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Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina↗

Diagnostic criteria for selenium toxicosis in aquatic birds: dietary exposure, tissue concentrations, and macroscopic effects

A feeding study with mallard ducks ( Anas platyrhynchos ) was conducted during March to July 1988 in Laurel, Maryland (USA), to identify diagnostic criteria for selenium toxicosis in birds. One-year-old male mallards in groups of 21 were fed diets containing 0, 10, 20, 40, or 80 parts per million (ppm) selenium, as seleno-DL-methionine, for 16 weeks. All ducks receiving 80 ppm died. Ducks receiving 40 or 80 ppm selenium consumed less feed than ducks in the other treatment groups. Body weights of ducks receiving 40 or 80 ppm selenium declined during the study. The post-breeding molt was delayed in ducks receiving 40 ppm; most ducks receiving 80 ppm selenium died prior to the onset of molt. At necropsy, numerous abnormalities were observed in ducks that died but only a small number of abnormalities were observed in ducks surviving to the end of the study in the 40 ppm group. Weights of the heart, spleen, and pancreas were mostly lower and weights of the kidney were higher for ducks dying during the study than for euthanized ducks. Liver weights were unaffected. Selenium accumulated in soft tissues approximately in proportion to dietary concentrations. Selenium concentrations in tissues of all ducks that died were different from those of surviving ducks in the 0, 10, and 20 ppm groups, but were not different from those of surviving ducks in the 40 ppm group. Proposed diagnostic criteria for fatal chronic selenosis were derived from body weight, macroscopic abnormalities, organ weights, and concentrations of selenium in the liver. Proposed diagnostic criteria for non-fatal chronic selenosis were derived from body weight, plumage condition, macroscopic abnormalities, concentrations of selenium in the liver, reproductive failure, and alterations of blood and tissue chemistries. Lead or dioxin poisoning have diagnostic criteria most similar to selenium toxicosis.

Journal of Wildlife Diseases↗

A hydrometric and geochemical approach to test the transmissivity feedback hypothesis during snowmelt

To test the transmissivity feedback hypothesis of runoff generation, surface and subsurface waters were monitored and sampled during the 1996 snowmelt at various topographic positions in a 41 ha forested headwater catchment at Sleepers River, Vermont. Two conditions that promote transmissivity feedback existed in the catchment during the melt period. First, saturated hydraulic conductivity increased toward land surface, from a geometric mean of 3.6 mm h-1 in glacial till to 25.6 mm h-1 in deep soil to 54.0 mm h-1 in shallow soil. Second, groundwater levels rose to within 0.3 m of land surface at all riparian sites and most hillslope sites at peak melt. The importance of transmissivity feedback to streamflow generation was tested at the catchment scale by examination of physical and chemical patterns of groundwater in near-stream (discharge) and hillslope (recharge/lateral flow) zones, and within a geomorphic hollow (convergent flow). The presence of transmissivity feedback was supported by the abrupt increase in streamflow as the water table rose into the surficial, transmissive zone; a flattening of the groundwater level vs. streamflow curve occurred at most sites. This relation had a clockwise hysteresis (higher groundwater level for given discharge on rising limb than at same discharge on falling limb) at riparian sites, suggesting that the riparian zone was the dominant source area during the rising limb of the melt hydrograph. Hysteresis was counterclockwise at hillslope sites, suggesting that hillslope drainage controlled the snowmelt recession. End member mixing analysis using Ca, Mg, Na, dissolved organic carbon (DOC), and Si showed that stream chemistry could be explained as a two-component mixture of groundwater high in base cations and an O-horizon/overland flow water high in DOC. The dominance of shallow flow paths during events was indicated by the high positive correlation of DOC with streamflow (r2 = 0.82). Despite the occurrence of transmissivity feedback, hillslope till and soil water were ruled out as end members primarily because their distinctive high-Si composition had little or no effect on streamwater composition. Till water from the geomorphic hollow had a chemistry very close to streamwater base flow, and may represent the base flow end member better than the more concentrated riparian groundwater. During snowmelt, streamwater composition shifted as this base flow was diluted - not by shallow groundwater from the hillslope, but rather by a more surficial O-horizon/overland flow water.Surface and subsurface waters were analyzed to test the transmissivity feedback of runoff generation during the 1996 snowmelt in a catchment at Sleepers River, Vermont. The importance of transmissivity feedback to stream flow generation was tested by examination of physical and chemical patterns of groundwater in near-stream and hillslope zones within a geomorphic hollow. End member mixing analysis of Ca, Mg, Na, dissolved organic carbon (DOC), and Si showed that stream chemistry could be explained as a two-component mixture of groundwater high in base cations and an O-horizon/overland flow water high in DOC. The dominance of shallow water paths during the events was indicated by the high positive correlation of DOC with streamflow (r2 = 0.82).

