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System controls on the aqueous distribution of mercury in the northern Florida Everglades

The forms and partitioning of aqueous mercury species in the canals and marshes of the Northern Florida Everglades exhibit strong spatial and temporal variability. In canals feeding Water Conservation Area (WCA) 2A, unfiltered total Hg (HgT(U)) is less than 3 ng L-1 and relatively constant. In contrast, methyl mercury (MeHg) exhibited a strong seasonal pattern, with highest levels entering WCA-2A marshes during July. Stagnation and reduced flows also lead to particle enrichment of MeHg. In the marshes of WCA-2A, 2B and 3A, HgT(U) is usually <5 ng L-1 with no consistent north-south patterns. However, for individual dates, aqueous unfiltered MeHg (MeHg(U)) levels increase from north to south with generally lowest levels in the eutrophied regions of northern WCA-2A. A strong relationship between filtered Hg species and dissolved organic carbon (DOC), evident for rivers draining wetlands in Wisconsin, was not apparent in the Everglades, suggesting either differences in the binding sites of DOC between the two regions, or non-organic Hg complexation in the Everglades.

Biogeochemistry↗

Diel variability of mercury phase and species distributions in the Florida Everglades

Preliminary studies of mercury (Hg) cycling in the Everglades revealed that dissolved gaseous mercury (DGM), total mercury (Hg(T)), and reactive mercury (Hg(R)) show reproducible, diel trends. Peak water-column DGM concentrations were observed on or about noon, with a 3 to 7 fold increase over night-time concentrations. Production of DGM appears to cease during dark periods, with nearly constant water column concentrations that were at or near saturation with respect to the overlying air. A simple mass balance shows that the flux of Hg to the atmosphere from diel DGM production and evasion represents about 10% of the annual input from atmospheric deposition. Production of DGM is likely the result of an indirect photolysis reaction that involves the production of reductive species and/or reduction by electron transfer. Diel variability in Hg(T) and Hg(R) appears to be controlled by two factors: inputs from rainfall and photolytic sorption/desorption processes. A possible mechanism involves photolysis of chromophores on the surface of a solid substrate (e.g., the periphyton mat) giving rise to destabilization of sorbed mercury and net desorption during daylight. At night, the sorption reactions predominate and the water-column Hg(T) decreases. Methylmercury (MeHg) also showed diel trends in concentration but were not clearly linked to the solar cycle or rainfall at the study site.

Biogeochemistry↗

Inorganic nitrogen and microbial biomass dynamics before and during spring snowmelt

Recent work in seasonally snow covered ecosystems has identified thawed soil and high levels of heterotrophic activity throughout the winter under consistent snow cover. We performed measurements during the winter of 1994 to determine how the depth and timing of seasonal snow cover affect soil microbial populations, surface water NO3/- loss during snowmelt, and plant N availability early in the growing season. Soil under early accumulating, consistent snow cover remained thawed during most of the winter and both microbial biomass and soil inorganic N pools gradually increased under the snowpack. At the initiation of snowmelt, microbial biomass N pools increased from 3.0 to 5.9 g N m-2, concurrent with a decrease in soil inorganic N pools. During the latter stages of snowmelt, microbial biomass N pools decreased sharply without a concurrent increase in inorganic N pools or significant leaching losses. In contrast, soil under inconsistent snow cover remained frozen during most of the winter. During snowmelt, microbial biomass initially increased from 1.7 to 3.1 g N m-2 and then decreased as sites became snow-free. In contrast to smaller pool sizes, NO3/-export during snowmelt from the inconsistent snow cover sites of 1.14 (??0.511) g N m-2 was significantly greater (p < 0.001) than the 0.27 (??0.16) g N m-2 exported from sites with consistent snow cover. These data suggest that microbial biomass in consistently snow-covered soil provides a significant buffer limiting the export of inorganic N to surface water during snowmelt. However, this buffer is very sensitive to changes in snowpack regime. Therefore, interannual variability in the timing and depth of snowpack accumulation may explain the year to year variability in inorganic N concentrations in surface water these ecosystems.

