Humic substances typically constitute 40-60% of the dissolved organic matter (DOM) in surface waters. However, little information is available regarding the metal binding properties of the nonhumic hydrophilic portion of the DOM. In this study, humic and nonhumic DOM samples were isolated from the South Platte River (Colorado, DOC = 2.6 mg·L-1, SUVA254 = 2.4 L/mg·m) using a two-column array of XAD-8 and XAD-4 resins. The three major isolated fractions of DOM, which accounted for 57% of the bulk DOM, were characterized using a variety of analytical tools. Proton and copper binding properties were studied for each fraction. The main objective of this work was to compare the structural and chemical characteristics of the isolated fractions and test models describing DOM reactivity toward metal ions. The characterization work showed significant structural differences between the three isolated fractions of DOM. The hydrophobic acid fraction (i.e., humic substances isolated from the XAD-8 resin) gave the largest C/H, C/O, and C/N ratios and aromatic carbon content among the three isolated fractions. The transphilic acid (TPHA) fraction ("transphilic" meaning fraction of intermediate polarity isolated from the XAD-4 resin) was found to incorporate the highest proportion of polysaccharides, whereas the transphilic neutral (TPHN) fraction was almost entirely proteinaceous. The gradual increase of the charge with pH for the three DOM fractions is most likely caused by a large distribution of proton affinity constants for the carboxylic groups, as well as a second type of group more generally considered to be phenolic. In the case of the DOM fraction enriched in proteinaceous material (i.e., TPHN fraction), the results showed that the amino groups are responsible for the charge reversal. For low copper concentrations, nitrogen-containing functional groups similar to those of amino acids are likely to be involved in complexation, in agreement with previously published data.
The San Francisco Bay/Sacramento-San Joaquin Delta system provides habitat for some 750 plant and animal species, provides drinking water for 22 million people, provides irrigation supplies for at least $27 billion in agriculture, and is a primary water source for California's trillion-dollar economy. Both the ecosystems and the resource systems of this remarkable system, however, are in trouble. The Bay-Delta system is neither a healthy ecosystem nor a reliable source to meet growing demands for high-quality water. Recognizing the decline of this system and the urgency of its restoration, more than 20 State and Federal agencies have banded together to establish the multi-billon dollar, 30-yr CALFED Bay-Delta Restoration Program, which will develop and implement a comprehensive plan to accomplish four ambitious objectives:
1. Improve the reliability of water supplies in California,
2. Improve water quality in the Bay-Delta system,
3. Restore ecosystems within the Bay/Delta watershed, and
4. Stabilize Sacramento-San Joaquin Delta levees.
The success of the CALFED Program depends, among many other factors, upon the robustness of its plans and actions to the considerable buffeting that California's highly variable climate will inevitably impose upon it. The Bay-Delta watershed spans the West Coast precipitation influences of the El Nino-Southern Oscillation climate variations, their interdecadal realization in the Pacific Decadal Oscillation, and other short- and (especially) long-term influences that are less well understood. In addition, recent observed winter-spring warming and streamflow-timing trends are either harbingers or analogs for future global warming effects in the State and threaten to unsettle crucial aspects of the State's water supply system by adversely impacting the State's snowpacks and snowmelt runoff. Recent studies of California's paleoclimate also provide worrying evidence that the erratic precipitation regimes that have been observed (and largely accomodated) during the several hundred years of California's development have beenby and largebenign and small in comparison to the precipitation variations over the past 1000 or more years. Thus, California's climate has varied in ways that CALFED must be prepared to accommodate, on time scales from years to decades, as evidenced in its past and present climates as well as in projections of its future climate. These climate fluctuations need to be characterized (i.e., monitored, predicted, projected, or described probabilistically, depending on circumstance) to provide a basis for scientifically sound planning and management actions by the CALFED Program.
Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations 5500 mg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 Å was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 Å was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations 5500 mg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 mg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.
Conditional distribution coefficients (KDOM') for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that KDOM' values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (1022.5±1.0-1023.5±1.0 L kg-1), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. KDOM' values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)-DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pKa = 10.3) and one other group (pKa = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)-DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).