Journal of Hydrology↗

Effect of canopy removal on snowpack quantity and quality, fraser experimental forest, Colorado

Snowpack peak water equivalent (PWE), ion concentration, content, and spatial distribution of ion load data from spring 1987-1996 in a 1 ha clearcut and adjacent forested plots vegetated by mature Picea engelmannii and Abies lasiocarpa in the Fraser experimental forest (FEF), Colorado are presented. Our objectives were: (1) to see if a forest opening might redistribute snowfall, snowpack moisture, and snowpack chemical content, and (2) to examine the importance of canopy interception on snowpack quantity and chemistry. On an average, the canopy intercepted 36% of snowfall. Interception was correlated with snowfall amount, snowpack PWE beneath the canopy, and air temperature. Canopy removal increased snowpack PWE to >90% cumulative snowfall inputs. Snowpack K-, H-, and NH4+ concentrations on the clearcut were lower and NO3- higher than in the snowpack beneath the forested plots. Cu mulative snowfall K+ input was less than in the clearcut snowpack; H+ inputs were greater in snowfall than in the snowpack of any plot; and inorganic N (NO3- and NH4+) inputs from snowfall to the clearcut were greater than to the forested plots. Processes accounting for the differences between snowfall inputs and snowpack ion content were leaching of organic debris in the snowpack, differential elution of the snowpack, and canopy retention. There were significant trends by year in snowpack ion content at PWE without similar trends in snowfall inputs. This finding coupled with snowpack ion elution bring into question the use of snowpack chemistry as an indicator of winter atmospheric inputs in short-term studies. ?? 2001 Elsevier Science B.V.

Journal of Hydrology↗

Arsenic Geochemistry and Hydrostratigraphy in Midwestern U.S. Glacial Deposits

Arsenic concentrations exceeding the U.S. EPA's 10 ??g/L standard are common in glacial aquifers in the midwestern United States. Previous studies have indicated that arsenic occurs naturally in these aquifers in association with metal-(hydr)oxides and is released to groundwater under reducing conditions generated by microbial oxidation of organic matter. Despite this delineation of the arsenic source and mechanism of arsenic mobilization, identification of arsenic-impacted aquifers is hindered by the heterogeneous and discontinuous nature of glacial sediments. In much of the Midwest, the hydrostratigraphy of glacial deposits is not sufficiently characterized to predict where elevated arsenic concentrations are likely to occur. This case study from southeast Wisconsin presents a detailed characterization of local stratigraphy, hydrostratigraphy, and geochemistry of the Pleistocene glacial deposits and underlying Silurian dolomite. Analyses of a single core, water chemistry data, and well construction reports enabled identification of two aquifers separated by an organic-rich aquitard. The upper, unconfined aquifer provides potable water, whereas arsenic generally exceeds 10 ??g/L in the deeper aquifer. Although coring and detailed hydrostratigraphic characterization are often considered impractical, our results demonstrate that a single core improved interpretation of the complex lithology and hydrostratigraphy. This detailed characterization of hydrostratigraphy facilitated development of well construction guidelines and lays the ground work for further studies of the complex interactions among aquifer sediments, hydrogeology, water chemistry, and microbiology that lead to elevated arsenic in groundwater. Copyright ?? 2009 The Author(s). Journal compilation ?? 2009 National Ground Water Association.