Biogeochemistry↗

The hyporheic zone as a source of dissolved organic carbon and carbon gases to a temperate forested stream

The objective of this study was to examine chemical changes in porewaters that occur over small scales (cm) as groundwater flows through the hyporheic zone and discharges to a stream in a temperate forest of northern Wisconsin. Hyporheic-zone porewaters were sampled at discrete depths of 2, 10, 15, 61, and 183 cm at three study sites in the study basin. Chemical profiles of dissolved organic carbon (DOC), CO2, CH4, and pH show dramatic changes between 61 cm sediment depth and the water-sediment interface. Unless discrete samples at small depth intervals are taken, these chemical profiles are not accounted for. Similar trends were observed at the three study locations, despite each site having very different hydraulic-flow regimes. Increases in DOC concentration by an order of magnitude from 61 to 15 cm depth with a corresponding decrease in pH and rapid decreases in the molecular weight of the DOC suggest that aliphatic compounds (likely organic acids) are being generated in the hyporheic zone. Estimated efflux rates of DOC, CO2, and CH4 to the stream are 6.2, 0.79, 0.13 moles m2 d-1, respectively, with the vast majority of these materials produced in the hyporheic zone. Very little of these materials are accounted for by sampling stream water, suggesting rapid uptake and/or volatilization.

Biogeochemistry↗

Nitrogen solutes in an Adirondack forested watershed: Importance of dissolved organic nitrogen

Nitrogen (N) dynamics were evaluated from 1 June 1995 through 31 May 1996 within the Arbutus Lake watershed in the Adirondack Mountains of New York State, U.S.A. At the Arbutus Lake outlet dissolved organic nitrogen (DON), NO3/- and NH4/+ contributed 61%, 33%, and 6% respectively, to the total dissolved nitrogen (TDN) flux (259 mol ha-1 yr-1). At the lake inlet DON, NO3/-, and NH4/+ constituted 36%, 61%, and 3% respectively, of TDN flux (349 mol ha-1 yr-1). Differences between the factors that control DON, NO3/-, and NH4+ stream water concentrations were evaluated using two methods for estimating annual N flux at the lake inlet. Using biweekly sampling NO3/- and NH4/+ flux was 10 and 4 mol ha-1 yr-1 respectively, less than flux estimates using biweekly plus storm and snowmelt sampling. DON flux was 18 mol ha-1 yr-1 greater using only biweekly sampling. These differences are probably not of ecological significance relative to the total flux of N from the watershed (349 mol ha-1 yr-1). Dissolved organic N concentrations were positively related to discharge during both the dormant (R2 = 0.31; P<0.01) and growing season (R2= 0.09; P<0.01). There was no significant relationship between NO3/- concentration and discharge during the dormant season, but a significant negative relationship was found during the growing season (R2 = 0.29; P<0.01). Biotic controls in the growing season appeared to have had a larger impact on stream water NO3- concentrations than on DON concentrations. Arbutus Lake had a major impact on stream water N concentrations of the four landscape positions sampled, suggesting the need to quantify within lake processes to interpret N solute losses and patterns in watershed-lake systems.

Biogeochemistry↗

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = -0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = -0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = -0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.

Biogeochemistry↗

Volcano fixes nitrogen into plant-available forms

Hawaiian montane ecosystems developing on recent tephra deposits contain more fixed nitrogen than conventional sources can explain. Heath and Huebert (1999) demonstrated that cloud water interception is the mechanism by which this extra nitrogen is deposited, but could not identify its source. We show here that atmospheric dinitrogen is fixed at the surface of active lava flows, producing concentrations of NO which are higher than those found in most urban rush hour air pollution. Over a period of hours this NO is blown away from the island and oxidized to nitrate. Interruptions in the trade wind flow can return this nitrate to the island to be deposited in cloud water. Thus, fixation on active lava flows is able to provide nitrogen to developing ecosystems on flows emplaced earlier.

