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David P. Krabbenhoft

Publications and source records attributed to David P. Krabbenhoft.

At least 109 records · Page 6Linked to original sources

Estimating groundwater exchange with lakes: 1. The stable isotope mass balance method

Groundwater inflow and outflow contributions to the hydrologic budget of lakes can be determined using a stable isotope ( 18 O/ 16 O) mass balance method. The stable isotope method provides a way of integrating the spatial and temporal complexities of the flow field around a lake, thereby offering an appealing alternative to the traditional time and labor intensive methods using seepage meters and an extensive piezometer network. In this paper the method is applied to a lake in northern Wisconsin, demonstrating that it can be successfully applied to lakes in the upper midwest where thousands of similar lakes exist. Inflow and outflow rates calculated for the Wisconsin lake using the isotope mass balance method are 29 and 54 cm/yr, respectively, which compare well to estimates, derived independently using a three-dimensional groundwater flow and solute transport model, of 20 and 50 cm/yr. Such a favorable comparison lends confidence to the use of the stable isotope method to estimate groundwater exchange with lakes. In addition, utilization of stable isotopes in studies of groundwater-lake systems lends insight into mixing processes occurring in the unsaturated zone and in the aquifer surrounding the lake and verifies assumed flow paths based on head measurements in piezometers.

Wisconsin

Estimating groundwater exchange with lakes: 2. Calibration of a three-dimensional, solute transport model to a stable isotope plume

A three-dimensional groundwater flow and solute transport model was calibrated to a plume of water described by measurements of δ 18 O and used to calculate groundwater inflow and outflow rates at a lake in northern Wisconsin. The flow model was calibrated to observed hydraulic gradients and estimated recharge rates. Calibration of the solute transport submodel to the configuration of a stable isotope ( 18 O) plume in the contiguous aquifer on the downgradient side of the lake provides additional data to constrain the model. A good match between observed and simulated temporal variations in plume configuration indicates that the model closely simulated the dynamics of the real system. The model provides information on natural variations of rates of groundwater inflow, lake water outflow, and recharge to the water table. Inflow and outflow estimates compare favorably with estimates derived by the isotope mass balance method (Krabbenhoft et al., this issue). Model simulations agree with field observations that show groundwater inflow rates are more sensitive to seasonal variations in recharge than outflow.

Wisconsin

Patterns of mercury dispersion from local and regional emission sources, rural Central Wisconsin, USA

Simultaneous real-time changes in mercury (Hg) speciation-reactive gaseous Hg (RGM), elemental Hg (Hg??), and fine particulate Hg (Hg-PM 2.5 ), were determined from June to November 2007, in ambient air at three locations in rural Central Wisconsin. Known Hg emission sources within the airshed of the monitoring sites include: 1) a 1114 megawatt (MW) coal-fired electric utility generating station; 2) a Hg-bed chlor-alkali plant; and 3) a smaller (465 MW) coal-burning electric utility. Monitoring sites, showing sporadic elevation of RGM, Hg o and Hg-PM 2.5 , were positioned at distances of 25, 50 and 100 km northward of the larger electric utility. A series of RGM events were recorded at each site. The largest, on 23 September, occurred under prevailing southerly winds, with a maximum RGM value (56.8 pg m -3 ) measured at the 100 km site, and corresponding elevated SO 2 (10.41 ppbv; measured at 50 km site). The finding that RGM, Hg o , and Hg-PM 2.5 are not always highest at the 25 km site, closest to the large generating station, contradicts the idea that RGM decreases with distance from a large point source. This may be explained if: 1) the 100 km site was influenced by emissions from the chlor-alkali facility or by RGM from regional urban sources; 2) the emission stack height of the larger power plant promoted plume transport at an elevation where the Hg is carried over the closest site; or 3) RGM was being generated in the plume through oxidation of Hg o . Operational changes at each emitter since 2007 should reduce their Hg output, potentially allowing quantification of the environmental benefit in future studies.

