Estimates of the assimilation and retention of trace elements from food by fish are useful for linking toxicity with the biogeochemical cycling of these elements through aquatic food webs. Here we use pulse-chase radiotracer techniques to estimate the assimilation and retention of Se and four trace metals, Ag, Am, Zn, and Cd, by 43- and 88-d-old juvenile striped bass, Morone saxatilis, from crustacean food. Brine shrimp nauplii, Artemia franciscana, or adult copepods, Acartia tonsa, were fed radiolabeled diatoms and then fed to juvenile striped bass. Assimilation efficiencies (AEs ± SD) for 43-d-old fish were 18 ± 2%, 6 ± 1%, 23 ± 4%, 33 ± 3%, and 23 ± 2% for Ag, Am, Cd, Se, and Zn, respectively. For 88-d-old fish, the AEs were 28 ± 1%, 42 ± 5%, and 40 ± 5% for Cd, Se, and Zn, respectively. The higher AEs in the older fish may result from longer gut passage times for larger fish. The 44-d-old fish excreted 5 ± 0.8%, 4 ± 2.0%, 7 ± 0.3%, 9 ± 0.4%, and 1.3 ± 0.9% of the Ag, Am, Cd, Se, and Zn, respectively, they ingested from food per day, whereas the 88-d-old fish excreted 3 ± 1.0%, 8 ± 0.5%, and 3 ± 0.5% of the assimilated Cd, Se, and Zn per day, respectively. Predictions of steady state Se concentrations in juvenile striped bass tissues made using a biokinetic model and the measured AE and efflux rates ranged from 1.8 to 3.0 mg Se g-1 dry wt for muscle tissue and 6.8 to 11.6 mg Se g-1 dry wt for gut tissue. These predictions agreed well with average values of 2.1 and 13 mg Se g-1 dry wt measured independently in North San Francisco Bay, where elevated Se concentrations are of concern. The model results imply that the planktonic food web, including juvenile striped bass, does not transfer Se as efficiently to top consumers as does the benthic food web.
Bekins, B.A., I.M. Cozzarelli, E. Warren, E. M. Godsy, 2002, Microbial ecology of a crude-oil contaminated aquifer, in Thornton, S.F., and Oswald, S.E., eds., Natural and Enhanced Restoration of Groundwater Pollution: International Association of Hydrological Sciences, IAHS Red Book Series no 275, p. 57-63.Detailed microbial analyses of a glacial outwash aquifer contaminated by crude oil provide insights into the pattern of microbial succession from iron reducing to methanogenic in the anaerobic portion of the contaminant plume. We analysed sediments from this area for populations of aerobes, iron reducers, fermenters and methanogens, using the most probable number method. On the basis of the microbial data the anaerobic area can be divided into distinct physiological zones dominated by either iron-reducers or a consortium of fermenters and methanogens. Chemistry and permeability data show that methanogenic conditions develop first in areas of high hydrocarbon flux. Thus, we find methanogens both in high permeability horizons and also where separate-phase crude oil is present in either the saturated or unsaturated zone. Microbial numbers peak at the top of the separate-phase oil suggesting that growth is most rapid in locations with access to both hydrocarbons and nutrients infiltrating from the surface.
Continuous, high-resolution d18O records from cored sediments of Pyramid Lake, Nevada, indicate that oscillations in the hydrologic balance occurred, on average, about every 150 years (yr) during the past 7630 calendar years (calyr). The records are not stationary; during the past 2740 yr, drought durations ranged from 20 to 100 yr and intervals between droughts ranged from 80 to 230 yr. Comparison of tree-ring-based reconstructions of climate change for the past 1200 yr from the Sierra Nevada and the El Malpais region of northwest New Mexico indicates that severe droughts associated with Anasazi withdrawal from Chaco Canyon at 820 calyrBP (calendar years before present) and final abandonment of Chaco Canyon, Mesa Verde, and the Kayenta area at 650 calyrBP may have impacted much of the western United States.During the middle Holocene (informally defined in this paper as extending from 8000 to 3000 calyrBP), magnetic susceptibility values of sediments deposited in Pyramid Lake's deep basin were much larger than late-Holocene (3000-0 calyrBP) values, indicating the presence of a shallow lake. In addition, the mean d18O value of CaCO3 precipitated between 6500 and 3430 calyrBP was 1.60/00 less than the mean value of CaCO3 precipitated after 2740 calyrBP. Numerical calculations indicate that the shift in the d18O baseline probably resulted from a transition to a wetter (>30%) and cooler (3-5°C) climate. The existence of a relatively dry and warm middle-Holocene climate in the Truckee River-Pyramid Lake system is generally consistent with archeological, sedimentological, chemical, physical, and biological records from various sites within the Great Basin of the western United States. Two high-resolution Holocene-climate records are now available from the Pyramid and Owens lake basins which suggest that the Holocene was characterized by five climatic intervals. TIC and d18O records from Owens Lake indicate that the first interval in the early Holocene (11,600-10,000 calyrBP) was characterized by a drying trend that was interrupted by a brief (200 yr) wet oscillation centered at 10,300 calyrBP. This was followed by a second early-Holocene interval (10,000-8000 calyrBP) during which relatively wet conditions prevailed. During the early part of the middle Holocene (8000-6500 calyrBP), high-amplitude oscillations in TIC in Owens Lake and d18O in Pyramid Lake indicate the presence of shallow lakes in both basins. During the latter part of the middle Holocene (6500-3800 calyrBP), drought conditions dominated, Owens Lake desiccated, and Lake Tahoe ceased spilling to the Truckee River, causing Pyramid Lake to decline. At the beginning of the late Holocene (~3000 calyrBP), Lake Tahoe rose to its sill level and Pyramid Lake increased in volume.
A simple hydrologic-isotopic-balance (HIBAL) model for application to paleolake d18O records is presented. Inputs to the model include discharge, on-lake precipitation, evaporation, and the d18O values of these fluid fluxes. Monthly values of climatic parameters that govern the fractionation of 18O and 16O during evaporation have been extracted from historical data sets and held constant in the model. The ability of the model to simulate changes in the hydrologic balance and the d18O evolution of the mixed layer has been demonstrated using measured data from Pyramid Lake, Nevada. Simulations of the response in d18O to step- and periodic-function changes in fluid inputs indicate that the hydrologic balance and d18O values lag climate change. Input of reconstructed river discharges and their d18O values to Pyramid and Walker lakes indicates that minima and maxima in simulated d18O records correspond to minima and maxima in the reconstructed volume records and that the overall shape of the volume and d18O records is similar. The model was also used in a simulation of abrupt oscillations in the d18O values of paleo-Owens Lake, California.
