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Methylmercury production in sediment from agricultural and non-agricultural wetlands in the Yolo Bypass, California, USA

As part of a larger study of mercury (Hg) biogeochemistry and bioaccumulation in agricultural (rice growing) and non-agricultural wetlands in California's Central Valley, USA, seasonal and spatial controls on methylmercury (MeHg) production were examined in surface sediment. Three types of shallowly-flooded agricultural wetlands (white rice, wild rice, and fallow fields) and two types of managed (non-agricultural) wetlands (permanently and seasonally flooded) were sampled monthly-to-seasonally. Dynamic seasonal changes in readily reducible ‘reactive’ mercury (Hg(II) R ), Hg(II)-methylation rate constants (k meth ), and concentrations of electron acceptors (sulfate and ferric iron) and donors (acetate), were all observed in response to field management hydrology, whereas seasonal changes in these parameters were more muted in non-agricultural managed wetlands. Agricultural wetlands exhibited higher sediment MeHg concentrations than did non-agricultural wetlands, particularly during the fall through late-winter (post-harvest) period. Both sulfate- and iron-reducing bacteria have been implicated in MeHg production, and both were demonstrably active in all wetlands studied. Stoichiometric calculations suggest that iron-reducing bacteria dominated carbon flow in agricultural wetlands during the growing season. Sulfate-reducing bacteria were not stimulated by the addition of sulfate-based fertilizer to agricultural wetlands during the growing season, suggesting that labile organic matter, rather than sulfate, limited their activity in these wetlands. Along the continuum of sediment geochemical conditions observed, values of k meth increased approximately 10,000-fold, whereas Hg(II) R decreased 100-fold. This suggests that, with respect to the often opposing trends of Hg(II)-methylating microbial activity and Hg(II) availability for methylation, microbial activity dominated the Hg(II)-methylation process, and that along this biogeochemical continuum, conditions that favored microbial sulfate reduction resulted in the highest calculated MeHg production potential rates. Rice straw management options aimed at limiting labile carbon supplies to surface sediment during the post-harvest fall–winter period may be effective in limiting MeHg production within agricultural wetlands.

California↗

Methylmercury production in and export from agricultural wetlands in California, USA: the need to account for physical transport processes into and out of the root zone

Concentration and mass balance analyses were used to quantify methylmercury (MeHg) loads from conventional (white) rice, wild rice, and fallowed fields in northern California's Yolo Bypass. These analyses were standardized against chloride to distinguish transport pathways and net ecosystem production (NEP). During summer, chloride loads were both exported with surface water and moved into the root zone at a 2:1 ratio. MeHg and dissolved organic carbon (DOC) behaved similarly with surface water and root zone exports at ~ 3:1 ratio. These trends reversed in winter with DOC, MeHg, and chloride moving from the root zone to surface waters at rates opposite and exceeding summertime root zone fluxes. These trends suggest that summer transpiration advectively moves constituents from surface water into the root zone, and winter diffusion, driven by concentration gradients, subsequently releases those constituents into surface waters. The results challenge a number of paradigms regarding MeHg. Specifically, biogeochemical conditions favoring microbial MeHg production do not necessarily translate to synchronous surface water exports; MeHg may be preserved in the soils allowing for release at a later time; and plants play a role in both biogeochemistry and transport. Our calculations show that NEP of MeHg occurred during both summer irrigation and winter flooding. Wild rice wet harvesting and winter flooding of white rice fields were specific practices that increased MeHg export, both presumably related to increased labile organic carbon and disturbance. Outflow management during these times could reduce MeHg exports. Standardizing MeHg outflow:inflow concentration ratios against natural tracers (e.g. chloride, EC) provides a simple tool to identify NEP periods. Summer MeHg exports averaged 0.2 to 1 μg m − 2 for the different agricultural wetland fields, depending upon flood duration. Average winter MeHg exports were estimated at 0.3 μg m − 2 . These exports are within the range reported for other shallow aquatic systems.

California↗

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ 34 S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over ecosystem sulfur biogeochemistry across relatively small spatial scales.