Atmospheric Chemistry and Physics Discussions

Source identification of Florida Bay's methylmercury problem: Mainland runoff versus atmospheric deposition and in situ production

The first advisory to limit consumption of Florida Bay fish due to mercury was issued in 1995. Studies done by others in the late 1990s found elevated water column concentrations of both total Hg (THg) and methylmercury (MeHg) in creeks discharging from the Everglades, which had its own recognized mercury problem. To investigate the significance of allochthonous MeHg discharging from the upstream freshwater Everglades, we collected surface water and sediment along two transects from 2000 to 2002. Concentrations of THg and MeHg, ranging from 0.36 ng THg/L to 5.98 ng THg/L and from <0.02 ng MeHg/L to 1.79 ng MeHg/L, were elevated in the mangrove transition zone when compared both to upstream canals and the open waters of Florida Bay. Sediment concentrations ranged from 5.8 ng THg/g to 145.6 ng THg/g and from 0.05 ng MeHg/g to 5.4 ng MeHg/g, with MeHg as a percentage of THg occasionally elevated in the open bay. Methylation assays indicated that sediments from Florida Bay have the potential to methylate Hg. Assessment of mass loading suggests that canals delivering stormwater from the northern Everglades are not as large a source as direct atmospheric deposition and in situ methylation, especially within the mangrove transition zone.

Florida

Response of a macrotidal estuary to changes in anthropogenic mercury loading between 1850 and 2000

Methylmercury (MeHg) bioaccumulation in marine food webs poses risks to fish-consuming populations and wildlife. Here we develop and test an estuarine mercury cycling model for a coastal embayment of the Bay of Fundy, Canada. Mass budget calculations reveal that MeHg fluxes into sediments from settling solids exceed losses from sediment-to-water diffusion and resuspension. Although measured methylation rates in benthic sediments are high, rapid demethylation results in negligible net in situ production of MeHg. These results suggest that inflowing fluvial and tidal waters, rather than coastal sediments, are the dominant MeHg sources for pelagic marine food webs in this region. Model simulations show water column MeHg concentrations peaked in the 1960s and declined by almost 40% by the year 2000. Water column MeHg concentrations respond rapidly to changes in mercury inputs, reaching 95% of steady state in approximately 2 months. Thus, MeHg concentrations in pelagic organisms can be expected to respond rapidly to mercury loading reductions achieved through regulatory controls. In contrast MeHg concentrations in sediments have steadily increased since the onset of industrialization despite recent decreases in total mercury loading. Benthic food web MeHg concentrations are likely to continue to increase over the next several decades at present-day mercury emissions levels because the deep active sediment layer in this system contains a large amount of legacy mercury and requires hundreds of years to reach steady state with inputs.

Environmental Science & Technology

Comparison of mercury in water, bottom sediment, and zooplankton in two Front Range reservoirs in Colorado, 2008-09

