Identification of groundwater solute sources using boron isotopic composition
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Differences between field and laboratory pH values reported by the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) monitoring program from 1984 through 1986 are investigated. Median differences in hydrogen ion concentration between laboratory and field pH determinations at sites averaged -4.6 μ equiv/L in natural precipitation samples on an annual basis. The median difference found in external quality assurance samples analyzed during the same time period was -11 μ equiv/L. The results suggest a systematic bias in pH values reported by the NADP/NTN network. The bias appears to have a fixed component of approximately -7 μ equiv/L, which can be attributed to the sampling bucket and lid, and a seasonal and regional component that ranges from +4 to -22 μ equiv/L at the 10th and 90th percentiles. Differences were found to be independent of sample pH and sample volume. The magnitude of the bias has implications for the interpretation of previously published pH and hydrogen ion concentration and deposition values in the western United States.
Two sediment cores were taken from the Rochester Basin of eastern Lake Ontario and analyzed for the radionuclides 210Pb and 137Cs and several high molecular weight chlorinated hydrocarbons (CHs). The two sites are geographically proximate but differ in sedimentation rate, permitting sedimentation-dependent processes to be factored out. The 210Pb chronology showed a mixed depth of 3-5 cm and an intrinsic time resolution of 11-14 years. Vertically integrated numbers of deposit-feeding oligochaete worms and burrowing organisms are insufficient to homogenize the sediment on the time scale of CH inputs, which are non steady state. U.S. production and sales of polychlorinated biphenyls (PCBs), DDT, Mirex, and hexachlorobenzene (HCB), as determinants of the shape of the input function, adequately predict the overall shape and, in many cases, details in the sedimentary profile. Sediment focusing factors (FF) inferred from 137Cs and 210Pb inventories averaged 1.17 and 1.74 for cores E-30 and G-32, respectively. This permitted CH accumulation rates to be corrected for focusing. Apparent molecular diffusion coefficients modeled for many of the CHs were about (1-3) ?? 10-9 cm2/s.
Detailed sampling and subsequent analyses of riverine suspended sediment obtained from six rivers in the United States indicate substantial differences in suspended sediment concentrations and possibly in some associated trace elements, depending on whether depth- and width-integrated, point, or pumping samples are used. In addition, the data from time-series, depth-integrated sampling indicate that there can be substantial short-term (on the order of 20-30 min) spatial and/or temporal variations in suspended-sediment concentrations. Despite this, major element concentrations are remarkably stable both spatially and temporally. Trace element concentrations are generally stable; however, some spatial and temporal variations may occur.
Volcanic ash, surface-water, and bottom-material samples obtained in the vicinity of Mount St. Helens after the May 18, 1980, eruption were analyzed for organic contaminants by using capillary gas chromatography-mass spectrometry-computer techniques. Classes of compounds identified include n -alkanes, fatty acids, dicarboxylic acids, aromatic acids and aldehydes, phenols, resin acids, terpenes, and insect juvenile hormones. The most probable source of these compounds is from pyrolysis of plant and soil organic matter during and after the eruption. The toxicity of selected compounds and their environmental significance are discussed.
Plutonium is present in very low concentrations in ground water near the disposal well at the Idaho Chemical Processing Plant but was not detected in waters at greater distances. Because of the absence of strong complexing agents, the plutonium is present as an uncomplexed (perhaps hydrolyzed) tetravalent species, which is readily precipitated or sorbed by basalt or sediments along the ground-water flow path.
Black carbon (BC) may be a major component of riverine carbon exported to the ocean, but its flux from large rivers is unknown. Furthermore, the global distribution of BC between natural and anthropogenic sources remains uncertain. We have determined BC concentrations in suspended sediments of the Mississippi River, the 7th largest river in the world in terms of sediment and water discharge, during high flow and low flow in 1999. The 1999 annual flux of BC from the Mississippi River was 5 × 10 - 4 petagrams (1 Pg = 10 15 g = 1 gigaton). We also applied a principal components analysis to particulate-phase high molecular weight polycyclic aromatic hydrocarbon isomer ratios in Mississippi River suspended sediments. In doing so, we determined that ∼27% of the BC discharged from the Mississippi River in 1999 originated from fossil fuel combustion (coal and smelter-derived combustion), implicating fluvial BC as an important source of anthropogenic BC contamination into the ocean. Using our value for BC flux and the annual estimate for BC burial in ocean sediments, we calculate that, in 1999, the Mississippi River discharged ∼5% of the BC buried annually in the ocean. These results have important implications, not only for the global carbon cycle but also for the fluvial discharge of particulate organic contaminants into the world's oceans.