Hawaii↗

Stable isotopes provide insight into sources and cycling of N compounds in the Sacramento-San Joaquin Delta, California, USA

River deltas and their diverse array of aquatic environments are increasingly impacted by anthropogenic inputs of nitrogen (N). These inputs can alter the N biogeochemistry of these systems and promote undesirable phenomena including harmful algae blooms and invasive aquatic macrophytes. To examine N sources and biogeochemical processes in the Sacramento-San Joaquin Delta, a river delta located in central California, USA, that is fed primarily by the Sacramento River, we utilized a multi-tracer approach that measured N species concentrations and stable isotope values monthly from April 2011 to November 2012 in samples collected from the channelized mainstem of the Sacramento River, two channelized distributaries of the Sacramento River, and the Cache Slough Complex, a network of Sacramento River tributaries and shallow water wetland habitat. We found that the Sacramento River and its channelized distributaries received N primarily in the form of NH 4 + from treated wastewater effluent and that NH 4 + was lost rapidly while NO 3 − was gained more slowly during subsequent downstream transit, driven by an array of biogeochemical processes whose identities could be constrained via examination of stable isotope values. The Cache Slough Complex, which was characterized by lower net flows and higher water residence times than the Sacramento River and its distributaries, received variable inputs of low conductivity water elevated in NH 4 + from the Sacramento River and higher conductivity water elevated in NO 3 − from landward tributaries. Deviations from expected conservative mixing of these sources were spatially variable but broadly indicative of local inputs of treated wastewater effluent NO 3 − , conversion of Sacramento River NH 4 + to NO 3 − via nitrification, uptake of NH 4 + and NO 3 − by phytoplankton, and remineralization of organic N. These findings highlight both the diversity in N dynamics in anthropogenically impacted river delta environments and the utility of a multi-tracer approach in constraining these processes in such complex systems.

California↗

Using mercury and lead stable isotopes to assess mercury, lead, and trace metal source contributions to Great Salt Lake, Utah, USA

Great Salt Lake is a critical habitat for migratory birds that is threatened by elevated metal concentrations, including mercury (Hg) and lead (Pb), and is subject to severe hydrologic changes, such as declining lake level. When assessing metal profiles recorded in Great Salt Lake sediment, a large data gap exists regarding the sources of metals within the system, which is complicated by various source inputs to the lake and complex biogeochemistry. Here, we leverage Hg and Pb stable isotopes to track relative changes in metal source contributions to Great Salt Lake over time. Mercury and Pb concentrations increase in sediments deposited after 1920 and peak between 1965 and 1995, following closure of several local smelters and the onset of increased emission controls. The nominal associations above are confirmed via Hg stable isotopes in pre-1920 background sediments, which reflect atmospheric inputs from regional and global origin, whereas Hg and Pb stable isotopes together indicate that elevated metal concentrations in mid-late 20th century sediments reflect increased mining/smelting inputs. The observed minimal rebound towards pre-1920 Pb isotope signatures in 21st century sediments indicates that mining/smelting inputs, though reduced, remain a primary source of Pb to Great Salt Lake. In contrast, the more pronounced rebound of Hg stable isotope signatures to pre-1920 values indicate a greater contribution of atmospheric inputs of regional/global origin to current Hg inputs, though Hg concentrations are ∼10 times greater than pre-1920 background values due to global increases in atmospheric Hg concentrations or possibly slow recovery from local contamination. The importance of regional/global Hg sources to the system suggests that reductions in Hg bioaccumulation in the open water food webs of Great Salt Lake are more dependent on national and global reductions in Hg emissions and management strategies to limit methylmercury production within system. This work highlights the utility of using coupled Hg and Pb stable isotope values to assess trace metal pollution sources and pathways in aquatic systems.