The isotopic composition of methyl bromide (CH3Br) has been suggested to be a potentially useful tracer for constraining the global CH3Br budget. In order to determine the carbon isotopic composition of CH3Br emitted from the most significant anthropogenic application (pre-plant fumigation) we directly measured the δ13C of CH3Br released during commercial fumigation. We also measured the isotopic fractionation associated with degradation in agricultural soil under typical field fumigation conditions. The isotopic composition of CH3Br collected in soil several hours after injection of the fumigant was -44.5‰ and this value increased to -20.7‰ over the following three days. The mean kinetic isotope effect (KIE) associated with degradation of CH3Br in agricultural soil (12‰) was smaller than the reported value for methylotrophic bacterial strain IMB-1, isolated from previously fumigated agricultural soil, but was similar to methylotrophic bacterial strain CC495, isolated from a pristine forest litter zone. Using this fractionation associated with the degradation of CH3Br in agricultural soil and the mean δ13C of the industrially manufactured CH3Br (-54.4‰), we calculate that the agricultural soil fumigation source has a carbon isotope signature that ranges from -52.8‰ to -42.0‰. Roughly 65% of industrially manufactured CH3Br is used for field fumigations. The remaining 35% is used for structural and post-harvest fumigations with a minor amount used during industrial chemical manufacturing. Assuming that the structural and post-harvest fumigation sources of CH3Br are emitted without substantial fractionation, we calculate that the δ13C of anthropogenically emitted CH3Br ranges from -53.2‰ to -47.5‰.
Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3H/3He) data were obtained from two arrays of nested piezometers located on the north limb of an anticline in fractured sedimentary rocks in the Valley and Ridge geologic province of Pennsylvania. The fracture geometry of the gently east-plunging fold is very regular and consists predominately of south dipping to subhorizontal to north-dipping bedding-plane parting and east-striking, steeply dipping axial planar spaced cleavage. In the area of the piezometer arrays, which trend north-south on the north limb of the fold, north-dipping bedding-plane parting is a more dominant fracture set than is steeply south-dipping axial-plane cleavage. The dating of ground water from the piezometer arrays reveals that ground water traveling along paths parallel to the dip direction of bedding-plane parting has younger 3H/3He and CFC model ages, or a greater component of young water, than does ground water traveling along paths opposite to the dip direction. In predominantly unmixed samples there is a strong positive correlation between age of the young fraction of water and dissolved sodium concentration. The travel times inferred from the model ages are significantly longer than those previously calculated by a ground water flow model, which assumed isotropically fractured layers parallel to topography. A revised model factors in the directional anisotropy to produce longer travel times. Ground water travel times in the watershed therefore appear to be more influenced by anisotropic fracture geometry than previously realized. This could have significant implications for ground water models in other areas underlain by similarly tilted or folded sedimentary rock, such as elsewhere in the Valley and Ridge or the early Mesozoic basins.
We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate. Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 mM NO3-), lack of interference by other solutes, and ease of sample preparation.
Measurements of the cosmogenically-produced 35S, a radioisotope of sulphur (t1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of 35S measurements were made during the summers of 1995 and 1996 (JulySeptember) at all three sites. The system is dominated by melting snow and an initial concentration of 1620 mBq L-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial 35S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, 35S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting 35S concentrations. The most likely explanation is that exchange with sediments or the biota was removing 35S from the lake and replacing it with older sulphate devoid of 35S. In September of 1995 and 1996, 35S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L-1 and averaged 2 mBq L-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.
We report measurements of seasonal variability in the C-N stable isotope ratios of plants collected across the habitat mosaic of San Francisco Bay, its marshes, and its tributary river system. Analyses of 868 plant samples were binned into 10 groups (e.g., terrestrial riparian, freshwater phytoplankton, salt marsh) to determine whether C-N isotopes can be used as biomarkers for tracing the origins of organic matter in this river-marsh-estuary complex. Variability of d13C and d15N was high (~5-100/00) within each plant group, and we identified three modes of variability: (1) between species and their microhabitats, (2) over annual cycles of plant growth and senescence, and (3) between living and decomposing biomass. These modes of within-group variability obscure any source specific isotopic signatures, confounding the application of C-N isotopes for identifying the origins of organic matter. A second confounding factor was large dissimilarity between the d13C- d15N of primary producers and the organic matter pools in the seston and sediments. Both confounding factors impede the application of C-N isotopes to reveal the food supply to primary consumers in ecosystems supporting diverse autotrophs and where the isotopic composition of organic matter has been transformed and become distinct from that of its parent plant sources. Our results support the advice of others: variability of C-N stable isotopes within all organic-matter pools is high and must be considered in applications of these isotopes to trace trophic linkages from primary producers to primary consumers. Isotope-based approaches are perhaps most powerful when used to complement other tools, such as molecular biomarkers, bioassays, direct measures of production, and compilations of organic-matter budgets.
A chemical survey of 69 high-altitude lakes in seven national parks in the western United States was conducted during the fall of 1999; the lakes were previously sampled during the fall of 1985, as part of the Western Lake Survey. Lakes in parks in the Sierra/southern Cascades (Lassen Volcanic, Yosemite, Sequoia/Kings Canyon National Parks) and in the southern Rocky Mountains (Rocky Mountain National Park) were very dilute; median specific conductance ranged from 4.4 to 12.2 μS cm-1 and median alkalinity concentrations ranged from 32.2 to 72.9 μeq L-1. Specific conductances and alkalinity concentrations were substantially higher in lakes in the central and northern Rocky Mountains parks (Grand Teton, Yellowstone, and Glacier National Parks), probably due to the prevalence of more reactive bedrock types. Regional patterns in lake concentrations of NO3 and SO4 were similar to regional patterns in NO3 and SO4 concentrations in precipitation, suggesting that the lakes are showing a response to atmospheric deposition. Concentrations of NO3 were particularly high in Rocky Mountain National Park, where some ecosystems appear to be undergoing nitrogen saturation.
We describe a laboratory investigation into the effect of turbulent hydrodynamic stresses on clam larvae in the settlement phase of the recruitment process. A two-component laser-Doppler anemometer (LDA) was used to measure time histories of the instantaneous turbulence structure at potential recruitment sites within reconstructed beds of the adult Asian clam, Potamocorbula amurensis. Measurements were made for two flow speeds over beds with three different clam densities and two different clam heights. We analyze the statistical effect of the turbulence on the larval flux to the bed and on the probability of successful anchoring to the substrate. It is shown that the anchoring probability depends on the nature of the instantaneous stress events rather than on mean stresses. The instantaneous turbulence structure near the bed is altered by the flow rate and the spacing and height of adult clams living in the substrate. The ability to anchor quickly is therefore extremely important, since the time sequence of episodic turbulent stress events influences larval settlement success. The probability of successful larval settlement is predicted to decrease as the spacing between adults decreases, implying that the hydrodynamics impose negative feedback on clam bed aggregation dynamics.
Large discharges of wastewater and particulate matter from the outfalls of the Los Angeles County Sanitation Districts onto the Palos Verdes shelf since 1937 have produced an effluent-affected sediment deposit characterized by low bulk density, elevated organic matter content, and a high percentage of fine silt and clay particles relative to underlying native sands and sandy silts. Comparison of the results of grain-size analyses using a gentle wet-sieving technique that preserves certain grain aggregates to the results of standard size analyses of disaggregated particles shows that high percentages (up to 50%) of the silt and clay fractions of the effluent-affected mud are incorporated in aggregates having intermediate diameters in the fine-to-medium sand size range (63-500µm). Scanning electron microscope images of the aggregates show that they are predominantly oval fecal pellets or irregularly shaped fragments of pellets. Deposit-feeding polychaete worms such as Capitella sp. and Mediomastus sp., abundant in the mud-rich effluent-affected sediment on Palos Verdes shelf, are probably responsible for most of the grain aggregates through fecal pellet production.