No abstract available.
In view of the current lack of reliable partition coefficients for organic compounds with carbohydrates ( K ch ), carefully measured values with cellulose and starch, the two major forms of carbohydrates, are provided for a wide range of compounds: short-chain chlorinated hydrocarbons, halogenated benzenes, alkyl benzenes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and organochlorine pesticides. To ensure the accuracy of the K ch data, solute concentrations in both water and carbohydrate phases are measured by direct solvent extraction of the samples. For a given compound, the observed partition coefficient with cellulose ( K cl ) is virtually the same as that with starch ( K st ). This finding expedites the evaluation of organic contamination with different forms of carbohydrates. The presently determined K ch values of 13 PAHs are substantially lower (by 3−66 times) than the literature data; the latter are suspect as they were obtained with (i) presumably impure carbohydrate samples or (ii) indirectly measured equilibrium solute concentrations in carbohydrate and water phases. Although the K ch values are generally considerably lower than the respective K ow (octanol−water) or K lipid (lipid−water), accurate K ch data are duly required to accurately estimate the contamination of carbohydrates by organic compounds because of the abundance of carbohydrates over lipids in crops and plants. To overcome the current lack of reliable K ch data for organic compounds, a close correlation of log K ch with log K ow has been established for predicting the unavailable K ch data for low-polarity compounds.
Within the Boundary Waters Canoe Area Wilderness in northeastern Minnesota, soils were collected from 116 sites in areas of primarily virgin forest with fire-origin stand years (year of last recognizable stand-killing wildfire) that range from the 1759 to 1976. Median concentrations for total mercury in soils for this span of 217 years range from 0.28 ± 0.088 ppm (1759) to 0.09 ± 0.047 ppm (1976) for A-horizon soils and from 0.23 ± 0.062 ppm (1759) to 0.09 ± 0.018 ppm (1976) for O-horizon soils. A separate study of soils collected from 30 sites within an area that burned in a 2004 wildfire at Voyageurs National Park, northern Minnesota, suggested that high soil burn severity resulted in significant mercury loss from both organic and mineral soils. Integrated data from these two studies and additional regional soil data demonstrate that older forests have progressively higher mercury concentrations in O-horizon soils (r 2 = 0.423) and A-horizon soils (r 2 = 0.456). These results support the hypotheses that an important factor for mercury concentrations in forest soils is time since stand-replacing fire and that high soil burn severity has the potential to reduce the concentration of mercury in burned soils for tens to hundreds of years.
Zinc is an important trace element pollutant in urban environments; however, the extent of Zn contamination and the sources of urban Zn pollution are often unclear. We measured Zn concentrations and isotopes in sediment cores collected from eight lakes or reservoirs across the United States. We paired these data with historical records of land use within each watershed to calculate a mean Zn concentration and δ 66 Zn for natural (less than 5% urban land use; 123 ± 21.7 mg/kg; +0.33 ± 0.08‰, n = 6 lakes) and urban (greater than 70% urban land use; 389 ± 200 mg/kg; +0.14 ± 0.07‰, n = 3 lakes) lake sediments. The relation between Zn concentration data and Zn isotope data allows us to create a mixing model between two end members: natural and urban. The δ 66 Zn of the urban end-member is consistent with Zn pollution from vehicle-related sources (tire wear and emissions). Application of this model to samples collected from lakes recording periods ranging from 5 to 70% urban land use in their surrounding watersheds indicates that the lakes and reservoirs were affected by large amounts of Zn from urban sources.
