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Metal biogeochemistry in surface-water systems; a review of principles and concepts

Metals are ubiquitous in natural surface-water systems, both as dissolved constituents and as particulate constituents. Although concentrations of many metals are generally very low (hence the common term 'trace metals'), their effects on the water quality and the biota of surfacewater systems are likely to be substantial. Biogeochemical partitioning of metals results in a diversity of forms, including hydrated or 'free' ions, colloids, precipitates, adsorbed phases, and various coordination complexes with dissolved organic and inorganic ligands. Much research has been dedicated to answering questions about the complexities of metal behavior and effects in aquatic systems. Voluminous literature on the subject has been produced. This paper synthesizes the findings of aquatic metal studies and describes some general concepts that emerge from such a synthesis. Emphasis is on sources, occurrence, partitioning, transport, and biological interactions of metals in freshwater systems of North America. Biological interactions, in this case, refer to bioavailability, effects of metals on ecological characteristics and functions of aquatic systems, and roles of biota in controlling metal partitioning. This discussion is devoted primarily to the elements aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc and secondarily to cobalt, molybdenum, selenium, silver, and vanadium. Sources of these elements are both natural and anthropogenic. Significant anthropogenic sources are atmospheric deposition, discharges of municipal and industrial wastes, mine drainage, and urban and agricultural runoff. Biogeochemical partitioning of metals is controlled by various characteristics of the water and sediments in which the metals are found. Among the most important controlling factors are pH, oxidation-reduction potential, hydrologic features, sediment grain size, and the existence and nature of clay minerals, organic matter, and hydrous oxides of manganese and iron. Partitioning is also controlled by biological processes that provide mechanisms for detoxification of metals and for enhanced uptake of nutritive metals. Partitioning is important largely because availability to biota is highly variable among different phases. Hence, accumulation in biological tissues and toxicity of an element are dependent not only on total concentration of the element but also on the factors that control partitioning.

Circular↗

Biogeochemistry of vanadium

Vanadium is known to occur in soils as vanadates of copper, zinc, lead, uranium, ferric iron, manganese, calcium, and potassium. Vanadium replaces aluminum in clays and occurs in porphyrin complexes in bituminous sediments. Small amounts of vanadium are stimulating to plants; large amounts are toxic. Ten to 20 ppm vanadium in nutrient solution is commonly harmful to plants, but larger amounts can be tolerated by specific legumes, which use vanadium in the nitrogen-fixation process. Old wood in vegetation contains more vanadium than young wood, and roots contain the greatest accumulations. Herbs are more efficient accumulators of vanadium than trees and shrubs. Allium and some species of Astragalus, Castilleja, and Chrysothamnus are shown to be accumulators of vanadium. The vanadium content of plants rooted in highly calcic soils is very low, and that of plants rooted in seleniferous soils is high. Outdoor plot experiments verify a decrease in the presence of selenium. The absorption and translocation of vanadium by several plant species was found to be in direct ratio to that of selenium. Plant species that absorb large amounts of calcium are most tolerant of high-vanadium soils as the vanadium is precipitated in the root. Vanadium occurs in all animals and is accumulated in large amounts by Ascidians and by Holothuroidians. Vanadium is probably essential to vertebrates. Vanadium has been shown to decrease dental caries in animals and children. Vanadium inhibits the biosynthesis of cholesterol in both animals and man. Seleniferous areas in the western conterminous United States may support vegetation that contains large amounts of vanadium. Many areas of this country on the other hand may be nutritionally deficient in vanadium.

Open-File Report↗

The biogeochemistry of wetlands in the San Luis Valley, Colorado: The effects of acid drainage from natural and mine sources

The Summitville Mine, located near the old mining town of Summitville in Rio Grande County, Colorado, operated between July 1986 and December 1992 as a large-tonnage open-pit heap-leach gold mine. During its 6 years of existence the trace metal levels in drainage water from the mine site were elevated over historical (pre-1986) levels (Moran and Wentz, 1974) due to input from three sources—heap leach water, seeps that occur throughout the mine workings, and an increase in the metal load of water coming from the old Reynolds Adit. Mine-drainage waters flow into Wightman Fork, a small tributary of the Alamosa River, which in turn flows east into the San Luis Valley. The increase in the trace metal burden of the Alamosa River watershed is of concern to farmers, land owners, and Federal and State wildlife agencies. The information presented here is largely abstracted from reports previously published (Balistrieri and others, 1995; Gough and others, 1995).