Particle settling rates and densities, and the concentrations of organic carbon and p,p´-DDE, a metabolite of the hydrophobic pesticide DDT, were determined for seven grain-size fractions in the effluent-affected sediment. Fecal pellet grain densities ranged from about 1.2 to 1.5g/cc, and their average settling rates were reduced to the equivalent of about one phi size relative to spherical quartz grains of the same diameter. However, repackaging of fine silt and clay grains into the sand-sized fecal pellets causes an effective settling rate increase of up to 3 orders of magnitude for the smallest particles incorporated in the pellets. Moreover, organic carbon and p,p´-DDE exhibit a bimodal distribution with relatively high concentrations in the finest size fraction (0-20µm), as expected, and a second concentration peak associated with the sand-sized fecal pellets. The repackaging of fine-grained particles along with their adsorbed chemical compounds into relatively fast-settling pellets has important implications for the mobilization and transport of the sediment and the desorption of chemicals from grain surfaces.
Measurements of chromium (Cr) stable-isotope fractionation in laboratory experiments and natural waters show that lighter isotopes reacted preferentially during Cr(VI) reduction by magnetite and sediments. The 53Cr/52CR ratio of the product was 3.4 ± 0.1 mil less than that of the reactant. 53Cr/52CR shifts in water samples indicate the extent of reduction, a critical process that renders toxic Cr(VI) in the environment immobile and less toxic.
A major campaign to quantify the magmatic carbon discharge in cold groundwaters around Mammoth Mountain volcano in eastern California was carried out from 1996 to 1999. The total water flow from all sampled cold springs was ³ 1.8×107 m3/yr draining an area that receives an estimated 2.5×107 m3/yr of recharge, suggesting that sample coverage of the groundwater system was essentially complete. Some of the waters contain magmatic helium with 3He/4He ratios as high as 4.5 times the atmospheric ratio, and a magmatic component in the dissolved inorganic carbon (DIC) can be identified in virtually every feature sampled. Many waters have a 14C of 0-5 pmC, a d13C near -50/00, and contain high concentrations (20-50 mmol/l) of CO2(aq); but are otherwise dilute (specific conductance=100-300 µS/cm) with low pH values between 5 and 6. Such waters have previously escaped notice at Mammoth Mountain, and possibly at many other volcanoes, because CO2 is rapidly lost to the air as the water flows away from the springs, leaving neutral pH waters containing only 1-3 mmol/l HCO3-. The total discharge of magmatic carbon in the cold groundwater system at Mammoth Mountain is ~20,000 t/yr (as CO2), ranging seasonally from about 30 to 90 t/day. Several types of evidence show that this high discharge of magmatic DIC arose in part because of shallow dike intrusion in 1989, but also demonstrate that a long-term discharge possibly half this magnitude (~10,000 t/yr) predated that intrusion. To sustain a 10,000 t/yr DIC discharge would require a magma intrusion rate of 0.057 km3 per century, assuming complete degassing of magma with 0.65 wt% CO2 and a density of 2.7 t/m3. The geochemical data also identify a small (<1 t/day) discharge of magmatic DIC that can be traced to the Inyo Domes area north of Mammoth Mountain and outside the associated Long Valley caldera. This research, along with recent studies at Lassen Peak and other western USA volcanoes, suggests that the amount of magmatic carbon in cold groundwaters is important to constraining rates of intrusion and edifice weathering at individual volcanoes and may even represent a significant fraction of the global carbon discharge from volcanoes.
Reactive transport simulations were conducted to model chemical reactions between metal-EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz-sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium-EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created by the sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal-hydroxypolymer coatings on the aquifer sediments by the metal-EDTA complexes was kinetically restricted. All other reactions, including metal-EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal-EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that the published solubility for ferrihydrite reasonably approximates the Fe solubility of the hydroxypolymer coatings on the sediments. Aluminum may be somewhat more soluble than represented by the equilibrium constant for gibbsite, and its dissolution may be rate controlled when reacting with Ca-EDTA complexes.
The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 mM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations £4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 Å. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ³ 0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.
The alluvial aquifer adjacent to Norman Landfill, OK, provides an excellent natural laboratory for the study of anaerobic processes impacting landfill-leachate contaminated aquifers. We collected groundwaters from a transect of seven multilevel wells ranging in depth from 1.3 to 11 m that were oriented parallel to the flow path. The center of the leachate plume was characterized by (1) high alkalinity and elevated concentrations of total dissolved organic carbon, reduced iron, and methane, and (2) negligible oxygen, nitrate, and sulfate concentrations. Methane concentrations and stable carbon isotope (d13C) values suggest anaerobic methane oxidation was occurring within the plume and at its margins. Methane d13C values increased from about -540/00 near the source to >-100/00 downgradient and at the plume margins. The isotopic fractionation associated with this methane oxidation was -13.6 ± 1.00/00. Methane d13C enrichment indicated that 80-90% of the original landfill methane was oxidized over the 210-m transect. First-order rate constants ranged from 0.06 to 0.23 per year, and oxidation rates ranged from 18 to 230 mM/y. Overall, hydrochemical data suggest that a sulfate reducer-methanogen consortium may mediate this methane oxidation. These results demonstrate that natural attenuation through anaerobic methane oxidation can be an important sink for landfill methane in aquifer systems.
A method is described that allows precise determination of 234U/238U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (±0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (±0.25% RSD, 1 sigma) and alpha particle spectrometry (±5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 mg/L to nearly 100 mg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.
A study was undertaken to measure aerobic respiration by indigenous bacteria in a sand and gravel aquifer on western Cape Cod, MA using tetrazolium salts and by direct oxygen consumption using gas chromatography (GC). In groundwater and aquifer slurries, the rate of aerobic respiration calculated from the direct GC assay was more than 600 times greater than that using the tetrazolium salt 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl tetrazolium chloride (INT). To explain this discrepancy, the toxicity of INT and two additional tetrazolium salts, sodium 3'-[1-(phenylamino)-carbonyl]-3,4-tetrazolium]-bis(4-methoxy-6-nitro) benzenesulfonic acid hydrate (XTT) and 5-cyano-2,3-ditolyl tetrazolium chloride (CTC), to bacterial isolates from the aquifer was investigated. Each of the three tetrazolium salts was observed to be toxic to some of the groundwater isolates at concentrations normally used in electron transport system (ETS) and viability assays. For example, incubation of cells with XTT (3 mM) caused the density of four of the five groundwater strains tested to decline by more than four orders of magnitude. A reasonable percentage (>57%) of cells killed by CTC and INT contained visible formazan crystals (the insoluble, reduced form of the salts) after 4 h of incubation. Thus, many of the cells reduced enough CTC or INT prior to dying to be considered viable by microscopic evaluation. However, one bacterium (Pseudomonas fluorescens) that remained viable and culturable in the presence of INT and CTC, did not incorporate formazan crystals into more than a few percent of cells, even after 24 h of incubation. This strain would be considered nonviable based on traditional tetrazolium salt reduction assays. The data show that tetrazolium salt assays are likely to dramatically underestimate total ETS activity in groundwater and, although they may provide a reasonable overall estimate of viable cell numbers in a community of groundwater bacteria, some specific strains may be falsely considered nonviable by this assay due to poor uptake or reduction of the salts.