Aqueous solutions of humic substances (HSs) and pure monomeric aromatics were irradiated to investigate the chemical controls upon carbon monoxide (CO) photoproduction from dissolved organic matter (DOM). HSs were isolated from lakes, rivers, marsh, and ocean. Inclusion of humic, fulvic, hydrophobic organic, and hydrophilic organic acid fractions from these environments provided samples diverse in source and isolation protocol. In spite of these major differences, HS absorption coefficients (a) and photoreactivities (a bleaching and CO production) were strongly dependent upon HS aromaticity ( r 2 >0.90; n = 11), implying aromatic moieties are the principal chromophores and photoreactants within HSs, and by extension, DOM. Carbonyl carbon and CO photoproduction were not correlated, implying that carbonyl moieties are not quantitatively important in CO photoproduction. CO photoproduction efficiency of aqueous solutions of monomeric aromatic compounds that are common constituents of organic matter varied with the nature of ring substituents. Specifically, electron donating groups increased, while electron withdrawing groups decreased CO photoproductivity, supporting our conclusion that carbonyl substituents are not quantitatively important in CO photoproduction. Significantly, aromatic CO photoproduction efficiency spanned 3 orders of magnitude, indicating that variations in the CO apparent quantum yields of natural DOM may be related to variations in aromatic DOM substituent group chemistry.
The concept of a nature reserve such as a National Park is to maintain a location for the enjoyment and study of a pristine environment. However, many pollutants are now known to spread far and wide from their (point[s] of) origin. To grasp the extent of pervasive and boundary-less pollution, the ambitious WACAP study evaluated contaminant data collected from Western U.S. National Parks in various media. In this Feature, Landers et al. summarize the report and speak to its utility moving forward.
Volatile organic compounds (VOCs) are compounds with chemical and physical properties that allow the compounds to move freely between the water and air phases of the environment. VOCs are widespread in the environment because of this mobility. Many VOCs have properties that make them suspected or known hazards to the health of humans and aquatic organisms. Consequently, understanding the processes affecting the concentration and distribution of VOCs in the environment is necessary. The transport, behavior, and fate of VOCs in streams are determined by combinations of chemical, physical, and biological processes. These processes are volatilization, absorption, wet and dry deposition, microbial degradation, sorption, hydrolysis, aquatic photolysis, oxidation, chemical reaction, biocon-centration, advection, and dispersion. The relative importance of each of these processes depends on the characteristics of the VOC and the stream. The U.S. Geological Survey National Water-Quality Assessment Program selected 55 VOCs for study. This article reviews the characteristics of the various processes that could affect the transport, behavior, and fate of these VOCs in streams.
The authors summarize the main findings of the Florida Coastal Everglades Long-Term Ecological Research (FCE-LTER) program in the EMER, within the context of the Comprehensive Everglades Restoration Plan (CERP), to understand how regional processes, mediated by water flow, control population and ecosystem dynamics across the EMER landscape. Tree canopies with maximum height <3 m cover 49% of the EMER, particularly in the SE region. These scrub/dwarf mangroves are the result of a combination of low soil phosphorus (P < 59 μg P g dw −1 ) in the calcareous marl substrate and long hydroperiod. Phosphorus limits the EMER and its freshwater watersheds due to the lack of terrigenous sediment input and the phosphorus-limited nature of the freshwater Everglades. Reduced freshwater delivery over the past 50 years, combined with Everglades compartmentalization and a 10 cm rise in coastal sea level, has led to the landward transgression (∼1.5 km in 54 years) of the mangrove ecotone. Seasonal variation in freshwater input strongly controls the temporal variation of nitrogen and P exports (99%) from the Everglades to Florida Bay. Rapid changes in nutrient availability and vegetation distribution during the last 50 years show that future ecosystem restoration actions and land use decisions can exert a major influence, similar to sea level rise over the short term, on nutrient cycling and wetland productivity in the EMER.
Scientists’ understanding of the role of tree islands in the Everglades has evolved from a plant community of minor biogeochemical importance to a plant community recognized as the driving force for localized phosphorus accumulation within the landscape. Results from this review suggest that tree transpiration, nutrient infiltration from the soil surface, and groundwater flow create a soil zone of confluence where nutrients and salts accumulate under the head of a tree island during dry periods. Results also suggest accumulated salts and nutrients are flushed downstream by regional water flows during wet periods. That trees modulate their environment to create biogeochemical hot spots and strong nutrient gradients is a significant ecological paradigm shift in the understanding of the biogeochemical processes in the Everglades. In terms of island sustainability, this new paradigm suggests the need for distinct dry-wet cycles as well as a hydrologic regime that supports tree survival. Restoration of historic tree islands needs further investigation but the creation of functional tree islands is promising.