Utah↗

Temporal variations in parameters reflecting terminal-electron-accepting processes in an aquifer contaminated with waste fuel and chlorinated solvents

A fundamental issue in aquifer biogeochemistry is the means by which solute transport, geochemical processes, and microbiological activity combine to produce spatial and temporal variations in redox zonation. In this paper, we describe the temporal variability of TEAP conditions in shallow groundwater contaminated with both waste fuel and chlorinated solvents. TEAP parameters (including methane, dissolved iron, and dissolved hydrogen) were measured to characterize the contaminant plume over a 3-year period. We observed that concentrations of TEAP parameters changed on different time scales and appear to be related, in part, to recharge events. Changes in all TEAP parameters were observed on short time scales (months), and over a longer 3-year period. The results indicate that (1) interpretations of TEAP conditions in aquifers contaminated with a variety of organic chemicals, such as those with petroleum hydrocarbons and chlorinated solvents, must consider additional hydrogen-consuming reactions (e.g., dehalogenation); (2) interpretations must consider the roles of both in situ (at the sampling point) biogeochemical and solute transport processes; and (3) determinations of microbial communities are often necessary to confirm the interpretations made from geochemical and hydrogeological measurements on these processes.

Michigan↗

Modeling hyporheic zone processes

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics.

Advances in Water Resources↗

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.

Applied Geochemistry↗

Wastewater disposal from unconventional oil and gas development degrades stream quality at a West Virginia injection facility

The development of unconventional oil and gas (UOG) resources has rapidly increased in recent years; however, the environmental impacts and risks are poorly understood. A single well can generate millions of liters of wastewater, representing a mixture of formation brine and injected hydraulic fracturing fluids. One of the most common methods for wastewater disposal is underground injection; we are assessing potential risks of this method through an intensive, interdisciplinary study at an injection disposal facility in West Virginia. In June 2014, waters collected downstream from the site had elevated specific conductance (416 μS/cm) and Na, Cl, Ba, Br, Sr, and Li concentrations, compared to upstream, background waters (conductivity, 74 μS/cm). Elevated TDS, a marker of UOG wastewater, provided an early indication of impacts in the stream. Wastewater inputs are also evident by changes in 87Sr/86Sr in streamwater adjacent to the disposal facility. Sediments downstream from the facility were enriched in Ra and had high bioavailable Fe(III) concentrations relative to upstream sediments. Microbial communities in downstream sediments had lower diversity and shifts in composition. Although the hydrologic pathways were not able to be assessed, these data provide evidence demonstrating that activities at the disposal facility are impacting a nearby stream and altering the biogeochemistry of nearby ecosystems.

Environmental Science & Technology↗

Mercury bioaccumulation in estuarine fishes: Novel insights from sulfur stable isotopes

Estuaries are transitional habitats characterized by complex biogeochemical and ecological gradients that result in substantial variation in fish total mercury concentrations (THg). We leveraged these gradients and used carbon (δ 13 C), nitrogen (δ 15 N), and sulfur (δ 34 S) stable isotopes to examine the ecological and biogeochemical processes underlying THg bioaccumulation in fishes from the San Francisco Bay Estuary. We employed a tiered approach that first examined processes influencing variation in fish THg among wetlands, and subsequently examined the roles of habitat and within-wetland processes in generating larger-scale patterns in fish THg. We found that δ 34 S, an indicator of sulfate reduction and habitat specific-foraging, was correlated with fish THg at all three spatial scales. Over the observed ranges of δ 34 S, THg concentrations in fish increased by up to 860% within wetlands, 560% among wetlands, and 291% within specific impounded wetland habitats. In contrast, δ 13 C and δ 15 N were not correlated with THg among wetlands and were only important in low salinity impounded wetlands, possibly reflecting more diverse food webs in this habitat. Together, our results highlight the key roles of sulfur biogeochemistry and ecology in influencing estuarine fish THg, as well as the importance of fish ecology and habitat in modulating the relationships between biogeochemical processes and Hg bioaccumulation.

California↗

Chitin: 'Forgotten' source of nitrogen: From modern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios

Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of δ 15 N values in chitin. δ 15 N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the δ 15 N value of chitin is indicated by the observation of increasing δ 15 N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence δ 15 N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk δ 15 N values. Hydrous pyrolysis of immature source rocks at 330°C in contact with 15 N-enriched NH 4 Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may partly result from reaction with ammonium-containing pore waters.