Biogeochemistry↗

Modeling the effects of snowpack on heterotrophic respiration across northern temperate and high latitude regions: Comparison with measurements of atmospheric carbon dioxide in high latitudes

Simulations by global terrestrial biogeochemical models (TBMs) consistently underestimate the concentration of atmospheric carbon dioxide (CO2) at high latitude monitoring stations during the nongrowing season. We hypothesized that heterotrophic respiration is underestimated during the nongrowing season primarily because TBMs do not generally consider the insulative effects of snowpack on soil temperature. To evaluate this hypothesis, we compared the performance of baseline and modified versions of three TBMs in simulating the seasonal cycle of atmospheric CO2 at high latitude CO2 monitoring stations; the modified version maintained soil temperature at 0 ??C when modeled snowpack was present. The three TBMs include the Carnegie-Ames-Stanford Approach (CASA), Century, and the Terrestrial Ecosystem Model (TEM). In comparison with the baseline simulation of each model, the snowpack simulations caused higher releases of CO2 between November and March and greater uptake of CO2 between June and August for latitudes north of 30??N. We coupled the monthly estimates of CO2 exchange, the seasonal carbon dioxide flux fields generated by the HAMOCC3 seasonal ocean carbon cycle model, and fossil fuel source fields derived from standard sources to the three-dimensional atmospheric transport model TM2 forced by observed winds to simulate the seasonal cycle of atmospheric CO2 at each of seven high latitude monitoring stations, in comparison to the CO2 concentrations simulated with the baseline fluxes of each TBM, concentrations simulated using the snowpack fluxes are generally in better agreement with observed concentrations between August and March at each of the monitoring stations. Thus, representation of the insulative effects of snowpack in TBMs generally improves simulation of atmospheric CO2 concentrations in high latitudes during both the late growing season and nongrowing season. These simulations highlight the global importance of biogeochemical processes during the nongrowing season in estimating carbon balance of ecosystems in northern high and temperate latitudes.

Biogeochemistry↗

Atmospheric deposition and watershed nitrogen export along an elevational gradient in the Catskill Mountains, New York

Cumulative effects of atmospheric N deposition may increase N export from watersheds and contribute to the acidification of surface waters, but natural factors (such as forest productivity and soil drainage) that affect forest N cycling can also control watershed N export. To identify factors that are related to stream-water export of N, elevational gradients in atmospheric deposition and natural processes were evaluated in a steep, first-order watershed in the Catskill Mountains of New York, from 1991 to 1994. Atmospheric deposition of SO4/2-, and probably N, increased with increasing elevation within this watershed. Stream-water concentrations of SO4/2- increased with increasing elevation throughout the year, whereas stream-water concentrations of NO3/- decreased with increasing elevation during the winter and spring snowmelt period, and showed no relation with elevation during the growing season or the fall. Annual export of N in stream water for the overall watershed equaled 12% to 17% of the total atmospheric input on the basis of two methods of estimation. This percentage decreased with increasing elevation, from about 25% in the lowest subwatershed to 7% in the highest subwatershed; a probable result of an upslope increase in the thickness of the surface organic horizon, attributable to an elevational gradient in temperature that slows decomposition rates at upper elevations. Balsam fir stands, more prevalent at upper elevations than lower elevations, may also affect the gradient of subwatershed N export by altering nitrification rates in the soil. Variations in climate and vegetation must be considered to determine how future trends in atmospheric deposition will effect watershed export of nitrogen.