Colorado↗

Mercury species and other selected constituent concentrations in water, sediment, and biota of Sinclair Inlet, Kitsap County, Washington, 2007-10

This report presents data collected for two U.S. Geological Survey field sampling projects related to mercury (Hg) in Sinclair Inlet: (1) the Watersheds Sources Project that evaluated the sources of mercury to Sinclair Inlet during December 2007 to March 2010, and (2) the Methylation and Bioaccumulation Project, a comprehensive examination of mercury biogeochemistry in sediment, water, and zooplankton during August 2008–February 2010. For the Watershed Sources project, nonpoint and point sources of mercury to Sinclair Inlet from the Bremerton naval complex (BNC) were evaluated by using filtered total mercury and particulate total mercury measured in water samples collected from 11 wells, 2 dry dock sump discharges, and a steam plant's effluent at the BNC. Methylmercury sources to the inlet were examined by determining filtered methylmercury concentrations in water samples collected from five wells, two dry dock sump discharges, a steam plant's effluent, five intertidal piezometers, and three stormwater drains on the BNC, as well as in samples from five creeks, two wastewater treatment facilities, and three stormwater drains in the Sinclair Inlet watershed outside of the BNC. An improved understanding of tidally modulated mercury migration to Sinclair Inlet from the BNC was gained through three intensive nearshore (tidal) sampling events of mercury species in groundwater and a nearby stormwater drain. The Methylation and Bioaccumulation Project included a comprehensive field study of mercury biogeochemistry in marine sediment, water, and zooplankton in Sinclair Inlet. Mercury, iron, and sulfur species in sediment porewater from six sites within and three sites outside of Sinclair Inlet were measured to provide insight into the processes that produce methylmercury in the sediments. Total mercury, methylmercury, dissolved organic carbon, and redox-sensitive species were measured in porewaters in the top 2 centimeters of sediment, and these data were paired with sedimentary flux measurements from core incubation experiments to connect sedimentary processes to the water column. A broad-scale study of mercury methylation potential and mercury species at 20-plus stations in Sinclair Inlet was conducted in February 2009 and 2010, June 2009, and August 2009. Sedimentary flux measurements and analysis of mercury and biogeochemicals in sediment porewater and bottom water were made at six of the broad-scale stations. Bioaccumulation processes in the water column in the context of the sedimentary flux of methylmercury were examined using monthly survey data collected between August 2008 and August 2009. The survey data included concentrations of methylmercury and isotope ratios of carbon and nitrogen in bulk zooplankton measured at four stations in Sinclair Inlet in the context of the population of bulk zooplankton ascertained by taxonomical identification. The analysis of filtered total mercury, total particulate mercury, filtered methylmercury, particulate methylmercury, chlorophyll a, isotopes of carbon and nitrogen in suspended matter, and other biogeochemical data will facilitate the examination of the biogeochemistry of mercury in Sinclair Inlet.

Washington↗

Organic matter integration, overprinting, and the relative fraction of optically active organic carbon in a human-impacted watershed

Rivers continually integrate terrestrial organic matter (OM) into their waters, in a process that transfers 1.9 Pg C yr –1 as the primary linkage between oceanic and terrestrial carbon cycles. Yet rivers are not simple, conservative OM integrators. Patchy local land uses (wetlands, bogs, agriculture) release OM that can disproportionately alter river biogeochemistry and overprint upstream carbon. These releases are quantifiable at the plot scale but remain unpredictable across river reaches and watersheds, critically inhibiting our ability to scale up terrestrial-aquatic linkages to regional/global carbon cycling models. We evaluated OM overprinting distance along a human-influenced watershed to quantify river integration of terrestrial OM and to bridge the quantification gap between habitats and waterway biogeochemistry. We investigated changes in dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition (lignin phenols, fluorescence excitation-emission spectra using parallel factor analysis [PARAFAC], and the relative fraction of optically active DOM [EEM DOC ]). DOC concentrations increased continually ( p < 0.001) downstream, from median 1.0 mg L –1 at 30 km (headwaters) to 3.3 mg L –1 at the river mouth. This rate of increase corresponded to a DOC overprinting distance—the longitudinal distance over which DOC concentrations double—of 13 km. Mainstem DOC overprinting distance ranged from 8 km (winter, rainy season) to 21 km (summer, dry season with irrigation), highlighting stronger overprinting during increased hydraulic connectivity. Stronger overprinting also correlated to higher EEM DOC ( p < 0.001). Overprinting distance effectively quantifies river integration of DOM along the terrestrial-aquatic interface, helping to refine bottom-up carbon cycle estimates, inform upscaling of site-specific fluxes, and to track land use and climate influence on river biogeochemistry.