 We interpret new chemical and isotopic data from samples collected between October 1998 and March 2002 from the NSF well (also called the Keller well), the only deep well on the summit of Kilauea Volcano, Hawaii. Sample collection followed cleaning of the well, which renewed access to the hydrothermal system very close to the loci of magmatic and fumarolic activity. The chemical and isotopic compositions of the new samples differ remarkably from data published previously. On the basis of the S/Cl ratio and carbon and helium isotopes we conclude that the thermal fluids formed by condensation of magmatic gas into shallow meteoric groundwater. Gas condensation was followed by a complex pattern of basalt dissolution accompanied by an increase of fluid pH and precipitation of secondary minerals. Geochemical modeling and geothermometry imply that the fluids equilibrated with an assemblage of secondary minerals at temperatures between 90 and 140°C. The significantly different chemical composition of the NSF well fluids from that of springs along the southern coast of the island indicates that mass transport from the summit region toward the lower flanks of the volcano is limited.
Radium activity in pore water of wetland sediments often differs from the amount expected from local production, decay, and exchange with solid phases. This disequilibrium results from vertical transport of radium with groundwater that flows between the underlying aquifer and surface water. In situations where groundwater recharge or discharge is significant, the rate of vertical water flow through wetland sediment can be determined from the radium disequilibrium by a combined model of transport, production, decay, and exchange with solid phases. We have developed and tested this technique at three sites in the freshwater portion of the Everglades by quantifying vertical advective velocities in areas with persistent groundwater recharge or discharge and estimating a coefficient of dispersion at a site that is subject to reversals between recharge and discharge. Groundwater velocities (v) were determined to be between 0 and -0.5 cm d-1 for a recharge site and 1.5 ± 0.4 cm d-1 for a discharge site near Levee 39 in the Everglades. Strong gradients in 223Ra and 224Ra usually occurred at the base of the peat layer, which avoided the problems of other tracers (e.g., chloride) for which greatest sensitivity occurs near the peat surface--a zone readily disturbed by processes unrelated to groundwater flow. This technique should be easily applicable to any wetland system with different production rates of these isotopes in distinct sedimentary layers or surface water. The approach is most straightforward in systems where constant pore-water ionic strength can be assumed, simplifying the modeling of radium exchange.
Roxarsone, 3-nitro-4-hydroxyphenylarsonic acid, is an organoarsenic compound that is used extensively in the feed of broiler poultry to control coccidial intestinal parasites, improve feed efficiency, and promote rapid growth. Nearly all the roxarsone in the feed is excreted unchanged in the manure. Poultry litter composed of the manure and bedding material has a high nutrient content and is used routinely as a fertilizer on cropland and pasture. Investigations were conducted to determine the fate of poultry-litter roxarsone in the environment. Experiments indicated that roxarsone was stable in fresh dried litter; the primary arsenic species extracted with water from dried litter was roxarsone. However, when water was added to litter at about 50 wt % and the mixture was allowed to compost at 40 oC, the speciation of arsenic shifted from roxarsone to primarily arsenate in about 30 days. Increasing the amount of water increased the rate of degradation. Experiments also suggested that the degradation process most likely was biotic in nature. The rate of degradation was directly proportional to the incubation temperature; heat sterilization eliminated the degradation. Biotic degradation also was supported by results from enterobacteriaceae growth media that were inoculated with litter slurry to enhance the biotic processes and to reduce the concomitant abiotic effects from the complex litter solution. Samples collected from a variety of litter windrows in Arkansas, Oklahoma, and Maryland also showed that roxarsone originally present had been converted to arsenate.
Glacier wastage has been pervasive during the last century; small glaciers and those in marginal environments are disappearing, large mid-latitude glaciers are shrinking slightly, and arctic glaciers are warming. Net mass balances during the last 40 years are predominately negative and both winter and summer balances (accumulation and ablation) and mass turnover are increasing, especially after 1988. Two principal components of winter balance time-series explain about 50% of the variability in the data. Glacier winter balances in north and central Europe correlate with the Arctic Oscillation, and glaciers in western North America correlate with the Southern Oscillation and Northern Hemisphere air temperature. The degree of synchronization for distant glaciers relates to changes in time of atmospheric circulation patterns as well as differing dynamic responses.