ACS Symposium Series↗

Methyl-mercury degradation pathways: A comparison among three mercury impacted ecosystems

We examined microbial methylmercury (MeHg) degradation in sediment of the Florida Everglades, Carson River (NV), and San Carlos Creek (CA), three freshwater environments that differ in the extent and type of mercury contamination and sediment biogeochemistry. Degradation rate constant ( k deg ) values increased with total mercury (Hg t ) contamination both among and within ecosystems. The highest k deg 's (2.8−5.8 d - 1 ) were observed in San Carlos Creek, at acid mine drainage impacted sites immediately downstream of the former New Idria mercury mine, where Hg t ranged from 4.5 to 21.3 ppm (dry wt). A reductive degradation pathway (presumably mer -detoxification) dominated degradation at these sites, as indicated by the nearly exclusive production of 14 CH 4 from 14 C-MeHg, under both aerobic and anaerobic conditions. At the upstream control site, and in the less contaminated ecosystems (e.g. the Everglades), k deg 's were low (≤0.2 d - 1 ) and oxidative demethylation (OD) dominated degradation, as evident from 14 CO 2 production. k deg increased with microbial CH 4 production, organic content, and reduced sulfur in the Carson River system and increased with decreasing pH in San Carlos Creek. OD associated CO 2 production increased with pore-water SO 4 2- in Everglades samples but was not attributable to anaerobic methane oxidation, as has been previously proposed. This ecosystem comparison indicates that severely contaminated sediments tend to have microbial populations that actively degrade MeHg via mer -detoxification, whereas OD occurs in heavily contaminated sediments as well but dominates in those less contaminated.

Environmental Science & Technology↗

Formation of nanocolloidal metacinnabar in mercury-DOM-sulfide systems

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM) −1 ) by combining solid phase extraction using C 18 resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C 18 resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury–sulfur bonds with a longer interatomic distance (2.51–2.53 Å) similar to the mercury–sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg –1 ) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form, and these species need to be considered when addressing mercury biogeochemistry.

Environmental Science & Technology↗

A multiisotope C and N modeling analysis of soil organic matter turnover and transport as a function of soil depth in a California annual grassland soil chronosequence

We examine soil organic matter (SOM) turnover and transport using C and N isotopes in soil profiles sampled circa 1949, 1978, and 1998 (a period spanning pulse thermonuclear 14 C enrichment of the atmosphere) along a 3‐million‐year annual grassland soil chronosequence. Temporal differences in soil Δ 14 C profiles indicate that inputs of recently living organic matter (OM) occur primarily in the upper 20–30 cm but suggest that OM inputs can occur below the primary rooting zone. A three‐pool SOM model with downward transport captures most observed variation in Δ 14 C, percentages of C and N, δ 13 C, and δ 15 N, supporting the commonly accepted concept of three distinct SOM pools. The model suggests that the importance of the decadal SOM pool in N dynamics is greatest in young and old soils. Altered hydrology and possibly low pH and/or P dynamics in highly developed old soils cause changes in soil C and N turnover and transport of importance for soil biogeochemistry models.

Global Biogeochemical Cycles↗

Climate change and Arctic ecosystems: 2. Modeling, paleodata-model comparisons, and future projections

Large variations in the composition, structure, and function of Arctic ecosystems are determined by climatic gradients, especially of growing-season warmth, soil moisture, and snow cover. A unified circumpolar classification recognizing five types of tundra was developed. The geographic distributions of vegetation types north of 55°N, including the position of the forest limit and the distributions of the tundra types, could be predicted from climatology using a small set of plant functional types embedded in the biogeochemistry-biogeography model BIOME4. Several palaeoclimate simulations for the last glacial maximum (LGM) and mid-Holocene were used to explore the possibility of simulating past vegetation patterns, which are independently known based on pollen data. The broad outlines of observed changes in vegetation were captured. LGM simulations showed the major reduction of forest, the great extension of graminoid and forb tundra, and the restriction of low- and high-shrub tundra (although not all models produced sufficiently dry conditions to mimic the full observed change). Mid-Holocene simulations reproduced the contrast between northward forest extension in western and central Siberia and stability of the forest limit in Beringia. Projection of the effect of a continued exponential increase in atmospheric CO 2 concentration, based on a transient ocean-atmosphere simulation including sulfate aerosol effects, suggests a potential for larger changes in Arctic ecosystems during the 21st century than have occurred between mid-Holocene and present. Simulated physiological effects of the CO 2 increase (to >700 ppm) at high latitudes were slight compared with the effects of the change in climate.