Ground water exchange affects the ecology of surface water by sustaining stream base flow and moderating water-level fluctuations of ground water-fed lakes. It also provides stable-temperature habitats and supplies nutrients and inorganic ions. Ground water input of nutrients can even determine the trophic status of lakes and the distribution of macrophytes. In streams the mixing of ground water and surface water in shallow channel and bankside sediments creates a unique environment called the hyporheic zone, an important component of the lotic ecosystem. Localized areas of high ground water discharge in streams provide thermal refugia for fish. Ground water also provides moisture to riparian vegetation, which in turn supplies organic matter to streams and enhances bank resistance to erosion. As hydrologists and ecologists interact to understand the impact of ground water on aquatic ecology, a new research field called "ecohydrology" is emerging.
Dissimilatory reduction of arsenate (DAsR) occurs in the arsenic-rich, anoxic water column of Mono Lake, California, yet the microorganisms responsible for this observed in situ activity have not been identified. To gain insight as to which microorganisms mediate this phenomenon, as well as to some of the biogeochemical constraints on this activity, we conducted incubations of arsenate-enriched bottom water coupled with inhibition/amendment studies and Denaturing Gradient Gel Electrophoresis (DGGE) characterization techniques. DAsR was totally inhibited by filter-sterilization and by nitrate, partially inhibited (~50%) by selenate, but only slightly (~25%) inhibited by oxyanions that block sulfate-reduction (molybdate and tungstate). The apparent inhibition by nitrate, however, was not due to action as a preferred electron acceptor to arsenate. Rather, nitrate addition caused a rapid, microbial re-oxidation of arsenite to arsenate, which gave the overall appearance of no arsenate loss. A similar microbial oxidation of As(III) was also found with Fe(III), a fact that has implications for the recycling of As(V) in Mono Lake's anoxic bottom waters. DAsR could be slightly (10%) stimulated by substrate amendments of lactate, succinate, malate, or glucose, but not by acetate, suggesting that the DAsR microflora is not electron donor limited. DGGE analysis of amplified 16S rDNA gene fragments from incubated arsenate-enriched bottom waters revealed the presence of two bands that were not present in controls without added arsenate. The resolved sequences of these excised bands indicated the presence of members of the epsilon (Sulfurospirillum) and delta (Desulfovibrio) subgroups of the Proteobacteria, both of which have representative species that are capable of anaerobic growth using arsenate as their electron acceptor.
In 1996, the Smithsonian Tropical Research Institute and the Republic of Panama's Environmental Authority, with support from the United States Agency for International Development, undertook a comprehensive program to monitor the ecosystem of the Panama Canal watershed. The goals were to establish baseline indicators for the integrity of forest communities and rivers. Based on satellite image classification and ground surveys, the 2790 km2 watershed had 1570 km2 of forest in 1997, 1080 km2 of which was in national parks and nature monuments. Most of the 490 km2 of forest not currently in protected areas lies along the west bank of the Canal, and its management status after the year 2000 turnover of the Canal from the U.S. to Panama remains uncertain. In forest plots designed to monitor forest diversity and change, a total of 963 woody plant species were identified and mapped. We estimate there are a total of 8501000 woody species in forests of the Canal corridor. Forests of the wetter upper reaches of the watershed are distinct in species composition from the Canal corridor, and have considerably higher diversity and many unknown species. These remote areas are extensively forested, poorly explored, and harbor an estimated 14002200 woody species. Vertebrate monitoring programs were also initiated, focusing on species threatened by hunting and forest fragmentation. Large mammals are heavily hunted in most forests of Canal corridor, and there was clear evidence that mammal density is greatly reduced in hunted areas and that this affects seed predation and dispersal. The human population of the watershed was 113 000 in 1990, and grew by nearly 4% per year from 1980 to 1990. Much of this growth was in a small region of the watershed on the outskirts of Panama City, but even rural areas, including villages near and within national parks, grew by 2% per year. There is no sewage treatment in the watershed, and many towns have no trash collection, thus streams near large towns are heavily polluted. Analyses of sediment loads in rivers throughout the watershed did not indicate that erosion has been increasing as a result of deforestation, rather, erosion seems to be driven largely by total rainfall and heavy rainfall events that cause landslides. Still, models suggest that large-scale deforestation would increase landslide frequency, and failure to detect increases in erosion could be due to the gradual deforestation rate and the short time period over which data are available. A study of runoff showed deforestation increased the amount of water from rainfall that passed directly into streams. As a result, dry season flow was reduced in a deforested catchment relative to a forested one. Currently, the Panama Canal watershed has extensive forest areas and streams relatively unaffected by humans. But impacts of hunting and pollution near towns are clear, and the burgeoning population will exacerbate these impacts in the next few decades. Changes in policies regarding forest protection and pollution control are necessary.
Although nutrient supply often underlies long-term changes in aquatic primary production, other regulatory processes can be important. The SacramentoSan Joaquin River Delta, a complex of tidal waterways forming the landward portion of the San Francisco Estuary, has ample nutrient supplies, enabling us to examine alternate regulatory mechanisms over a 21-yr period. Delta-wide primary productivity was reconstructed from historical water quality data for 19751995. Annual primary production averaged 70 g C m-2, but it varied by over a factor of five among years. At least four processes contributed to this variability: (1) invasion of the clam Potamocorbula amurensis led to a persistent decrease in phytoplankton biomass (chlorophyll a) after 1986; (2) a long-term decline in total suspended solids-probably at least partly because of upstream dam constructionincreased water transparency and phytoplankton growth rate; (3) river inflow, reflecting climate variability, affected biomass through fluctuations in flushing and growth rates through fluctuations in total suspended solids; and (4) an additional pathway manifesting as a long-term decline in winter phytoplankton biomass has been identified, but its genesis is uncertain. Overall, the Delta lost 43% in annual primary production during the period. Given the evidence for food limitation of primary consumers, these findings provide a partial explanation for widespread Delta species declines over the past few decades. Turbid nutrient-rich systems such as the Delta may be inherently more variable than other tidal systems because certain compensatory processes are absent. Comparisons among systems, however, can be tenuous because conclusions about the magnitude and mechanisms of variability are dependent on length of data record
Active reflux may occur during periods of platform-top brine generation, but the role and fate of these brines after reflux events are uncertain. We have used a numerical flow model to investigate and quantify the response of reflux brines to changes in platform-top salinity. Simulations suggest that reflux brines, originally concentrated to gypsum saturation (150?), have a relatively long platform residence time, on the order of 100 times the duration of the reflux event. When brine-generating conditions cease, brines will continue to sink through the platform, entraining seawater, a variant of reflux circulation we term latent reflux. Mesosaline brines intercepted by drilling of carbonate margins by the Ocean Drilling Program may have originated from Pleistocene reflux event(s) on the adjacent platform top and be currently moving by latent reflux. Latent-reflux circulation could deliver a significant quantity of dissolved reactants to platform carbonates, including Mg for dolomitization.
