Geology topics

D. P. Krabbenhoft

Publications and source records attributed to D. P. Krabbenhoft.

48 records · Page 3Linked to original sources

USGS2002

Mercury deposition in snow near an industrial emission source in the western U.S. and comparison to ISC3 model predictions

Mercury (total and methyl) was evaluated in snow samples collected near a major mercury emission source on the Idaho National Engineering and Environmental Laboratory (INEEL) insoutheastern Idaho and 160 km downwind in Teton Range in westernWyoming. The sampling was done to assess near-field (<12 km)deposition rates around the source, compare them to those measured in a relatively remote, pristine downwind location, andto use the measurements to develop improved, site-specific modelinput parameters for precipitation scavenging coefficient and thefraction of Hg emissions deposited locally. Measured snow waterconcentrations (ng L -1 ) were converted to deposition (ugm -2 ) using the sample location snow water equivalent. Thedeposition was then compared to that predicted using the ISC3 airdispersion/deposition model which was run with a range ofparticle and vapor scavenging coefficient input values. Acceptedmodel statistical performance measures (fractional bias andnormalized mean square error) were calculated for the differentmodeling runs, and the best model performance was selected. Measured concentrations close to the source (average = 5.3 ngL -1 ) were about twice those measured in the Teton Range(average = 2.7 ng L -1 ) which were within the expected rangeof values for remote background areas. For most of the samplinglocations, the ISC3 model predicted within a factor of two of theobserved deposition. The best modeling performance was obtainedusing a scavenging coefficient value for 0.25 μm diameterparticulate and the assumption that all of the mercury isreactive Hg(II) and subject to local deposition. A 0.1 μm particle assumption provided conservative overprediction of thedata, while a vapor assumption resulted in highly variable predictions. Partitioning a fraction of the Hg emissions to elemental Hg(0) (a U.S. EPA default assumption for combustion facility risk assessments) would have underpredicted the observed fallout.

Idaho↗

USGS1999

Mercury methylation in periphyton of the Florida Everglades

Trophic accumulation of mercury (Hg) in aquatic ecosystems is of global concern due to health effects associated with eating fish with elevated Hg levels. The methylated form of Hg bioaccumulates so it is important to understand how inorganic Hg is transformed to methylmercury in the environment. Here, a new site for Hg methylation, the periphyton communities that are prevalent in the Florida Everglades, is described. It is hypothesized that periphyton communities that support an active microbial sulfur cycle support Hg methylation. This new methylation site has implications for trophic transfer of methylmercury since periphyton can be the base of the food web in aquatic ecosystems.

Limnology and Oceanography↗

USGS1998

Trophic transfer of methyl mercury in the northern Florida Everglades

There are spatial differences in methyl mercury (MeHg) concentrations in biota in Water Conservation Areas 2 and 3 in the Everglades, with higher concentrations generally found in the southern areas. Fish and hemipterans had the most MeHg on a wet weight basis, with levels exceeding 30 ng g-1. The magnitude of MeHg accumulation in biota varies seasonally and does not always appear to be associated with changes in water column concentration. This is exemplified by periphyton, the base of the foodweb in the Everglades, at a high nutrient sampling site. Although limited in scope, MeHg concentrations presented for biota provide insight into beginning to understand the dynamic nature of Hg transfer in the Everglades foodweb on a spatial and temporal basis.

Biogeochemistry↗

USGS1998

System controls on the aqueous distribution of mercury in the northern Florida Everglades

The forms and partitioning of aqueous mercury species in the canals and marshes of the Northern Florida Everglades exhibit strong spatial and temporal variability. In canals feeding Water Conservation Area (WCA) 2A, unfiltered total Hg (HgT(U)) is less than 3 ng L-1 and relatively constant. In contrast, methyl mercury (MeHg) exhibited a strong seasonal pattern, with highest levels entering WCA-2A marshes during July. Stagnation and reduced flows also lead to particle enrichment of MeHg. In the marshes of WCA-2A, 2B and 3A, HgT(U) is usually <5 ng L-1 with no consistent north-south patterns. However, for individual dates, aqueous unfiltered MeHg (MeHg(U)) levels increase from north to south with generally lowest levels in the eutrophied regions of northern WCA-2A. A strong relationship between filtered Hg species and dissolved organic carbon (DOC), evident for rivers draining wetlands in Wisconsin, was not apparent in the Everglades, suggesting either differences in the binding sites of DOC between the two regions, or non-organic Hg complexation in the Everglades.