The U.S. Geological Survey, in cooperation with the Colorado Department of Public Health and Environment, conducted a study to investigate environmental factors that may contribute to the bioaccumulation of mercury in two Front Range reservoirs. One of the reservoirs, Brush Hollow Reservoir, currently (2009) has a fish-consumption advisory for mercury in walleye (Stizostedion vitreum), and the other, Pueblo Reservoir, which is nearby, does not. Water, bottom sediment, and zooplankton samples were collected during 2008 and 2009, and a sediment-incubation experiment was conducted in 2009. Total mercury concentrations were low in midlake water samples and were not substantially different between the two reservoirs. The only water samples with detectable methylmercury were collected in shallow areas of Brush Hollow Reservoir during spring. Mercury concentrations in reservoir bottom sediments were similar to those reported for stream sediments from unmined basins across the United States. Despite higher concentrations of fish-tissue mercury in Brush Hollow Reservoir, concentrations of methylmercury in sediment were as much as 3 times higher in Pueblo Reservoir. Mercury concentrations in zooplankton were at the low end of concentrations reported for temperate lakes in the Northeastern United States and were similar between sites, which may reflect the seasonal timing of sampling. Factors affecting bioaccumulation of mercury were assessed, including mercury sources, water quality, and reservoir characteristics. Atmospheric deposition was determined to be the dominant source of mercury; however, due to the proximity of the reservoirs, atmospheric inputs likely are similar in both study areas. Water-quality constituents commonly associated with elevated concentrations of mercury in fish (pH, alkalinity, sulfate, nutrients, and dissolved organic carbon) did not appear to explain differences in fish-tissue mercury concentrations between the reservoirs. Low methylmercury concentrations in hypolimnetic water indicate low potential for increased methylmercury production following the development of anoxic conditions in summer. Based on the limited dataset, water-level fluctuations and shoreline characteristics appear to best explain differences in fish-tissue mercury concentrations between the reservoirs. Due to the shallow depth and the large annual water-level fluctuations at Brush Hollow Reservoir, proportionally larger areas of shoreline at Brush Hollow Reservoir are subjected to annual reflooding compared to Pueblo Reservoir. Moreover, presence of macrophyte beds and regrowth of terrestrial vegetation likely increase the organic content of near-shore sediments in Brush Hollow Reservoir, which may stimulate methylmercury production in littoral areas subject to reflooding. Results of a laboratory incubation experiment were consistent with this hypothesis.

Colorado

Use of oxygen-18 and deuterium to assess the hydrology of groundwater-lake systems

A thorough understanding of a lake's hydrology is essential for many lake studies. In some situations the interactions between groundwater systems and lakes are complex; in other cases the hydrology of a multilake system needs to be quantified. In such places, stable isotopes offer an alternative to the more traditional piezometer networks, which are costly to install and time-consuming to maintain. The stable-isotope mass-balance relations presented here can be used to estimate groundwater exchange rates for individual lakes and geographically clustered lakes. These relations also can be used to estimate other hydrological factors, such as average relative humidity. In places where the groundwater system is unstable (e.g., where flow reversals occur), natural solute tracers may provide a better alternative than stable isotopes for estimating rates of groundwater flow to and from lakes.

Book chapter

Cycling of mercury across the sediment-water interface in seepage lakes: Chapter 13, Advances in Chemistry

The magnitude and direction of Hg fluxes across the sediment&mdash;water interface were estimated by groundwater, dry bulk sediment, sediment pore water, sediment trap, and water-column analyses in two northern Wisconsin seepage lakes. Little Rock Lake (Treatment Basin) received no groundwater discharge during the study period (1988&mdash;1990), and Follette Lake received continuous groundwater discharge. In Little Rock Lake, settling of particulate matter accounted for the major Hg delivery mechanism to the sediment&mdash;water interface. Upward diffusion of Hg from sediment pore waters below 2&mdash;4-cm sediment depth was apparently a minor source during summer stratification. Time-series comparisons suggested that the observed buildup of Hg in the hypolimnion of Little Rock Lake was attributable to dissolution and diffusion of Hg from recently fallen particulate matter close to the sediment&mdash;water interface. Groundwater inflow represented an important source of new Hg, and groundwater outflow accounted for significant removal of Hg from Pallette Lake. Equilibrium speciation calculations revealed that association of Hg with organic matter may control solubility in well-oxygenated waters, whereas in anoxic environments sulfur (polysulfide and bisulfide) complexation governs dissolved total Hg levels.