The association between protists, bacteria, and dissolved organic carbon (DOC) in an oxygen-depleted, 6 km-long wastewater contaminant plume within a sandy aquifer (Cape Cod, MA) was investigated by comparing abundance patterns along longitudinal and vertical transects and at a control site. Strong linear correlations were observed between unattached bacterial abundance and DOC for much of the upgradient-half of the plume (0.1-2.5 km downgradient from the source) that is characterized by quasi-steady state chemistry. However, a logarithmic decrease was observed between the number of protists supported per mg of DOC and the estimated age of the DOC within the plume. The relatively labile dissolved organic contaminants that characterize the groundwater sampled from the plume £0.1 km downgradient from the contaminant source appeared to indirectly support 3-4 times as many protists (per mg of DOC) as the older, more recalcitrant DOC in the alkylbenzene sulfonate (ABS)-contaminated zone at 3 km downgradient (~30 years travel time). Substantive numbers of protists (>104/cm3) were recovered from suboxic zones of the plume. The higher than expected ratios of protists to unattached bacteria (10 to 100:1) observed in much of the plume suggest that protists may be grazing upon both surface-associated and unattached bacterial communities to meet their nutritional requirements. In closed bottle incubation experiments, the presence of protists caused an increase in bacterial growth rate, which became more apparent at higher amendments of labile DOC (3-20 mgC/L). The presence of protists resulted in an increase in the apparent substrate saturation level for the unattached bacterial community, suggesting an important role for protists in the fate of more-labile aquifer organic contaminants.
Watersheds in mineralized zones may contain many mines, each of which can contribute to acidity and the metal load of a stream. In this study the authors delineate hydrogeologic characteristics determining the transport of metals from the watershed to the stream in the watershed of Cement Creek, Colorado. Combining the injection of a chemical tracer, to determine a discharge, with synoptic sampling, to obtain chemistry of major ions and metals, spatially detailed load profiles are quantified. Using the discharge and load profiles, the authors (1) identified sampled inflow sources which emanate from undisturbed as well as previously mined areas; (2) demonstrate, based on simple hydrologic balance, that unsampled, likely dispersed subsurface, inflows are significant; and (3) estimate attenuation. For example, along the 12-km study reach, 108 kg per day of Zn were added to Cement Creek. Almost half of this load came from 10 well-defined areas that included both mined and non-mined parts of the watershed. However, the combined effect of many smaller inflows also contributed a substantial load that could limit the effectiveness of remediation. Of the total Zn load, 58.3 kg/day came from stream segments with no visible inflow, indicating the importance of contributions from dispersed subsurface inflow. The subsurface inflow mostly occurred in areas with substantial fracturing of the bedrock or in areas downstream from tributaries with large alluvial fans. Despite a pH generally less than 4.5, there was 58.4 kg/day of Zn attenuation that occurred in mixing zones downstream from inflows with high pH. Mixing zones can have local areas of pH that are high enough for sorption and precipitation reactions to have an effect. Principal component analysis classified inflows into 7 groups with distinct chemical signatures that represent water-rock interaction with different mineral-alteration suites in the watershed. The present approach provides a detailed snapshot of metal load for the watershed to support remediation decisions, and quantifies processes affecting metal transport.
To provide the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) in water resources, the U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 OWCs in water samples from a network of 139 streams across 30 states during 1999 and 2000. The selection of sampling sites was biased toward streams susceptible to contamination (i.e. downstream of intense urbanization and livestock production). OWCs were prevalent during this study, being found in 80% of the streams sampled. The compounds detected represent a wide range of residential, industrial, and agricultural origins and uses with 82 of the 95 OWCs being found during this study. The most frequently detected compounds were coprostanol (fecal steroid), cholesterol (plant and animal steroid), N-N-diethyltoluamide (insect repellant), caffeine (stimulant), triclosan (antimicrobial disinfectant), tri(2-chloroethyl)phosphate (fire retardant), and 4-nonylphenol (nonionic detergent metabolite). Measured concentrations for this study were generally low and rarely exceeded drinking-water guidelines, drinking-water health advisories, or aquatic-life criteria. Many compounds, however, do not have such guidelines established. The detection of multiple OWCs was common for this study, with a median of seven and as many as 38 OWCs being found in a given water sample. Little is known about the potential interactive effects (such as synergistic or antagonistic toxicity) that may occur from complex mixtures of OWCs in the environment. In addition, results of this study demonstrate the importance of obtaining data on metabolites to fully understanding not only the fate and transport of OWCs in the hydrologic system, but also their ultimate overall effect on human health and the environment.
Studies worldwide have shown that mercury (Hg) is a ubiquitous contaminant, reaching even the most remote environments such as high-altitude lakes via atmospheric pathways. However, very few studies have been conducted to assess Hg contamination levels of these systems. We sampled 90 mid-latitude, high-altitude lakes from seven national parks in the western United States during a four-week period in September 1999. In addition to the synoptic survey, routine monitoring and experimental studies were conducted at one of the lakes (Mills Lake) to quantify MeHg flux rates and important process rates such as photo-demethylation. Results show that overall, high-altitude lakes have low total mercury (HgT) and methylmercury (MeHg) levels (1.07 and 0.05 ng L-1, respectively), but a very good correlation of Hg to MeHg (r2 = 0.82) suggests inorganic Hg(II) loading is a primary controlling factor of MeHg levels in dilute mountain lakes. Positive correlations were also observed for dissolved organic carbon (DOC) and both Hg and MeHg, although to a much lesser degree. Levels of MeHg were similar among the seven national parks, with the exception of Glacier National Park where lower concentrations were observed (0.02 ng L-1), and appear to be related to naturally elevated pH values there. Measured rates of MeHg photo-degradation at Mills Lake were quite fast, and this process was of equal importance to sedimentation and stream flow for removing MeHg. Enhanced rates of photo-demethylation are likely an important reason why high-altitude lakes, with typically high water clarity and sunlight exposure, are low in MeHg.
A complex mixture of hydrocarbons is present in the recent sediment of the Monterey Bay National Marine Sanctuary. Eighteen samples from the continental shelf between San Francisco and Monterey contain aliphatic and aromatic hydrocarbons showing biological contributions from both marine and terrigenous sources, with the terrigenous indicators more pronounced near Monterey. Of particular interest, however, is a low-level background of petroleum-related compounds, including 28,30-bisnorhopane and 18a+b(H)-oleanane, which are characteristic of many crude oils from the Monterey Formation of California. Thus, the sediments are overprinted by a regional chemical signature which may be derived from eroded Monterey Formation rocks and from onshore and offshore seeps releasing petroleum from Monterey Formation source rocks.