Journal of Geophysical Research D: Atmospheres↗

Ca cycling and isotopic fluxes in forested ecosystems in Hawaii

Biogeochemical processes fractionate Ca isotopes in plants and soils along a 4 million year developmental sequence in the Hawaiian Islands. We observed that plants preferentially take up 40Ca relative to 44Ca, and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44Ca in soil exchangeable pools. Our results imply moderate fluxes enriched in 44Ca from strongly nutrient-depleted old soils, in contrast with high 40Ca fluxes in young and little weathered environments. In addition, biological fractionation controls divergent geochemical pathways of Ca and Sr in the plant-soil system. While Ca depletes progressively with increasing soil age, Sr/Ca ratios increase systematically. Sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems, but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial Ca cycle. Ca isotopes in combination with Sr/ Ca ratios reveal more complex processes involved in the biogeochemistry of Ca and Sr. Copyright 2005 by the American Geophysical Union.

Geophysical Research Letters↗

State factor relationships of dissolved organic carbon and nitrogen losses from unpolluted temperate forest watersheds

We sampled 100 unpolluted, old-growth forested watersheds, divided among 13 separate study areas over 5 years in temperate southern Chile and Argentina, to evaluate relationships among dominant soil-forming state factors and dissolved carbon and nitrogen concentrations in watershed streams. These watersheds provide a unique opportunity to examine broad-scale controls over carbon (C) and nitrogen (N) biogeochemistry in the absence of significant human disturbance from chronic N deposition and land use change. Variations in the ratio dissolved organic carbon (DOC) to nitrogen (DON) in watershed streams differed by underlying soil parent material, with average C:N = 29 for watersheds underlain by volcanic ash and basalt versus C:N = 73 for sedimentary and metamorphic parent materials, consistent with stronger adsorption of low C:N hydrophobic materials by amorphous clays commonly associated with volcanic ash and basalt weathering. Mean annual precipitation was related positively to variations in both DOC (range: 0.2-9.7 mg C/L) and DON (range: 0.008-0.135 mg N/L) across study areas, suggesting that variations in water volume and concentration may act synergistically to influence C and N losses across dry to wet gradients in these forest ecosystems. Dominance of vegetation by broadleaf versus coniferous trees had negligible effects on organic C and N concentrations in comparison to abiotic factors. We conclude that precipitation volume and soil parent material are important controls over chemical losses of dissolved organic C and N from unpolluted temperate forest watersheds. Our results raise the possibility that biotic imprints on watershed C and N losses may be less pronounced in naturally N-poor forests than in areas impacted by land use change and chronic N deposition. Copyright 2007 by the American Geophysical Union.

Journal of Geophysical Research G: Biogeosciences↗

Research needs for finely resolved fossil carbon emissions

Scientific research on the global carbon cycle has emerged as a high priority in biogeochemistry, climate studies, and global change policy. The emission of carbon dioxide (CO 2 ) from fossil fuel combustion is a dominant driver of the current net carbon fluxes between the land, the oceans, and the atmosphere, and it is a key contributor to the rise in modern radiative forcing. Contrary to a commonly held perception, our quantitative knowledge about these emissions is insufficient to satisfy current scientific and policy needs. A more highly spatially and temporally resolved quantification of the social and economic drivers of fossil fuel combustion, and the resulting CO 2 emissions, is essential to supporting scientific and policy progress. In this article, a new community of emissions researchers called the CO 2 Fossil Fuel Emission Effort (CO 2 FFEE) outlines a research agenda to meet the need for improved fossil fuel CO 2 emissions information and solicits comment from the scientific community and research agencies.

Eos, Transactions, American Geophysical Union↗