Ground Water↗

Forest soil chemistry and terrain attributes in a Catskills watershed

Knowledge of soil chemistry is useful in assessing the sensitivity of forested areas to natural and anthropogenic disturbances, but characterizing large areas is expensive because of the large sample numbers required and the cost of soil chemical analyses. We collected and chemically analyzed soil samples from 72 sites within a 214-ha watershed in the Catskill Mountains of New York to evaluate factors that influence soil chemistry and whether terrain features could be used to predict soil chemical properties. Using geographic information system (GIS) techniques, we determined five terrain attributes at each sampling location: (i) slope, (ii) aspect, (iii) elevation, (iv) topographic index, and (v) flow accumulation. These attributes were ineffective in predicting the chemical properties of organic and mineral soil samples; together they explained only 4 to 25% of the variance in pH(w), effective cation-exchange capacity (CEC(e)), exchangeable bases, exchangeable acidity, total C, total N, and C/N ratio. Regressions among soil properties were much better; total C and pH(w) together explained 33 to 66% of the variation in exchangeable bases and CEC(e). Total C was positively correlated with N (r = 0.91 and 0.96 in Oa horizons and mineral soil, respectively), exchangeable bases (r = 0.65, 0.76), and CEC(e) (r = 0.54, 0.44), indicating the importance of organic matter to the chemistry of these acidic soils. The fraction of CEC(e) occupied by H explained 44% of the variation in pH(w). Soil chemical properties at this site vary on spatial scales finer than typical GIS analyses, resulting in relationships with poor predictive power. Thus, interrelationships among soil properties are more reliable for prediction.Knowledge of soil chemistry is useful in assessing the sensitivity of forested areas to natural and anthropogenic disturbances, but characterizing large areas is expensive because of the large sample numbers required and the cost of soil chemical analyses. We collected and chemically analyzed soil samples from 72 sites within a 214-ha watershed in the Catskill Mountains of New York to evaluate factors that influence soil chemistry and whether terrain features could be used to predict soil chemical properties. Using geographic information system (GIS) techniques, we determined five terrain attributes at each sampling location: (i) slope, (ii) aspect, (iii) elevation, (iv) topographic index, and (v) flow accumulation. These attributes were ineffective in predicting the chemical properties of organic and mineral soil samples; together they explained only 4 to 25% of the variance in pHw, effective cation-exchange capacity (CECe), exchangeable bases, exchangeable acidity, total C, total N, and C/N ratio. Regressions among soil properties were much better; total C and pHw together explained 33 to 66% of the variation in exchangeable bases and CECe. Total C was positively correlated with N (r = 0.91 and 0.96 in Oa horizons and mineral soil, respectively), exchangeable bases (r = 0.65, 0.76), and CECe (r = 0.54, 0.44), indicating the importance of organic matter to the chemistry of these acidic soils. The fraction of CECe occupied by H explained 44% of the variation in pHw. Soil chemical properties at this site vary on spatial scales finer than typical GIS analyses, resulting in relationships with poor predictive power. Thus, interrelationships among soil properties are more reliable for prediction.

New York↗

The significance of microbial processes in hydrogeology and geochemistry

Microbial processes affect the chemical composition of groundwater and the hydraulic properties of aquifers in both contaminated and pristine groundwater systems. The patterns of water-chemistry changes that occur depend upon the relative abundance of electron donors and electron acceptors. In many pristine aquifers, where microbial metabolism is limited by the availability of electron donors (usually organic matter), dissolved inorganic carbon (DIC) accumulates slowly along aquifer flow paths and available electron acceptors are consumed sequentially in the order dissolved oxygen > nitrate > Fe(III) > sulfate > CO2 (methanogenesis). In aquifers contaminated by anthropogenic contaminants, an excess of available organic carbon often exists, and microbial metabolism is limited by the availability of electron acceptors. In addition to changes in groundwater chemistry, the solid matrix of the aquifer is affected by microbial processes. The production of carbon dioxide and organic acids can lead to increased mineral solubility, which can lead to the development of secondary porosity and permeability. Conversely, microbial production of carbonate, ferrous iron, and sulfide can result in the precipitation of secondary calcite or pyrite cements that reduce primary porosity and permeability in groundwater systems.