Following the aggressive invasion of the bivalve, Potamocorbula amurensis, in the San Francisco Bay-Delta in 1986, selenium contamination in the benthic food web increased. Concentrations in this dominant (exotic) bivalve in North Bay were three times higher in 1995-1997 than in earlier studies, and 1990 concentrations in benthic predators (sturgeon and diving ducks) were also higher than in 1986. The contamination was widespread, varied seasonally and was greater in P. amurensis than in co-occurring and transplanted species. Selenium concentrations in the water column of the Bay were enriched relative to the Sacramento River but were not as high as observed in many contaminated aquatic environments. Total Se concentrations in the dissolved phase never exceeded 0.3 µg Se per l in 1995 and 1996; Se concentrations on particulate material ranged from 0.5 to 2.0 µg Se per g dry weight (dw) in the Bay. Nevertheless, concentrations in P. amurensis reached as high as 20 µg Se per g dw in October 1996. The enriched concentrations in bivalves (6-20 µg Se per g dw) were widespread throughout North San Francisco Bay in October 1995 and October 1996. Concentrations varied seasonally from 5 to 20 µg Se per g dw, and were highest during the periods of lowest river inflows and lowest after extended high river inflows. Transplanted bivalves (oysters, mussels or clams) were not effective indicators of either the degree of Se contamination in P. amurensis or the seasonal increases in contamination in the resident benthos. Se is a potent environmental toxin that threatens higher trophic level species because of its reproductive toxicity and efficient food web transfer. Bivalves concentrate selenium effectively because they bioaccumulate the element strongly and lose it slowly; and they are a direct link in the exposure of predaceous benthivore species. Biological invasions of estuaries are increasing worldwide. Changes in ecological structure and function are well known in response to invasions. This study shows that changes in processes such as cycling and effects of contaminants can accompany such invasions.
Samples from four geographically and tectonically discrete cold seeps named Clam Flat, Clamfield, Horseshoe Scarp South, and Tubeworm City, within the Monterey Bay National Marine Sanctuary were analyzed for their hydrocarbon content. The sediment contains gaseous hydrocarbons and CO2, as well as high molecular weight aliphatic and aromatic hydrocarbons with various combinations of thermogenic and biogenic contributions from petroleum, marine, and terrigenous sources. Of particular interest is the cold seep site at Clamfield which is characterized by the presence of thermogenic hydrocarbons including oil that can likely be correlated with oil-saturated strata at Majors Creek near Davenport, CA, USA. At Clam Flat, the evidence for thermogenic hydrocarbons is equivocal. At Horseshoe Scarp South and Tubeworm City, hydrocarbon gases, mainly methane, are likely microbial in origin. These varied sources of hydrocarbon gases highlight the diverse chemical systems that appear at cold seep communities.
We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different 87Sr/86Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system could be either the Cenozoic volcanic rocks that make up a small portion of the till deposited in the valley during the Last Glacial Maximum or from marble derived from the local basement rocks. The more radiogenic ratios from Lake Bonney originate from ancient salt deposits that flow into the lake from Taylor Glacier and the weathering of minerals with more radiogenic Sr isotopic ratios within the tills. The Sr isotopic data from the streams and lakes of Taylor Valley strongly support the notion documented by previous investigators that chemical weathering has been, and is currently, a major process in determining the overall aquatic chemistry of these lakes in this polar desert environment.
A method of distributing an executable version of a geo-scientific model over the web is described. The method includes the conversion of model code into Java programming language and distributing the model from the internet using Java Web Start, making possible the delivery of (1) executable programs; (2) model documentation and (3) a robust GUI for model operation, all in a single Java archive file. This method enables model developers to distribute an executable version of a model that will operate on all computer systems and has several advantages over traditional methods: (1) only one version of the model needs to be maintained by model developers; (2) the distributed model will run on any computer system; (3) model installation is easy; (4) users automatically receive updated versions of the model and (5) model developers have more time to devote to model development and improvement as less time will be spent on model maintenance and distribution. Security issues also are addressed.
Use of methyl bromide (MeBr) as a quarantine, commodity, or structural fumigant is under scrutiny because its release to the atmosphere contributes to the depletion of stratospheric ozone. A closed-system bioreactor consisting of 0.5 L of a growing culture of a previously described bacterium, strain IMB-1, removed MeBr (>110 mmol L-1) from recirculating air. Strain IMB-1 grew slowly to high cell densities in the bioreactor using MeBr as its sole carbon and energy source. Bacterial oxidation of MeBr produced CO2 and hydrobromic acid (HBr), which required continuous neutralization with NaOH for the system to operate effectively. Strain IMB-1 was capable of sustained oxidation of large amounts of MeBr (170 mmol in 46 d). In an open-system bioreactor (10-L fermenter), strain IMB-1 oxidized a continuous supply of MeBr (220 mmol L-1 in air). Growth was continuous, and 0.5 mol of MeBr was removed from the air supply in 14 d. The specific rate of MeBr oxidation was 7 × 10-16 mol cell-1 h-1. Bioreactors such as these can therefore be used to remove large quantities of contaminant MeBr, which opens the possibility of biodegradation as a practical means for its disposal.
Applications of transport time scales are pervasive in biological, hydrologic, and geochemical studies yet these times scales are not consistently defined and applied with rigor in the literature. We compare three transport time scales (flushing time, age, and residence time) commonly used to measure the retention of water or scalar quantities transported with water. We identify the underlying assumptions associated with each time scale, describe procedures for computing these time scales in idealized cases, and identify pitfalls when real-world systems deviate from these idealizations. We then apply the time scale definitions to a shallow 378 ha tidal lake to illustrate how deviations between real water bodies and the idealized examples can result from: (1) non-steady flow; (2) spatial variability in bathymetry, circulation, and transport time scales; and (3) tides that introduce complexities not accounted for in the idealized cases. These examples illustrate that no single transport time scale is valid for all time periods, locations, and constituents, and no one time scale describes all transport processes. We encourage aquatic scientists to rigorously define the transport time scale when it is applied, identify the underlying assumptions in the application of that concept, and ask if those assumptions are valid in the application of that approach for computing transport time scales in real systems.
We studied the chemical and optical changes in the dissolved organic matter (DOM) from two freshwater lakes and a Sphagnum bog after exposure to solar radiation. Stable carbon isotopes and solid-state 13C-NMR spectra of DOM were used together with optical and chemical data to interpret results from experimental exposures of DOM to sunlight and from seasonal observations of two lakes in northeastern Pennsylvania. Solar photochemical oxidation of humic-rich bog DOM to smaller LMW compounds and to DIC was inferred from losses of UV absorbance, optical indices of molecular weight and changes in DOM chemistry. Experimentally, we observed a 1.20/00 enrichment in d13C and a 47% loss in aromatic C functionality in bog DOM samples exposed to solar UVR. Similar results were observed in the surface waters of both lakes. In late summer hypolimnetic water in humic Lake Lacawac, we observed 3 to 4.50/00 enrichments in d13C and a 30% increase in aromatic C relative to early spring values during spring mixing. These changes coincided with increases in molecular weight and UV absorbance. Anaerobic conditions of the hypolimnion in Lake Lacawac suggest that microbial metabolism may be turning over allochthonous C introduced during spring mixing, as well as autochthonous C. This metabolic activity produces HMW DOM during the summer, which is photochemically labile and isotopically distinct from allochthonous DOM or autochthonous DOM. These results suggest both photooxidation of allochthonous DOM in the epilimnion and autotrophic production of DOM by bacteria in the hypolimnion cause seasonal trends in the UV absorbance of lakes.