Biogeochemistry↗

USGS1998

Diel variability of mercury phase and species distributions in the Florida Everglades

Preliminary studies of mercury (Hg) cycling in the Everglades revealed that dissolved gaseous mercury (DGM), total mercury (Hg(T)), and reactive mercury (Hg(R)) show reproducible, diel trends. Peak water-column DGM concentrations were observed on or about noon, with a 3 to 7 fold increase over night-time concentrations. Production of DGM appears to cease during dark periods, with nearly constant water column concentrations that were at or near saturation with respect to the overlying air. A simple mass balance shows that the flux of Hg to the atmosphere from diel DGM production and evasion represents about 10% of the annual input from atmospheric deposition. Production of DGM is likely the result of an indirect photolysis reaction that involves the production of reductive species and/or reduction by electron transfer. Diel variability in Hg(T) and Hg(R) appears to be controlled by two factors: inputs from rainfall and photolytic sorption/desorption processes. A possible mechanism involves photolysis of chromophores on the surface of a solid substrate (e.g., the periphyton mat) giving rise to destabilization of sorbed mercury and net desorption during daylight. At night, the sorption reactions predominate and the water-column Hg(T) decreases. Methylmercury (MeHg) also showed diel trends in concentration but were not clearly linked to the solar cycle or rainfall at the study site.

Biogeochemistry↗

USGS1998

The hyporheic zone as a source of dissolved organic carbon and carbon gases to a temperate forested stream

The objective of this study was to examine chemical changes in porewaters that occur over small scales (cm) as groundwater flows through the hyporheic zone and discharges to a stream in a temperate forest of northern Wisconsin. Hyporheic-zone porewaters were sampled at discrete depths of 2, 10, 15, 61, and 183 cm at three study sites in the study basin. Chemical profiles of dissolved organic carbon (DOC), CO2, CH4, and pH show dramatic changes between 61 cm sediment depth and the water-sediment interface. Unless discrete samples at small depth intervals are taken, these chemical profiles are not accounted for. Similar trends were observed at the three study locations, despite each site having very different hydraulic-flow regimes. Increases in DOC concentration by an order of magnitude from 61 to 15 cm depth with a corresponding decrease in pH and rapid decreases in the molecular weight of the DOC suggest that aliphatic compounds (likely organic acids) are being generated in the hyporheic zone. Estimated efflux rates of DOC, CO2, and CH4 to the stream are 6.2, 0.79, 0.13 moles m2 d-1, respectively, with the vast majority of these materials produced in the hyporheic zone. Very little of these materials are accounted for by sampling stream water, suggesting rapid uptake and/or volatilization.

Biogeochemistry↗

USGS1998

Methyl mercury dynamics in littoral sediments of a temperate seepage lake

The sites and rates of methyl mercury (MeHg) production and transport in littoral zone sediments were investigated at Pallette Lake in northern Wisconsin. In littoral areas where groundwater inflow occurs, sulfate supply from groundwater creates profiles of electron acceptors (sulfate) and donors (methane, sulfide) that are reversed from those found in sediments whose sulfate supply is delivered from overlying water. The highest MeHg concentrations in porewaters and the maximal advective MeHg flux rates (4.5-61.7 ng ·m -2 ·day -1 ) were observed in the spring, while highest bulk phase concentrations occur later in the summer. These estimated MeHg fluxes are greater than the mean areal production rates estimated previously for the water column and are similar to the atmospheric flux. Gross MeHg production was measured using the addition of 203 Hg as a tracer to sediments. The depth at which maximal 203 Hg methylation occurred coincided with the observed maximums in solid-phase and porewater MeHg concentrations. Because input, advection, and accumulation of MeHg in these sediments were measured directly, an independent estimate of MeHg production could be made and compared with 203 Hg-derived rates. This comparison suggests that that the 203 Hg tracer method provides reasonable estimates of gross methylation rates and that a substantial fraction of solid-phase Hg is available for methylation