Biogeochemistry↗

Dissolved organic nitrogen budgets for upland, forested ecosystems in New England

Relatively high deposition of nitrogen (N) in the northeastern United States has caused concern because sites could become N saturated. In the past, mass-balance studies have been used to monitor the N status of sites and to investigate the impact of increased N deposition. Typically, these efforts have focused on dissolved inorganic forms of N (DIN = NH4-N + NO3-N) and have largely ignored dissolved organic nitrogen (DON) due to difficulties in its analysis. Recent advances in the measurement of total dissolved nitrogen (TDN) have facilitated measurement of DON as the residual of TDN - DIN. We calculated DON and DIN budgets using data on precipitation and streamwater chemistry collected from 9 forested watersheds at 4 sites in New England. TDN in precipitation was composed primarily of DIN. Net retention of TDN ranged from 62 to 89% (4.7 to 10 kg ha-1 yr-1) of annual inputs. DON made up the majority of TDN in stream exports, suggesting that inclusion of DON is critical to assessing N dynamics even in areas with large anthropogenic inputs of DIN. Despite the dominance of DON in streamwater, precipitation inputs of DON were approximately equal to outputs. DON concentrations in streamwater did not appear significantly influenced by seasonal biological controls, but did increase with discharge on some watersheds. Streamwater NO3-N was the only fraction of N that exhibited a seasonal pattern, with concentrations increasing during the winter months and peaking during snowmelt runoff. Concentrations of NO3-N varied considerably among watersheds and are related to DOC:DON ratios in streamwater. Annual DIN exports were negatively correlated with streamwater DOC:DON ratios, indicating that these ratios might be a useful index of N status of upland forests.

Biogeochemistry↗

Chemical and optical changes in freshwater dissolved organic matter exposed to solar radiation

We studied the chemical and optical changes inthe dissolved organic matter (DOM) from twofreshwater lakes and a Sphagnum bog afterexposure to solar radiation. Stable carbonisotopes and solid-state 13 C-NMR spectraof DOM were used together with optical andchemical data to interpret results fromexperimental exposures of DOM to sunlight andfrom seasonal observations of two lakes innortheastern Pennsylvania. Solar photochemicaloxidation of humic-rich bog DOM to smaller LMWcompounds and to DIC was inferred from lossesof UV absorbance, optical indices of molecularweight and changes in DOM chemistry. Experimentally, we observed a 1.2‰ enrichment in δ 13 $C and a 47% loss in aromaticC functionality in bog DOM samples exposed tosolar UVR. Similar results were observed inthe surface waters of both lakes. In latesummer hypolimnetic water in humic LakeLacawac, we observed 3 to 4.5‰enrichments in δ 13 C and a 30% increase inaromatic C relative to early spring valuesduring spring mixing. These changes coincidedwith increases in molecular weight and UVabsorbance. Anaerobic conditions of thehypolimnion in Lake Lacawac suggest thatmicrobial metabolism may be turning overallochthonous C introduced during springmixing, as well as autochthonous C. Thismetabolic activity produces HMW DOM during thesummer, which is photochemically labile andisotopically distinct from allochthonous DOM orautochthonous DOM. These results suggest bothphotooxidation of allochthonous DOM in theepilimnion and autotrophic production of DOM bybacteria in the hypolimnion cause seasonaltrends in the UV absorbance of lakes.

Biogeochemistry↗

A comparison of models for estimating the riverine export of nitrogen from large watersheds

We evaluated the accuracy of six watershed models of nitrogen export in streams (kg km2 yr-1) developed for use in large watersheds and representing various empirical and quasi-empirical approaches described in the literature. These models differ in their methods of calibration and have varying levels of spatial resolution and process complexity, which potentially affect the accuracy (bias and precision) of the model predictions of nitrogen export and source contributions to export. Using stream monitoring data and detailed estimates of the natural and cultural sources of nitrogen for 16 watersheds in the northeastern United States (drainage sizes = 475 to 70,000 km2), we assessed the accuracy of the model predictions of total nitrogen and nitrate-nitrogen export. The model validation included the use of an error modeling technique to identify biases caused by model deficiencies in quantifying nitrogen sources and biogeochemical processes affecting the transport of nitrogen in watersheds. Most models predicted stream nitrogen export to within 50% of the measured export in a majority of the watersheds. Prediction errors were negatively correlated with cultivated land area, indicating that the watershed models tended to over predict export in less agricultural and more forested watersheds and under predict in more agricultural basins. The magnitude of these biases differed appreciably among the models. Those models having more detailed descriptions of nitrogen sources, land and water attenuation of nitrogen, and water flow paths were found to have considerably lower bias and higher precision in their predictions of nitrogen export.