Wisconsin

Experimental removal of wetland emergent vegetation leads to decreased methylmercury production in surface sediment

We performed plant removal (devegetation) experiments across a suite of ecologically diverse wetland settings (tidal salt marshes, river floodplain, rotational rice fields, and freshwater wetlands with permanent or seasonal flooding) to determine the extent to which the presence (or absence) of actively growing plants influences the activity of the Hg(II)-methylating microbial community and the availability of Hg(II) to those microbes. Vegetated control plots were paired with neighboring devegetated plots in which photosynthetic input was terminated 4–8 months prior to measurements, through clipping aboveground biomass, severing belowground connections, and shading the sediment surface to prevent regrowth. Across all wetlands, devegetation decreased the activity of the Hg(II)-methylating microbial community (k meth ) by 38%, calculated MeHg production potential (MP) rates by 36%, and pore water acetate concentration by 78%. Decreases in MP were associated with decreases in microbial sulfate reduction in salt marsh settings. In freshwater agricultural wetlands, decreases in MP were related to indices of microbial iron reduction. Sediment MeHg concentrations were also significantly lower in devegetated than in vegetated plots in most wetland settings studied. Devegetation effects were correlated with live root density (percent volume) and were most profound in vegetated sites with higher initial pore water acetate concentrations. Densely rooted wetlands had the highest rates of microbial Hg(II)-methylation activity but often the lowest concentrations of bioavailable reactive Hg(II). We conclude that the exudation of labile organic carbon (e.g., acetate) by plants leads to enhanced microbial sulfate and iron reduction activity in the rhizosphere, which results in high rates of microbial Hg(II)-methyation and high MeHg concentrations in wetland sediment.

Journal of Geophysical Research: Biogeosciences

Mercury in fish, bed sediment, and water from streams across the United States, 1998-2005

Mercury (Hg) was examined in top-predator fish, bed sediment, and water from streams that spanned regional and national gradients of Hg source strength and other factors thought to influence methylmercury (MeHg) bioaccumulation. Sampled settings include stream basins that were agricultural, urbanized, undeveloped (forested, grassland, shrubland, and wetland land cover), and mined (for gold and Hg). Each site was sampled one time during seasonal low flow. Predator fish were targeted for collection, and composited samples of fish (primarily skin-off fillets) were analyzed for total Hg (THg), as most of the Hg found in fish tissue (95-99 percent) is MeHg. Samples of bed sediment and stream water were analyzed for THg, MeHg, and characteristics thought to affect Hg methylation, such as loss-on-ignition (LOI, a measure of organic matter content) and acid-volatile sulfide in bed sediment, and pH, dissolved organic carbon (DOC), and dissolved sulfate in water. Fish-Hg concentrations at 27 percent of sampled sites exceeded the U.S. Environmental Protection Agency human-health criterion of 0.3 micrograms per gram wet weight. Exceedances were geographically widespread, although the study design targeted specific sites and fish species and sizes, so results do not represent a true nationwide percentage of exceedances. The highest THg concentrations in fish were from blackwater coastal-plain streams draining forests or wetlands in the eastern and southeastern United States, as well as from streams draining gold- or Hg-mined basins in the western United States (1.80 and 1.95 micrograms THg per gram wet weight, respectively). For unmined basins, length-normalized Hg concentrations in largemouth bass were significantly higher in fish from predominantly undeveloped or mixed-land-use basins compared to urban basins. Hg concentrations in largemouth bass from unmined basins were correlated positively with basin percentages of evergreen forest and also woody wetland, especially with increasing proximity of these two land-cover types to the sampling site; this underscores the greater likelihood for Hg bioaccumulation to occur in these types of settings. Increasing concentrations of MeHg in unfiltered stream water, and of bed-sediment MeHg normalized by LOI, and decreasing pH and dissolved sulfate were also important in explaining increasing Hg concentrations in largemouth bass. MeHg concentrations in bed sediment correlated positively with THg, LOI, and acid-volatile sulfide. Concentrations of MeHg in water correlated positively with DOC, ultraviolet absorbance, and THg in water, the percentage of MeHg in bed sediment, and the percentage of wetland in the basin.