Monthly censusing of reproductive condition of the Asian clam Potamocorbula amurensis at four sites in northern San Francisco Bay over a 9-yr period revealed year-to-year differences in local reproductive activity that are associated with patterns of hydrologic variability. Between 1989 and 1992, Northern California experienced a drought, whereas the period between 1993 and 1998 was marked by a mix of wet and dry years. We took advantage of the extreme year-to-year differences to examine reproductive responses to river inflow patterns. Populations of P. amurensis at the upstream sites in Suisun Bay and Carquinez Strait were more reproductively active during wet years than dry years. Conversely, at the downstream site in San Pablo Bay, the population was more reproductively active during dry years than wet years. We suggest that the different reproductive patterns observed reflect the clam's response to different sources of food. During wet years, organic matter from the rivers augments food supplies in Suisun Bay. During dry years, when inflow into the San Francisco Bay Estuary from the rivers is reduced, water transported from the adjacent ocean into the estuary as far as San Pablo Bay provides a supplemental food supply for the local production. The populations take advantage of these spatially distinct food supplies by initiating and maintaining local reproductive activity. We conclude that the ability of P. amurensis to consume and use various types of food to regulate its reproductive activity is part of the reason for its success as an invasive species.
Mass balances of total arsenic and copper for a suburban lake in densely populated northern Virginia were calculated using data collected during 1998. Mass-balance terms were precipitation; stream inflow, including road runoff; stream outflow; and contributions from leaching of pressure-treated lumber. More mass of arsenic and copper was input to the lake than was output; the 1998 lake-retention rates were 70% for arsenic and 20% for copper. The arsenic mass balance compared well with a calculated annual mass accumulation in the top 1 cm of the lake sediments; however, the calculated contribution of copper to the lake was insufficient to account for the amount of copper in this zone. Leaching experiments were conducted on lumber treated with chromated copper arsenate (CCA) to quantify approximate amounts of arsenic and copper contributed by this source. Sources to lake sediments included leaching of CCA-treated lumber (arsenic, 50%; copper, 4%), streamwater (arsenic, 50%; copper, 90%), and atmospheric deposition (arsenic, 1%; copper, 3%). Results of this study suggest that CCA-treated lumber and road runoff could be significant nonpoint sources of arsenic and copper, respectively, in suburban catchments.
Roesler, C.S., Culbertson, C.W., Etheridge, S.M, Goericke, R., Kiene, R.P., Miller, L.G., and Oremland, R.S., 2002, Distribution, production, and ecophysiology of Picocycstis strain ML in Mono Lake, CA: Limnology and Oceanography, v. 47, p. 440-452.
A recently described unicellular chlorophytic alga isolated from meromictic Mono Lake, California, occupies a niche that spans two environments: the upper oxic mixolimnion and the deeper anoxic and highly reducing monimolimnion. This organism, Picocystis sp. strain ML, accounts for nearly 25% of the primary production during the winter bloom and more than 50% at other times of the year. In incubations, it is heavily grazed by the brine shrimp, Artemia monica. We assessed growth and photosynthetic parameters over broad ranges of irradiance, salinity, and pH and under oxic and anoxic conditions. Picocystis appears to be particularly adapted to low irradiance; we observed an order of magnitude increase in the cellular pigment concentrations, as well as marked increases in cellspecific photosynthetic parameters for cells acclimated to low-growth irradiance. Growth rates of 0.31.5 d-1 were observed over a salinity range of 0260? and a pH range of 412, with maximal growth at ~50 mmol photons m-2 s-1, 40?, and pH 610. Growth and oxygenic photosynthesis were observed under anoxic conditions at rates comparable to those measured under oxic conditions. The ability of the organism to acclimate and grow under such a broad range of environmental conditions makes it an important component of the Mono Lake ecosystem and likely contributes to its dominance of the monimolimnion/mixolimnion interface.
Field and laboratory experiments were conducted to investigate inactivation of viruses attached to mineral surfaces. In a natural gradient transport field experiment, bacteriophage PRD1, radiolabeled with 32P, was injected into a ferric oxyhydroxide-coated sand aquifer with bromide and linear alkylbenzene sulfonates. In a zone of the aquifer contaminated by secondary sewage infiltration, small fractions of infective and 32P-labeled PRD1 broke through with the bromide tracer, followed by the slow release of 84% of the 32P activity and only 0.011% of the infective PRD1. In the laboratory experiments, the inactivation of PRD1, labeled with 35S (protein capsid), and MS2, dual radiolabeled with 35S (protein capsid) and 32P (nucleic acid), was monitored in the presence of groundwater and sediment from the contaminated zone of the field site. Release of infective viruses decreased at a much faster rate than release of the radiolabels, indicating that attached viruses were undergoing surface inactivation. Disparities between 32P and 35S release suggest that the inactivated viruses were released in a disintegrated state. Comparison of estimated solution and surface inactivation rates indicates solution inactivation is ~3 times as fast as surface inactivation. The actual rate of surface inactivation may be substantially underestimated owing to slow release of inactivated viruses.
The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 mm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.
The U.S. Geological Survey is contributing scientific findings and synthesized results from its South Florida Ecosystem Program toward development and implementation of the Comprehensive Everglades Restoration Plan. Findings derived from hydrological and ecological studies and extensive data collected to monitor and characterize the Everglades ecosystem are being integrated into the development of numerical models to guide and evaluate restoration decisions. A coupled surface-water/groundwater hydrodynamic/transport model is being developed for the coastal marine and freshwater wetland ecosystems of Everglades National Park. The multi-dimensional model is facilitating the development of estuarine ecological models by providing insight into the nature and extent of saltwater/freshwater mixing in the land-margin ecosystems that encompass the mangrove ecotone. Dynamic salinity transport simulations are being designed and generated to test the development of estuarine indicator species models for use as performance measures to evaluate the effectiveness of restoration actions. Projects contributing hydrologic process-study findings and data for development of the hydrodynamic/transport model are identified and the integration and use of the study results and data in the model are discussed in this paper.
Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall d18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 30/00 in d18O and 21 in dD compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui d18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area.
The Salton Sea is a 1000-km2 terminal lake located in the desert area of southeastern California. This saline (~44 000 mg l-1 dissolved solids) lake started as fresh water in 190507 by accidental flooding of the Colorado River, and it is maintained by agricultural runoff of irrigation water diverted from the Colorado River. The Salton Sea and surrounding wetlands have recently acquired substantial ecological importance because of the death of large numbers of birds and fish, and the establishment of a program to restore the health of the Sea. In this report, we present new data on the salinity and concentration of selected chemicals in the Salton Sea water, porewater and sediments, emphasizing the constituents of concern: nutrients (N and P), Se and salinity. Chemical profiles from a Salton Sea core estimated to have a sedimentation rate of 2.3 mm yr-1 show increasing concentrations of OC, N, and P in younger sediment that are believed to reflect increasing eutrophication of the lake. Porewater profiles from two locations in the Sea show that diffusion from bottom sediment is only a minor source of nutrients to the overlying water as compared to irrigation water inputs. Although loss of N and Se by microbial-mediated volatilization is possible, comparison of selected element concentrations in river inputs and water and sediments from the Salton Sea indicates that most of the N (from fertilizer) and virtually all of the Se (delivered in irrigation water from the Colorado River) discharged to the Sea still reside within its bottom sediment. Laboratory simulation on mixtures of sediment and water from the Salton Sea suggest that sediment is a potential source of N and Se to the water column under aerobic conditions. Hence, it is important that any engineered changes made to the Salton Sea for remediation or for transfer of water out of the basin do not result in remobilization of nutrients and Se from the bottom sediment into the overlying water.
