be responsible for the positive relation observed between fluxes of weathering products and water input rates.

Chemical Geology

Characterization of selected radionuclides in sediment and surface water in Standley Lake, Great Western Reservoir, and Mower Reservoir, Jefferson County, Colorado, 1992

Lake sediment and surface water from Standley Lake, Great Western Reservoir, and Mower Reservoir, near Denver, Colorado, were sampled and analyzed for selected radionuclides during August through October, 1992. Sample concentrations were summarized and compared to results from a study conducted in 1983-84. Median plutonium-239,240 (239,240Pu) concentrations in lake-sediment grab samples from Standley Lake, Great Western Reservoir, and Mower Reservoir were 0.037, 0.105, and 0.351 picocuries per gram (pCi/g). The maximum concen- tration of 239,240Pu dissolved in lake water was 0.009 picocuries per liter, substantially below limits suggested by the Colorado Department of Health and the Environment. Dissolved concentrations of gross alpha and uranium isotopes were below National Drinking Water Standards in all water samples. There was no statistically significant difference between 239,240Pu concentration in lake-sediment grab samples collected from Standley Lake in 1983-84 and in 1992; however, there was a small, but statistically significant, difference at Great Western Reservoir (p<0.05). In 1992 at Great Western Reservoir, median 239,240Pu concentrations were 0.040 pCi/g lower than in 1983-84. There was a small, but statistically significant (p<0.05) difference in 239,240Pu concentrations in lake- bottom-sediment cores collected in 1983-84 and in 1992. Measured concentrations tended to be higher in 1983-84 than in 1992. The differences were greatest at concentrations above 1.5 pCi/g; in those samples concentrations were 10 to 30% higher in 1983-84 than in 1992.

Colorado