Scientific Investigations Report

Geological, geochemical, and geophysical studies by the U.S. Geological Survey in Big Bend National Park, Texas

Big Bend National Park (BBNP), Tex., covers 801,163 acres (3,242 km 2 ) and was established in 1944 through a transfer of land from the State of Texas to the United States. The park is located along a 118-mile (190-km) stretch of the Rio Grande at the United States-Mexico border. The park is in the Chihuahuan Desert, an ecosystem with high mountain ranges and basin environments containing a wide variety of native plants and animals, including more than 1,200 species of plants, more than 450 species of birds, 56 species of reptiles, and 75 species of mammals. In addition, the geology of BBNP, which varies widely from high mountains to broad open lowland basins, also enhances the beauty of the park. For example, the park contains the Chisos Mountains, which are dominantly composed of thick outcrops of Tertiary extrusive and intrusive igneous rocks that reach an altitude of 7,832 ft (2,387 m) and are considered the southernmost mountain range in the United States. Geologic features in BBNP provide opportunities to study the formation of mineral deposits and their environmental effects; the origin and formation of sedimentary and igneous rocks; Paleozoic, Mesozoic, and Cenozoic fossils; and surface and ground water resources. Mineral deposits in and around BBNP contain commodities such as mercury (Hg), uranium (U), and fluorine (F), but of these, the only significant mining has been for Hg. Because of the biological and geological diversity of BBNP, more than 350,000 tourists visit the park each year. The U.S. Geological Survey (USGS) has been investigating a number of broad and diverse geologic, geochemical, and geophysical topics in BBNP to provide fundamental information needed by the National Park Service (NPS) to address resource management goals in this park. Scientists from the USGS Mineral Resources and National Cooperative Geologic Mapping Programs have been working cooperatively with the NPS and several universities on several research studies within BBNP. Because the last geologic map of the entire BBNP was published in the 1960s, one of the primary goals of the USGS is to provide a new geologic map of BBNP at a scale 1:100,000; this work is ongoing among the USGS, NPS, the Texas Bureau of Economic Geology, and university scientists. This USGS Circular summarizes eight studies funded and primarily carried out by the USGS, but it is not intended to be a comprehensive reference of work conducted in BBNP. This Circular describes topical research of the recently completed interdisciplinary USGS project, which has provided information leading to a more complete understanding of the following topics in BBNP: Tectonic and geologic history (Chapters 1, 2, and 3), Age and formation processes of a skarn mineral deposit (Chapter 4), Geoenvironmental effects of abandoned mercury mines (Chapter 5), Age, source, and geochemistry of surface and subsurface water resources (Chapter 6), Isotopic tracing of food sources of bears (Chapter 7), and Geophysical characteristics of surface and subsurface geology (Chapter 8). Additional information and the geochemical and geophysical data of the USGS studies in BBNP are available on line at http://minerals.cr.usgs.gov/projects/big_bend/index.html.

Texas

Total mercury, methylmercury, methylmercury production potential, and ancillary streambed-sediment and pore-water data for selected streams in Oregon, Wisconsin, and Florida, 2003-04

Mercury contamination of aquatic ecosystems is an issue of national concern, affecting both wildlife and human health. Detailed information on mercury cycling and food-web bioaccumulation in stream settings and the factors that control these processes is currently limited. In response, the U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) conducted detailed studies from 2002 to 2006 on various media to enhance process-level understanding of mercury contamination, biogeochemical cycling, and trophic transfer. Eight streams were sampled for this study: two streams in Oregon, and three streams each in Wisconsin and Florida. Streambed-sediment and pore-water samples were collected between February 2003 and September 2004. This report summarizes the suite of geochemical and microbial constituents measured, the analytical methods used, and provides the raw data in electronic form for both bed-sediment and pore-water media associated with this study.

Oregon, Wisconsin, Florida

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations.