The link between stress and hydrologic properties was examined at two sites that are distinguished by different rock types and different stress states. This investigation is based upon the analysis and interpretation of geophysical logs obtained in water wells at the two locations. At the northeast site (Newark Basin), the hydrologic characteristics of sedimentary rocks are dependent upon the relationship to the current regional stress field of two primary types of orthogonal features that serve as preferential pathways for fluid flow. Subhorizontal bedding-plane partings are highly transmissive near the surface and delineate transversely isotropic fluid flow at shallow depths. With increasing depth, the subhorizontal planes become less dominant and steeply dipping fractures become more influential hydrologically. These high-angle features define anisotropic flow pathways that are preferentially oriented along strike. At the southwest site (west Texas), extrusive rocks are subjected to topographically modified tectonic and gravitational stresses that vary spatially within a valley setting. The attendant changes in stress invariants cause fracture connectivity within the rock mass to systematically increase with depth along the valley flanks, but to remain relatively low in the central valley. The degree of fracture connectivity predicted within this valley configuration is consistent with variations in transmissivity determined at several well locations. In each of these cases, the idealized understanding of the hydrologic system is enhanced by considering the effects of regional and local stresses that act upon the fractured-rock aquifer.
Arsenic is a metalloid whose name conjures up images of murder. Nonetheless, certain prokaryotes use arsenic oxyanions for energy generation, either by oxidizing arsenite or by respiring arsenate. These microbes are phylogenetically diverse and occur in a wide range of habitats. Arsenic cycling may take place in the absence of oxygen and can contribute to organic matter oxidation. In aquifers, these microbial reactions may mobilize arsenic from the solid to the aqueous phase, resulting in contaminated drinking water. Here we review what is known about arsenic-metabolizing bacteria and their potential impact on speciation and mobilization of arsenic in nature.
Poultry litter often contains arsenic as a result of organo-arsenical feed additives. When the poultry litter is applied to agricultural fields, the arsenic is released to the environment and may result in increased arsenic in surface and groundwater and increased uptake by plants. The release of arsenic from poultry litter, litter-amended soils, and soils without litter amendment was examined by extraction with water and strong acids (HCl and HNO3). The extracts were analyzed for As, C, P, Cu, Zn, and Fe. Copper, zinc, and iron are also poultry feed additives. Soils with a known history of litter application and controlled application rate of arsenic-containing poultry litter were obtained from the University of Maryland Agricultural Experiment Station. Soils from fields with long-term application of poultry litter were obtained from a tilled field on the Delmarva Peninsula (MD) and an untilled Oklahoma pasture. Samples from an adjacent forest or nearby pasture that had no history of litter application were used as controls. Depth profiles were sampled for the Oklahoma pasture soils. Analysis of the poultry litter showed that 75% of the arsenic was readily soluble in water. Extraction of soils shows that weakly bound arsenic mobilized by water correlates positively with C, P, Cu, and Zn in amended fields and appears to come primarily from the litter. Strongly bound arsenic correlates positively with Fe in amended fields and suggests sorption or coprecipitation of As and Fe in the soil column.
Calculations indicate that the impact of an asteroid or comet on the Atlantic Coastal Plain 35 million years ago created subsequent hydrothermal activity and conditions suitable for phase separation and the creation of the brine observed in the groundwater at the site today. A calculation of groundwater velocity using Darcy's law suggests flow rates are insufficient to have moved the water out of the crater within 35 million years. A similar calculation using Fick's law demonstrates that solutes cannot have escaped by molecular diffusion since the impact. Simulations from other investigators using shock-physics codes indicate that the crust would have been vaporized or melted down to at least 2 km at the time of impact. Based on these calculations, a simulation of heat conduction was made assuming a 1000 jC initial crustal temperature. The hot crust acted as a heat source, with temperatures peaking in the overlying sediment about 10,000 years later. The pressure and temperature conditions within the sediment during that time would have been favorable for phase separation and generation of a residual brine, which may be found today in the inner crater.
Inorganic N transformations were examined in streambed sediments from the Shingobee River using sediment perfusion cores. The experimental design simulated groundwaterstream water mixing within sediment cores, which provided a well-defined one-dimensional representation of in situ hydrologic conditions. Two distinct hydrologic and chemical settings were preserved in the sediment cores: the lowermost sediments, perfused with groundwater, remained anaerobic during the incubations, whereas the uppermost sediments, perfused with oxic water pumped from the overlying water column, simulated stream water penetration into the bed. The maintenance of oxic and anoxic zones formed a biologically active aerobic-anaerobic interface. Ammonium (NH+4) dissolved in groundwater was transported conservatively through the lower core zone but was removed as it mixed with aerated recycle water. Concurrently, a small quantity of nitrate (NO-3 ) equaling ~25% of the NH+4 loss was produced in the upper sedi-ments. The NH+4 and NO-3 profiles in the uppermost sediments resulted from coupled nitrification-denitrification, because assimilation and sorption were negligible. We hypothesize that anaerobic microsites within the aerated upper sediments supported denitrification. Rates of nitrification and denitrification in the perfusion cores ranged 42209 and 53160 mg N m-2 day-1, respectively. The use of modified perfusion cores permitted the identification and quantification of N transformations and verified process control by surface water exchange into the shallow hyporheic zone of the Shingobee River.
Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 mM SO4-2·day-1, respectively. The concentration of sulfate in the core of the leachate plume was well below 20 mM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (~100 mM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.
The use of airborne hyperspectral remote sensing imagery for automated mapping of submerged aquatic vegetation (SAV) in the tidal Potomac River was investigated for near to real-time resource assessment and monitoring. Airborne hyperspectral imagery and field spectrometer measurements were obtained in October of 2000. A spectral library database containing selected ground-based and airborne sensor spectra was developed for use in image processing. The spectral library is used to automate the processing of hyperspectral imagery for potential real-time material identification and mapping. Field based spectra were compared to the airborne imagery using the database to identify and map two species of SAV (Myriophyllum spicatum and Vallisneria americana). Overall accuracy of the vegetation maps derived from hyperspectral imagery was determined by comparison to a product that combined aerial photography and field based sampling at the end of the SAV growing season. The algorithms and databases developed in this study will be useful with the current and forthcoming space-based hyperspectral remote sensing systems.
Winter, T.C., Buso, D.C., Rosenberry, D.O., Likens, G.E., Sturrock, A.M., and Mau, D.P, 2003, Evaporation determined by the energy-budget method for Mirror Lake, New Hampshire: Limnology and Oceanography, v. 48, no. 3, p. 995-1009
Evaporation was determined by the energy-budget method for Mirror Lake during the open water periods of 1982-1987. For all years, evaporation rates were low in spring and fall and highest during the summer. However,the times of highest evaporation rates varied during the 6 yr. Evaporation reached maximum rates in July for three of the years, in June for two of the years, and in August for one of the years. The highest evaporation rate during the 6-yr study was 0.46 cm d-1 during 27 May4 June 1986 and 1521 July 1987. Solar radiation and atmospheric radiation input to the lake and long-wave radiation emitted from the lake were by far the largest energy fluxes to and from the lake and had the greatest effect on evaporation rates. Energy advected to and from the lake by precipitation, surface water, and ground water had little effect on evaporation rates. In the energy-budget method, average evaporation rates are determined for energy-budget periods, which are bounded by the dates of thermal surveys of the lake. Our study compared evaporation rates calculated for short periods, usually ~1 week, with evaporation rates calculated for longer periods, usually ~2 weeks. The results indicated that the shorter periods showed more variability in evaporation rates, but seasonal patterns, with few exceptions, were similar.
Winter, T.C., Buso, D.C., Rosenberry, D.O., Likens, G.E., Sturrock, A.M., and Mau, D.P, 2003, Evaporation determined by the energy-budget method for Mirror Lake, New Hampshire: Limnology and Oceanography, v. 48, no. 3, p. 995-1009.
Evaporation was determined by the energy-budget method for Mirror Lake during the open water periods of 19821987. For all years, evaporation rates were low in spring and fall and highest during the summer. However,the times of highest evaporation rates varied during the 6 yr. Evaporation reached maximum rates in July for three of the years, in June for two of the years, and in August for one of the years. The highest evaporation rate during the 6-yr study was 0.46 cm d-1 during 27 May4 June 1986 and 1521 July 1987. Solar radiation and atmospheric radiation input to the lake and long-wave radiation emitted from the lake were by far the largest energy fluxes to and from the lake and had the greatest effect on evaporation rates. Energy advected to and from the lake by precipitation, surface water, and ground water had little effect on evaporation rates. In the energy-budget method, average evaporation rates are determined for energy-budget periods, which are bounded by the dates of thermal surveys of the lake. Our study compared evaporation rates calculated for short periods, usually ~1 week, with evaporation rates calculated for longer periods, usually ~2 weeks. The results indicated that the shorter periods showed more variability in evaporation rates, but seasonal patterns, with few exceptions, were similar.