Hydrogeology Journal↗

Changes in the isotopic and chemical composition of ground water resulting from a recharge pulse from a sinking stream

The Little River, an ephemeral stream that drains a watershed of approximately 88 km2 in northern Florida, disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer, the source of water supply in northern Florida. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques. Nine monitoring wells were installed open to the uppermost part of the aquifer in areas near the sinks where numerous subterranean karst solution features were identified using ground penetrating radar. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Rapid recharge of river water into some parts of the aquifer during high-flow conditions was indicated by enriched values of delta 18O and delta deuterium (-1.67 to -3.17 per mil and -9.2 to -15.6 per mil, respectively), elevated concentrations of tannic acid, higher (more radiogenic) 87Sr/86Sr ratios, and lower concentrations of 222Rn, silica, and alkalinity compared to low-flow conditions. The proportion of river water that mixed with ground water ranged from 0.10 to 0.67 based on binary mixing models using the tracers 18O, deuterium, tannic acid, silica, 222Rn, and 87Sr/86Sr. On the basis of mass-balance modeling during steady-state flow conditions, the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter.The Little River of northern Florida disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques. Nine monitoring wells were installed open to the uppermost part of the aquifer. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Based on mass-balance modeling during steady-state flow conditions, it was found that the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter.

Journal of Hydrology↗

Sensitive strata in Bootlegger Cove Formation

Sensitivity magnitudes are interpreted from remolded strength values in recent subsurface geologic, geotechnical, and geochemical data from the Bootlegger Cove Formation adjacent to the Turnagain Heights Landslide. The results show that strata composed of highly sensitive clays occur in both the middle and lower zones of the formation, and that between these strata the clays are generally of low-to-medium sensitivity. The most sensitive stratum is in the middle zone between two sand layers, and its sensitivity increases from both clay-sand interfaces to a maximum at the center of the stratum. The pore fluid chemistry of the highly sensitive materials differs from that in the materials of low to medium sensitivity only in their concentrations of organic carbon, chloride, bicarbonate, and sulfate. The total dissolved solids concentration is low, and the ratio of monovalent to divalent cations is very high throughout the middle and lower zones of the formation. Of the known causes of high and extremely high sensitivities, only organic and/or anionic dispersants are consistent with these findings.

Journal of Geotechnical Engineering↗

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41 K to 39 K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41 K/ 39 K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2, N=108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41 K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings1, 2. Although our average bulk-silicate Earth value (-0.54‰) is indistinguishable from previously published values, we find systematic δ 41 K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ 41 K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems.

Journal of Analytical Atomic Spectrometry↗

Correlation of resource plays and biodiversity patterns: accumulation of organic-rich shale tracks taxonomic turnover

Similar paleogeographic and paleotectonic settings characterize most self-sourced shale hydrocarbon plays. Their deposition occurred within similar orders of magnitude of eustatic events and during geologic periods characterized by “warm” (or transitional) climates and calcitic seas. In addition, the stratigraphic occurrence of shale plays parallels certain historical patterns of marine metazoan biodiversity. Such strong agreement among several correlation tools elucidates why these resources may be limited to discrete intervals of geological time. Correlation of self-sourced shale with biodiversity trends indicates that the factors controlling the deposition of marine organic matter may not be independent of those that induced taxonomic turnover. Paleoecological changes promoted accumulation and preservation of Type II kerogen. Deposition of self-sourced shale appears to correspond to reductions in absolute biodiversity and declining percentages of bioturbating taxa, with concomitant increases in proportions of pelagic taxa relative to infaunal and epifaunal organisms. Whereas upwelling and anoxia may have contributed to the deposition of kerogen in source rocks throughout much of the sedimentary record, diminished consumption of biomass by benthic metazoans likely augmented the preservation of organic carbon during deposition of this shale type. Rapid tectonic-plate reconfiguration induced coeval events, creating basins with sufficiently high rates of accommodation creation necessary to preserve additional organic material accumulating as the heterotrophic benthos suffered in response to rapidly changing environments. Combining sea-level curves, paleogeography, climate, and seawater chemistry provides a first-order approximation of the distribution of potential self-sourced shale in the geologic record. A model that predicts the stratigraphic distribution of self-sourced-shale deposition can aid in exploration of continuous hydrocarbon accumulations in self-sourced reservoirs globally.