Biogeochemistry↗

Allocation of extracellular enzymatic activity in relation to litter composition, N deposition, and mass loss

Decomposition of plant material is a complex process that requires interaction among a diversity of microorganisms whose presence and activity is subject to regulation by a wide range of environmental factors. Analysis of extracellular enzyme activity (EEA) provides a way to relate the functional organization of microdecomposer communities to environmental variables. In this study, we examined EEA in relation to litter composition and nitrogen deposition. Mesh bags containing senescent leaves of Quercus borealis (red oak), Acer rubrum (red maple) and Cornus florida (flowering dogwood) were placed on forest floor plots in southeastern New York. One-third of the plots were sprayed monthly with distilled water. The other plots were sprayed monthly with NH4NO3 solution at dose rates equivalent to 2 or 8 g N m-2 y-1. Mass loss, litter composition, fungal mass, and the activities of eight enzymes were measured on 13 dates for each litter type. Dogwood was followed for one year, maple for two, oak for three, For each litter type and treatment, enzymatic turnover activities were calculated from regressions of LN (%mass remaining) vs. cumulative activity. The decomposition of dogwood litter was more efficient than that of maple and oak. Maple litter had the lowest fungal mass and required the most enzymatic work to decompose, even though its mass loss rate was twice that of oak. Across litter types, N amendment reduced apparent enzymatic efficiencies and shifted EEA away from N acquisition and toward P acquisition, and away from polyphenol oxidation and toward polysaccharide hydrolysis. The effect of these shifts on decomposition rate varied with litter composition: dogwood was stimulated, oak was inhibited and maple showed mixed effects. The results show that relatively small shifts in the activity of one or two critical enzymes can significantly alter decomposition rates.

Biogeochemistry↗

Cycling of beryllium and carbon through hillslope soils in Iowa

Isotopes of Be and C were used to reconstruct loess accumulation, hillslope evolution, and agricultural modification in soils of western Iowa. While both elements are derived from additions by the atmosphere (via plants in the case of carbon), the differences in element cycling allow erosional and depositional processes to be separated from biochemical processing. Based on 10Be, loess accumulation likely occurred simultaneously with hillslope degradation. Rates of loess accumulation declined five-fold between early stages (late Pleistocene and early Holocene) and later stages (late Holocene) of accumulation, but the absolute timing of accumulation requires independent dating methods. Based on 14C measurements, plant inputs and decomposition are significant near the surface, but below 1-1.5 m carbon inputs are minimal and decomposition is nearly arrested. The amount of carbon below 1.5 m is constant (0.1%) and is composed of soil organic matter that was buried by loess. Agricultural modification results in a dramatic redistribution of 10Be through soil erosion and deposition. By contrast, the redistribution of soil organic matter is masked by the rapid cycling of C through the topsoil as it continually decomposes and is replaced by plant inputs.

Biogeochemistry↗

Nitrogen vs. phosphorus limitation across an ecotonal gradient in a mangrove forest