Mercury (Hg) contamination of aquatic ecosystems and subsequent methylmercury bioaccumulation are significant environmental problems of global extent. At regional to global scales, the primary mechanism of Hg contamination is atmospheric Hg transport. Thus, a better understanding of the long-term history of atmospheric Hg cycling and quantification of the sources is critical for assessing the regional and global impact of anthropogenic Hg emissions. Ice cores collected from the Upper Fremont Glacier (UFG), Wyoming, contain a high-resolution record of total atmospheric Hg deposition (ca. 1720-1993). Total Hg in 97 ice-core samples was determined with trace-metal clean handling methods and low-level analytical procedures to reconstruct the first and most comprehensive atmospheric Hg deposition record of its kind yet available from North America. The record indicates major atmospheric releases of both natural and anthropogenic Hg from regional and global sources. Integrated over the past 270-year ice-core history, anthropogenic inputs contributed 52%, volcanic events 6%, and background sources 42%. More significantly, during the last 100 years, anthropogenic sources contributed 70% of the total Hg input. Unlike the 2-7-fold increase observed from preindustrial times (before 1840) to the mid-1980s in sediment-core records, the UFG record indicates a 20-fold increase for the same period. The sediment-core records, however, are in agreement with the last 10 years of this ice-core record, indicating declines in atmospheric Hg deposition.
The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotol- uene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.
T15NT was added to a soil of low organic carbon content and composted for 20 days in an aerobic bench scale reactor. The finished whole compost and fulvic acid, humic acid, humin, and lignocellulose fractions extracted from the compost were analyzed by solid-state CP/MAS and DP/MAS 15N NMR. 15N NMR spectra provided direct spectroscopic evidence for reduction of TNT followed by covalent binding of the reduced metabolites to organic matter of the composted soil, with the majority of metabolite found in the lignocellulose fraction, by mass also the major fraction of the compost. In general, the types of bonds formed between soil organic matter and reduced TNT amines in controlled laboratory reactions were observed in the spectra of the whole compost and fractions, confirming that during composting TNT is reduced to amines that form covalent bonds with organic matter through aminohydroquinone, aminoquinone, heterocyclic, and imine linkages, among others. Concentrations of imine nitrogens in the compost spectra suggest that covalent binding by the diamines 2,4DANT and 2,6DANT is a significant process in the transformation of TNT into bound residues. Liquid-phase 15N NMR spectra of the fulvic acid and humin fractions provided possible evidence for involvement of phenoloxidase enzymes in covalent bond formation.
Interacting river discharge, tidal oscillation, and tropical rainfall across the 22,000 km2 Orinoco delta plain support diverse fresh and brackish water ecosystems. To develop environmental baseline information for this largely unpopulated region, we evaluate major coastal plain, shallow marine, and river systems of northeastern South America, which serves to identify principal sources and controls of water and sediment flow into, through, and out of the Orinoco Delta.
The regional analysis includes a summary of the geology, hydrodynamics, sediment dynamics, and geomorphic characteristics of the Orinoco drainage basin, river, and delta system. Because the Amazon River is a major source of sediment deposited along the Orinoco coast, we summarize Amazon water and sediment input to the northeastern South American littoral zone. We investigate sediment dynamics and geomorphology of the Guiana coast, where marine processes and Holocene history are similar to the Orinoco coast.
Major factors controlling Orinoco Delta water and sediment dynamics include the pronounced annual flood discharge; the uneven distribution of water and sediment discharge across the delta plain; discharge of large volumes of water with low sediment concentrations through the Río Grande and Araguao distributaries; water and sediment dynamics associated with the Guayana littoral current along the northeastern South American coast; inflow of large volumes of Amazon sediment to the Orinoco coast; development of a fresh water plume seaward of Boca Grande; disruption of the Guayana Current by Trinidad, Boca de Serpientes, and Gulf of Paria; and the constriction at Boca de Serpientes.
"Two-line" ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10-5 to 10-3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.
Webb, R.H., 2002, Recovery of severely compacted soils in the Mojave Desert, California, USA: Arid Land Research and Management, v. 16, p. 291-305.
Often as a result of large-scale military maneuvers in the past, many soils in the Mojave Desert are highly vulnerable to soil compaction, particularly when wet. Previous studies indicate that natural recovery of severely compacted desert soils is extremely slow, and some researchers have suggested that subsurface compaction may not recover. Poorly sorted soils, particularly those with a loamy sand texture, are most vulnerable to soil compaction, and these soils are the most common in alluvial fans of the Mojave Desert. Recovery of compacted soil is expected to vary as a function of precipitation amounts, wetting-and-drying cycles, freeze-thaw cycles, and bioturbation, particularly root growth. Compaction recovery, as estimated using penetration depth and bulk density, was measured at 19 sites with 32 site-time combinations, including the former World War II Army sites of Camps Ibis, Granite, Iron Mountain, Clipper, and Essex. Although compaction at these sites was caused by a wide variety of forces, ranging from human trampling to tank traffic, the data do not allow segregation of differences in recovery rates for different compaction forces. The recovery rate appears to be logarithmic, with the highest rate of change occurring in the first few decades following abandonment. Some higher-elevation sites have completely recovered from soil compaction after 70 years. Using a linear model of recovery, the full recovery time ranges from 92 to 100 years; using a logarithmic model, which asymptotically approaches full recovery, the time required for 85% recovery ranges from 105-124 years.
Aquifer-atmosphere interactions can be important in regions where the water table is shallow (<2 m). A shallow water table provides moisture for the soil and vegetation and thus acts as a source term for evapotranspiration to the atmosphere. A coupled aquifer-land surface-atmosphere model has been developed to study aquifer-atmosphere interactions in watersheds, on decadal timescales. A single column vertically discretized atmospheric model is linked to a distributed soil-vegetation-aquifer model. This physically based model was able to reproduce monthly and yearly trends in precipitation, stream discharge, and evapotranspiration, for a catchment in northeastern Kansas. However, the calculated soil moisture tended to drop to levels lower than were observed in drier years. The evapotranspiration varies spatially and seasonally and was highest in cells situated in topographic depressions where the water table is in the root zone. Annually, simulation results indicate that from 5-20% of groundwater supported evapotranspiration is drawn from the aquifer. The groundwater supported fraction of evapotranspiration is higher in drier years, when evapotranspiration exceeds precipitation. A long-term (40 year) simulation of extended drought conditions indicated that water table position is a function of groundwater hydrodynamics and cannot be predicted solely on the basis of topography. The response time of the aquifer to drought conditions was on the order of 200 years indicating that feedbacks between these two water reservoirs act on disparate time scales. With recent advances in the computational power of massively parallel supercomputers, it may soon become possible to incorporate physically based representations of aquifer hydrodynamics into general circulation models (GCM) land surface parameterization schemes.
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