GCAGS Journal↗

Denitrification in sediments from the hyporheic zone adjacent to a small forested stream

Denitrifying potentials increased with increasing distance from the stream channel. Dissolved oxygen was 100% of the concentration expected in equilibrium with the atmosphere in water obtained from monitoring wells immediately adjacent to the stream but was as low as 7% of the expected value in water 11.4 m inland. Both nitrate and dissolved organic carbon decreased over summer in wells at the base of the alder-forested slope. A 48-h injection of nitrate-amended stream water into hyporheic water 8.4 m inland stimulated nitrous oxide production in the presence of acetylene. Nitrous oxide was generated as nitrate and acetylene were co-transported to a well 13 m down-gradient. Acetylene-block experiments coupled with the chemistry data suggest that denitrification can modify the chemistry of water during passage through the hyporheic zone. -from Authors

Canadian Journal of Fisheries and Aquatic Sciences↗

Nearshore versus offshore copper loading in Lake Superior sediments: Implications for transport and cycling

A thorough understanding of the fate and transport of metals in Lake Superior is necessary in order to predict the ability of Lake Superior to recover from anthropogenic perturbations (copper mining). Sediment cores were collected from nearshore and offshore sites in Lake Superior and used to evaluate spatial and temporal variations in copper loading associated with mining-related activities. Although both settings have been strongly affected by anthropogenic releases of copper, copper concentrations in nearshore cores are significantly greater than those found in offshore cores, implying that nearshore copper loading is dominated by simple deposition and burial of sediment generated from mining activities. Temporal variations in copper profiles in sediments from nearshore environments closelymimic copper production rates. Conversely, copper loading histories derived from offshore sediments are not well correlated to production rates. The offshore sediment cores, when compared with analogous cores from Lakes Ontario and Michigan, show that the average, lake-wide intensity of copper loading in Lake Superior is comparable to the other two lakes, despite the fact that Lake Superior has received the largest total burden of anthropogenic copper. Cu/Zn ratios, used to evaluate the amount of copper loading derived from mining discharges, vary strongly in nearshore environments in response to loading. Cu/Zn ratios in offshore sediments are much less variable, implying that copper loading may be regulated by additional mechanisms (solution chemistry and/or biologic uptake). Study of trace metal partitioning within Lake Superior sediments indicates that the organic fraction of the sediment contains the majority of the copper. Copper concentrations in offshore sediments are significantly correlated to organic carbon content of the sediment whereas copper concentrations in nearshore sediments are not. These findings support the model that transport and deposition of particles released from mining discharges dominate copper loading in nearshore sediments, whereas biologic uptake and settling of particulate organic matter may regulate copper loading in offshore sediments.

Journal of Great Lakes Research↗

Determination of uranium concentration in water by liquid anion exchange-delayed neutron analysis

Dissolved uranium is selectively removed from 11 of filtered, acidified water using a liquid anion exchange resin (Amberlite LA-1) dissolved in 10 ml of purified kerosene. The organic phase is then analyzed by a standard delayed neutron counting technique. Yields of removed uranium are consistently greater than 90 percent over a measured concentration range of 1.0 to 100 ppb uranium. The absolute detection limit based on 11 of water is 0.06 ppb. Elemental interferences are minimal and the results compare favorably with fluorometric analyses of natural waters.