Canadian Journal of Fisheries and Aquatic Sciences↗

USGS1997

Resolution of matrix effects on analysis of total and methyl mercury in aqueous samples from the Florida Everglades

Aqueous samples from the Florida Everglades present several problems for the analysis of total mercury (HgT) and methyl mercury (MeHg). Constituents such as dissolved organic carbon (DOC) and sulfide at selected sites present particular challenges due to interferences with standard analytical techniques. This is manifested by 1) the inability to discern when bromine monochloride (BrCl) addition is sufficient for sample oxidation for HgT analysis; and 2) incomplete spike recoveries using the distillation/ethylation technique for MeHg analysis. Here, we suggest ultra-violet (UV) oxidation prior to addition of BrCl to ensure total oxidation of DOC prior to HgT analysis and copper sulfate (CuSO 4 ) addition to aid in distillation in the presence of sulfide for MeHg analysis. Despite high chloride (Cl - ) levels, we observed no effects on MeHg distillation/ethylation analyses.

Fresenius' Journal of Analytical Chemistry↗

USGS1997

Assessing hydrogeochemical heterogeneity in natural and constructed wetlands

While 'water quality function' is cited as an important wetland function to design for and preserve, we demonstrate that the scale at which hydrochemical samples are collected can significantly influence interpretations of biogeochemical processes in wetlands. Subsurface, chemical profiles for both nutrients and major ions were determined at a site in southwestern Wisconsin that contained areas of both natural and constructed wetlands. Sampling was conducted on three different scales: (1) a large scale (3 m between sampling points), (2) an intermediate scale (0.15 m between sampling points), and (3) a small scale (1.5 cm between sampling points). In most cases, significant vertical heterogeneity was observed at the 0.15 m scale, which was much larger than previously reported for freshwater wetlands and not detected by sampling water table wells screened over the same interval. However, profiles of ammonia and total phosphorus showed tenfold changes in the upper 0.2 meters of the saturated zone when sampled at the small (1.5 cm) scale, that was not depicted by sampling at the intermediate scale. At the intermediate scale of observation, one constructed wetland site differed geochemically from the natural wetlands and the other constructed wetland site due to application of off-site salvaged marsh surface and downward infiltration of rain. While important differences in dissolved inorganic phosphorus and dissolved inorganic carbon concentrations existed between the constructed wetland and the natural wetlands, we also observed substantial differences between the natural wetland sites for these constituents. A median-polishing analysis of our data showed that temporal variations in constituent concentrations within profiles, although extensively recognized in the literature, were not as important as spatial variability.

Biogeochemistry↗

USGS1996

Kinetic and mineralogic controls on the evolution of groundwater chemistry and 87Sr/86Sr in a sandy silicate aquifer, northern Wisconsin, USA