California↗

Selenium biotransformations into proteinaceous forms by foodweb organisms of selenium-laden drainage waters in California

Selenium contamination represents one of the few clear cases where environmental pollution has led to devastation of wildlife populations, most notably in agricultural drainage evaporation and power plant coal-fly ash receiving ponds. Complex biogeochemistry, in particular extensive biotransformations and foodchain transfer, governs Se ecotoxicology and toxicology, for which the mechanism(s) are still elusive. However, total waterborne Se concentration has been widely used as a criterion for regulating and mitigating Se risk in aquatic ecosystems, which does not account for Se biogeochemistry and its site-dependence. There is a need for more reliable indicator(s) that encompass Se ecotoxicity and/or toxicity. Selenomethionine warrants special attention since it simulates Se toxicosis of wildlife in laboratory feeding studies. While low in free selenomethionine, microphytes isolated from Se-laden agricultural evaporation ponds were abundant in proteinaceous selenomethionine. This prompted a more extensive survey of Se speciation in foodchain organisms including microphytes, macroinvertebrates, fish, and bird embryos residing mainly in the agricultural drainage systems of the San Joaquin Valley, California. Total Se in biomass, water-soluble fractions, and protein-rich fractions were measured along with GC-MS analysis of proteinaceous selenomethionine. In all foodchain organisms, water-soluble Se constituted the major fraction of total biomass Se, while proteinaceous Se was a substantial, if not dominant, fraction of the water-soluble Se. In turn, proteinaceous selenomethionine comprised an important fraction of proteinaceous Se. In terms of total biomass Se, an average 1400-fold of Se biomagnification from water to microphytes was observed while subsequent transfer from microphytes to macroinvertebrates exhibited an average of only 1.9-fold. The latter transfer was more consistent and greater in extent for proteinaceous Se and proteinaceous selenomethionine, which is consistent with their importance in foodchain transfer. Proteinaceous Se in the omnivorous carp (Cyprinus carpio) liver also demonstrated a relation to ovarian lesions, while deformed stilt (Himantopus mexicanus) embryo was more abundant in proteinaceous selenomethionine than were normal embryos. Although limited in the number of organisms surveyed, these findings provide an impetus for further field and laboratory feeding studies to substantiate the hypothesis that proteinaceous selenomethionine underlies Se ecotoxicity, which may in turn prove to be a reliable indicator of Se risk in aquatic ecosystems. Copyright ?? 2002 Elsevier Science B.V.

Aquatic Toxicology↗

Linking meso-scale spatial variation in methylmercury production to bioaccumulation in tidal marsh food webs

Differences in sediment biogeochemistry among tidal marsh features with different hydrological and geomorphological characteristics, including marsh interiors, marsh edges, first-order channels, and third-order channels, can result in spatial variation in MeHg production and availability. To better understand the link between MeHg production in sediments and bioaccumulation in primary and secondary consumer invertebrates and fish, we characterized mesoscale spatial variation in sediment biogeochemistry and MeHg concentrations of sediments, water, and consumer tissues among marsh features. Our results indicated that marsh interiors had biogeochemical conditions, including greater concentrations of organic matter and sulfate reduction rates, that resulted in greater MeHg concentrations in sediments and surface water particulates from marsh interiors compared to other features. Tissue MeHg concentrations of consumers also differed among features, with greater concentrations from marsh edges and interiors compared to channels. This spatial mismatch of MeHg concentrations in sediments and water compared to those in consumers may have resulted from differences in behavior and physiology among consumers that influenced the spatial scale over which MeHg was integrated into tissues. Our results highlight the importance of sampling across a suite of marsh features and considering the behavioral and physiological traits of sentinel taxa for contaminant monitoring studies.