Journal of Radioanalytical and Nuclear Chemistry↗

Hydrologic landscapes on the Delmarva Peninsula - Part 2: Estimates of base-flow nitrogen load to Chesapeake Bay

ABSTRACT: The relation between landscape characteristics and water chemistry on the Delmarva Peninsula can be determined through a principal-component analysis of basin characteristics. Two basin types were defined by factor scores: (1) well-drained basins, characterized by combinations of a low percentage of forest cover, a low percentage of poorly drained soil, and elevated channel slope; and (2) poorly drained basins, characterized by a combinations of an elevated percentage of forest cover, an elevated percentage of poorly drained soil, and low channel slopes. Results from base-flow sampling of 29 basins during spring 1991 indicate that water chemistry of the two basin types differ significantly. Concentrations of calcium, magnesium, potassium, alkalinity, chloride, and nitrate are elevated in well-drained basins, and specific conductance is elevated. Concentrations of aluminum, dissolved organic carbon, sodium, and silica are elevated in poorly drained basins whereas specific conductance is low. The chemical patterns found in well-drained basins can be attributed to the application of agricultural chemicals, and those in poorly drained basins can be attributed to ground-water flowpaths. These results indicate that basin types determined by a quantitative analysis of basin characteristics can be related statistically to differences in base-flow chemistry, and that the observed statistical differences can be related to major processes that affect water chemistry.

Journal of the American Water Resources Associatio↗

Cyclic biogeochemical processes and nitrogen fate beneath a subtropical stormwater infiltration basin

A stormwater infiltration basin in north–central Florida, USA, was monitored from 2007 through 2008 to identify subsurface biogeochemical processes, with emphasis on N cycling, under the highly variable hydrologic conditions common in humid, subtropical climates. Cyclic variations in biogeochemical processes generally coincided with wet and dry hydrologic conditions. Oxidizing conditions in the subsurface persisted for about one month or less at the beginning of wet periods with dissolved O 2 and NO 3 - showing similar temporal patterns. Reducing conditions in the subsurface evolved during prolonged flooding of the basin. At about the same time O 2 and NO 3 - reduction concluded, Mn, Fe and SO 4 2 - reduction began, with the onset of methanogenesis one month later. Reducing conditions persisted up to six months, continuing into subsequent dry periods until the next major oxidizing infiltration event. Evidence of denitrification in shallow groundwater at the site is supported by median NO 3 -–N less than 0.016 mg L -1 , excess N 2 up to 3 mg L -1 progressively enriched in δ 15 N during prolonged basin flooding, and isotopically heavy δ 15 N and δ 18 O of NO 3 - (up to 25‰ and 15‰, respectively). Isotopic enrichment of newly infiltrated stormwater suggests denitrification was partially completed within two days. Soil and water chemistry data suggest that a biogeochemically active zone exists in the upper 1.4 m of soil, where organic carbon was the likely electron donor supplied by organic matter in soil solids or dissolved in infiltrating stormwater. The cyclic nature of reducing conditions effectively controlled the N cycle, switching N fate beneath the basin from NO 3 - leaching to reduction in the shallow saturated zone. Results can inform design of functionalized soil amendments that could replace the native soil in a stormwater infiltration basin and mitigate potential NO 3 - leaching to groundwater by replicating the biogeochemical conditions under the observed basin.

Florida↗

Measurements of210Pb,137Cs, organic carbon and trace elements in sediments of the Illinois and Mississippi rivers

Radiometric dating of sediment accumulations by137Cs and210Pb has been successfully initiated in the Illinois and Mississippi Rivers. Sedimentation rates measured at 13 locations range from 0.7 to 3.6 cm/y. Chemical analysis has been completed for up to 45 major and trace elements in core samples. The upper Illinois River contains higher metal levels than the Mississippi River. The amount of carbon (energy) lost to sediments in large floodplain rivers is estimated between 370 and 4000 g/m2/y. ?? 1987 Akade??miai Kiado??.

Journal of Radioanalytical and Nuclear Chemistry A↗

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Journal of Chromatography A↗