Substantial flowpath-related variability of 87Sr/86Sr is observed in groundwaters collected from the Trout Lake watershed of northern Wisconsin. In the extensive shallow aquifer composed of sandy glacial outwash, groundwater is recharged either by seepage from lakes or by precipitation that infiltrates the inter-lake uplands. 87Sr/86Sr of groundwater derived mainly as seepage from a precipitation-dominated lake near the head of the watershed decreases with progressive water chemical evolution along its flowpath due primarily to enhanced dissolution of relatively unradiogenic plagioclase. In contrast, 87Sr/86Sr of groundwater derived mainly from precipitation that infiltrates upland areas is substantially greater than that of precipitation collected from the watershed, due to suppression of plagioclase dissolution together with preferential leaching of Sr from radiogenic phases such as K-feldspar and biotite. The results of a column experiment that simulated the effects of changing residence time of water in the aquifer sand indicate that mobile waters obtain relatively unradiogenic Sr, whereas stagnant waters obtain relatively radiogenic Sr. Nearly the entire range of strontium-isotope composition observed in groundwaters from the watershed was measured in the experimental product waters. The constant mobility of water along groundwater recharge flowpaths emanating from the lakes promotes the dissolution of relatively unradiogenic plagioclase, perhaps due to effective dispersal of clay mineral nuclei resulting from dissolution reactions. In contrast, episodic stagnation in the unsaturated zone along the upland recharge flowpaths suppresses plagioclase dissolution, perhaps due to accumulation of clay mineral nuclei on its reactive surfaces. Differences in redox conditions along these contrasting flowpaths probably enhance the observed differences in strontium isotope behavior. This study demonstrates that factors other than the calculated state of mineral saturation must be considered when attempting to simulate chemical evolution along flowpaths, and that reaction models must be able to incorporate changing contributions from reacting minerals in the calculations.

Geochimica et Cosmochimica Acta↗

USGS1995

Mercury cycling in the Allequash Creek watershed, northern Wisconsin

Although there have been recent significant gains in our understanding of mercury (Hg) cycling in aquatic environments, few studies have addressed Hg cycling on a watershed scale in particular, attention to Hg species transfer between watershed components (upland soils, groundwater, wetlands, streams, and lakes) has been lacking. This study describes spatial and temporal distributions of total Hg and MeHg among watershed components of the Allequash Creek watershed (northern Wisconsin, USA). Substantial increases in total Hg and MeHg were observed as groundwater discharged through peat to form springs that flow into the stream, or rivulets that drain across the surface of the wetland. This increase was concomitant with increases in DOC. During fall, when the Allequash Creek wetland released a substantial amount of DOC to the stream, a 23 fold increase in total Hg concentrations was observed along the entire length of the stream. Methylmercury, however, did not show a similar response. Substantial variability was observed in total Hg (0.9 to 6.3) and MeHg (<0.02 to 0.33) concentrations during synoptic surveys of the entire creek. For the Allequash Creek watershed, the contributing groundwater basin is about 50% larger than the topographic drainage basin. Total Hg concentrations in groundwater, the area of the groundwater basin, and annual stream flow data give a watershed-yield rate of 12 mg/km2/d, which equates to a retention rate of 96%. The calculated MeHg yield rate for the wetland area is 0.6 to 1.5 mg/km2/d, a value that is 3-6 fold greater than the atmospheric deposition rate.

Water, Air, & Soil Pollution↗

USGS1992

Data on water quality, lake sediment, and lake-level fluctuation, St. Croix Indian Reservation, Wisconsin, 1981-87

This report is a compilation of data on surface- and ground-water quality, lake sediment, and lake-level fluctuation collected by the U.S. Geological Survey (USGS) during 1981- 87 on or near the St. Croix Indian Reservation. The purpose of this report is to provide baseline data on selected aspects of the water resources of the St. Croix Indian Reservation as a referenceby which future hydrologic changes can be discerned. The tribal lands are adjacent to Bashaw, BigRound, Big Sand, Clam, Gaslyn, Rice, and Sand Lakes and the Danbury Settlement along the St. Croix River. Water samples from each of these lakes and Bear Lake, which is not adjacent to tribal land, were analyzed for water-quality indicators. Lakelevel fluctuations also were measured for each lake except Big Round Lake. Grain-size and chemical analyses were done on lake-sediment samples from Bashaw, Rice, Clam, Gaslyn, and Bear Lakes. Ground-water samples from wells on or near tribal land in Burnett County (27 wells) and Polk County (3 wells) were collected and analyzed for water quality.

Wisconsin↗