Nevada

Whole-ecosystem study shows rapid fish-mercury response to changes in mercury deposition

Methylmercury contamination of fisheries from centuries of industrial atmospheric emissions negatively impacts humans and wild-life worldwide. The response of fish methylmercury concentrations to changes in mercury deposition has been difficult to establish because sediments/soils contain large pools of historical contamination, and many factors in addition to deposition affect fish mercury. To test directly the response of fish contamination to changing mercury deposition, we conducted a whole-ecosystem experiment, increasing the mercury load to a lake and its watershed by the addition of enriched stable mercury isotopes. The isotopes allowed us to distinguish between experimentally applied mercury and mercury already present in the ecosystem and to examine bioaccumulation of mercury deposited to different parts of the watershed. Fish methylmercury concentrations responded rapidly to changes in mercury deposition over the first 3 years of study. Essentially all of the increase in fish methylmercury concentrations came from mercury deposited directly to the lake surface. In contrast, <1% of the mercury isotope deposited to the watershed was exported to the lake. Steady state was not reached within 3 years. Lake mercury isotope concentrations were still rising in lake biota, and watershed mercury isotope exports to the lake were increasing slowly. Therefore, we predict that mercury emissions reductions will yield rapid (years) reductions in fish methylmercury concentrations and will yield concomitant reductions in risk. However, a full response will be delayed by the gradual export of mercury stored in watersheds. The rate of response will vary among lakes depending on the relative surface areas of water and watershed.

Proceedings of the National Academy of Sciences of

Evasion of added isotopic mercury from a northern temperate lake

Isotopically enriched Hg (90% 202Hg) was added to a small lake in Ontario, Canada, at a rate equivalent to approximately threefold the annual direct atmospheric deposition rate that is typical of the northeastern United States. The Hg spike was thoroughly mixed into the epilimnion in nine separate events at two-week intervals throughout the summer growing season for three consecutive years. We measured concentrations of spike and ambient dissolved gaseous Hg (DGM) concentrations in surface water and the rate of volatilization of Hg from the lake on four separate, week-long sampling periods using floating dynamic flux chambers. The relationship between empirically measured rates of spike-Hg evasion were evaluated as functions of DGM concentration, wind velocity, and solar illumination. No individual environmental variable proved to be a strong predictor of the evasion flux. The DGM-normalized flux (expressed as the mass transfer coefficient, k) varied with wind velocity in a manner consistent with existing models of evasion of volatile solutes from natural waters but was higher than model estimates at low wind velocity. The empirical data were used to construct a description of evasion flux as a function of total dissolved Hg, wind, and solar illumination. That model was then applied to data for three summers for the experiment to generate estimates of Hg re-emission from the lake surface to the atmosphere. Based on ratios of spike Hg to ambient Hg in DGM and dissolved total Hg pools, ratios of DGM to total Hg in spike and ambient Hg pools, and flux estimates of spike and ambient Hg, we concluded that the added Hg spike was chemically indistinguishable from the ambient Hg in its behavior. Approximately 45% of Hg added to the lake over the summer was lost via volatilization.

Ontario

Local and regional factors affecting atmospheric mercury speciation at a remote location

Atmospheric concentrations of elemental (Hg0), reactive gaseous (RGM), and particulate (PHg) mercury were measured at two remote sites in the midwestern United States. Concurrent measurements of Hg0, PHg, and RGM obtained at Devil's Lake and Mt. Horeb, located approximately 65 km apart, showed that Hg0 and PHg concentrations were affected by regional, as well as local sources, while RGM was mainly impacted by local sources. Plumes reaching the Devil's Lake site from a nearby coal-fired power plant significantly impacted SO2 and RGM concentrations at Devil's Lake, but had little impact on Hg0. Our findings suggest that traditional modeling approaches to assess sources of mercury deposited that utilize source emissions and large-scale grids may not be sufficient to predict mercury deposition at sensitive locations due to the importance of small-scale sources and processes. We suggest the use of a receptor-based monitoring to better understand mercury source-receptor relationships.

Wisconsin