Mangrove forests are characterized by distinctive tree-height gradients that reflect complex spatial, within-stand differences in environmental factors, including nutrient dynamics, salinity, and tidal inundation, across narrow gradients. To determine patterns of nutrient limitation and the effects of nutrient availability on plant growth and within-stand nutrient dynamics, we used a factorial experiment with three nutrient treatment levels (control, N, P) and three zones along a tree-height gradient (fringe, transition, dwarf) on offshore islands in Belize. Transects were laid out perpendicular to the shoreline across a mangrove forest from a fringe stand along the seaward edge, through a stand of intermediate height, into a dwarf stand in the interior of the island. At three sites, three trees were fertilized per zone for 2 yr. Although there was spatial variability in response, growth by R. mangle was generally nitrogen (N) -limited in the fringe zone; phosphorus (P) -limited in the dwarf zone; and, N- and/or P-limited in the transition zone. Phosphorus-resorption efficiency decreased in all three zones, and N-resorption efficiency increased in the dwarf zone in response to P enrichment. The addition of N had no effect on either P or N resorption efficiencies. Belowground decomposition was increased by P enrichment in all zones, whereas N enrichment had no effect. This study demonstrated that essential nutrients are not uniformly distributed within mangrove ecosystems; that soil fertility can switch from conditions of N to P limitation across narrow ecotonal gradients; and, that not all ecological processes respond similarly to, or are limited by, the same nutrient.

Biogeochemistry↗

Controls of streamwater dissolved inorganic carbon dynamics in a forested watershed

I investigated controls of stream dissolved inorganic carbon (DIC) sources and cycling along a stream size and productivity gradient in a temperate forested watershed in northern California. Dissolved CO2 (CO2 (aq)) dynamics in heavily shaded streams contrasted strongly with those of larger, open canopied sites. In streams with canopy cover > 97%, CO2 (aq) was highest during baseflow periods (up to 540 ??M) and was negatively related to discharge. Effects of algal photosynthesis on CO2 (aq) were minimal and stream CO2 (aq) was primarily controlled by groundwater CO2 (aq) inputs and degassing losses to the atmosphere. In contrast to the small streams. CO2 (aq) in larger, open-canopied streams was often below atmospheric levels at midday during baseflow and was positively related to discharge. Here, stream CO2 (aq) was strongly influenced by the balance between autotrophic and heterotrophic processes. Dynamics of HCO3- were less complex. HCO3- and Ca2+ were positively correlated, negatively related to discharge, and showed no pattern with stream size. Stable carbon isotope ratios of DIC (i.e. ??13C DIC) increased with stream size and discharge, indicating contrasting sources of DIC to streams and rivers. During summer baseflows, ??13C DIC were 13C-depleted in the smallest streams (minimum of -17.7???) due to the influence of CO2 (aq) derived from microbial respiration and HCO3- derived from carbonate weathering. ??13C DIC were higher (up to -6.6???) in the larger streams and rivers due to invasion of atmospheric CO2 enhanced by algal CO2 (aq) uptake. While small streams were influenced by groundwater inputs, patterns in CO2 (aq) and evidence from stable isotopes demonstrate the strong influence of stream metabolism and CO2 exchange with the atmosphere on stream and river carbon cycles.

Biogeochemistry↗

Mechanisms underlying export of N from high-elevation catchments during seasonal transitions

Mechanisms underlying catchment export of nitrogen (N) during seasonal transitions (i.e., winter to spring and summer to autumn) were investigated in high-elevation catchments of the Sierra Nevada using stable isotopes of nitrate and water, intensive monitoring of stream chemistry and detailed catchment N-budgets. We had four objectives: (1) determine the relative contribution of snowpack and soil nitrate to the spring nitrate pulse, (2) look for evidence of biotic control of N losses at the catchment scale, (3) examine dissolved organic nitrogen (DON) export patterns to gain a better understanding of the biological and hydrological controls on DON loss, and (4) examine the relationship between soil physico-chemical conditions and N export. At the Emerald Lake watershed, nitrogen budgets and isotopic analyses of the spring nitrate pulse indicate that 50 to 70% of the total nitrate exported during snowmelt (ca. April to July) is derived from catchment soils and talus; the remainder is snowpack nitrate. The spring nitrate pulse occurred several weeks after the start of snowmelt and was different from export patterns of less biologically labile compounds such as silica and DON suggesting that: (1) nitrate is produced and released from soils only after intense flushing has occurred and (2) a microbial N-sink is operating in catchment soils during the early stages of snowmelt. DON concentrations varied less than 20-30% during snowmelt, indicating that soil processes tightly controlled DON losses.

Biogeochemistry↗