Environmental Science and Technology↗

Estuarine exchange flow in the Albemarle-Pamlico estuarine system

Estuarine exchange flow controls the salt balance and regulates biogeochemistry in an estuary. The Albemarle-Pamlico estuarine system (APES) is the largest coastal lagoon in the U.S. and historically susceptible to a series of environmental issues including salt water intrusion and eutrophication, yet its estuarine exchange flow is poorly understood. Here, we investigate the estuarine exchange flow in the APES, its tributary estuaries (Pamlico and Neuse), and sub-basin Albemarle Sound using the total exchange flow analysis framework based on results from a deterministic numerical model. We find the following: (a) Dynamics controlling estuarine exchange flow in the APES vary spatially and depend on timescales considered. At inlets, estuarine exchange flows respond to both tidal prism and residual water levels at weather-to-spring/neap timescales. At a long quasi-steady timescale represented as annual means, estuarine exchange flow is dominated by barotropic flow. Within the tributary estuaries, estuarine exchange flows at timescales of wind periods are controlled by wind-induced straining, whereas the quasi-steady state condition is dominated by gravitational circulation. At Albemarle Sound, exchange flow is dominated by the residual water levels at weather-to-spring/neap timescales, while at quasi-steady state it is controlled by barotropic flow. (b) At the quasi-steady annual timescale, the salt content decreases with river discharge. At the weather-to-spring/neap timescales, salt content is insensitive to variations in estuarine exchange flow, except for within Albemarle Sound. (c) Estuarine exchange flow likely influences the biogeochemistry of the APES by playing a key role in regulating the flushing efficiency and material exchange, a role that has been previously overlooked.

North Carolina↗

Mercury methylation and bioaccumulation in Sinclair Inlet, Kitsap County, Washington

The U.S. Geological Survey evaluated the transformation of mercury to bioavailable methylmercury in Sinclair Inlet, Kitsap County, Washington, and assessed the effect of the transformation processes on the mercury burden in marine organisms and sediment. In August 2008, samples of sediment, water, and biota from six sites in Sinclair Inlet and three bays representative of Puget Sound embayments were collected. The extensive sediment sampling included analysis of methylmercury in sediment and porewater, estimates of methylation production potential, and analyses of ancillary constituents associated with organic carbon and reduction-oxidation (redox) conditions to assist in interpreting the mercury results. Analyses of methylmercury in water overlying incubated cores provided an estimate of the release of methylmercury to the water column. Collection of samples for mercury species in the aqueous, particulate (suspended solids), and biological phases, and for ancillary carbon and nitrogen constituents in surface water, continued, on about a monthly schedule, at four stations through August 2009. In February, June, and August 2009, seasonal sediment samples were collected at 20 stations distributed between greater Sinclair Inlet and Operable Unit B Marine of the Bremerton naval complex, Bremerton, Washington, to examine geographical and seasonal patterns of mercury biogeochemistry of sediment in Sinclair Inlet. At six of these seasonal sediment stations, porewater was collected and triplicate core incubation experiments were done. Median sediment-methylmercury concentrations were not statistically different between the representative bays and Sinclair Inlet. The percentage of sediment methylmercury (relative to total mercury) was actually lower in the Sinclair Inlet sites compared with the representative bays, reflecting the higher sediment total mercury concentration for the Sinclair Inlet stations compared with the representative bays. Likewise, median sediment methylmercury concentrations were not statistically different between the greater Sinclair Inlet stations and the Bremerton naval complex stations; whereas the percentage of sediment methylmercury to total mercury was lower in the Bremerton naval complex due to higher sediment total mercury concentrations than the greater Sinclair Inlet stations. The biogeochemical characteristics of each station, measured by redox, organic carbon, and the seasonal availability of nutrients controlled methylmercury biogeochemistry. Mercury methylation production potential was a function of temperature, concentration of total mercury in sediment, and the percentage of ferrous iron (relative to total measured iron) across all sites. Methylmercury porewater concentrations were best described by using concentrations of dissolved organic carbon and reduction-oxidation conditions. Likewise, the variable fluxes of methylmercury from incubated cores were best described using dissolved organic carbon and reduction-oxidation conditions. Sinclair Inlet exhibited the classic Puget Sound biological cycle, with spring and autumn phytoplankton blooms resulting in depletion of nitrate, orthophosphate, and silicate in the surface water. Although variable in timing between 2008 and 2009, a strong corresponding seasonal trend of increased availability, incorporation, and bioaccumulation of methylmercury into the food web of Sinclair Inlet occurred during the early spring and summer growing season.

Washington↗