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River nutrient loads and catchment size

We have used a total of 496 sample sites to calibrate a simple regression model for calculating dissolved inorganic nutrient fluxes via runoff to the ocean. The regression uses the logarithms of runoff and human population as the independent variables and estimates the logarithms of dissolved inorganic nitrogen and phosphorus loading with R 2 values near 0.8. This predictive capability is about the same as has been derived for total nutrient loading with process-based models requiring more detailed information on independent variables. We conclude that population and runoff are robust proxies for the more detailed application, landscape modification, and in-stream processing estimated by more process-based models. The regression model has then been applied to a demonstration data set of 1353 river catchments draining to the sea from the North American continent south of the Canadian border. The geographic extents of these basins were extracted from a 1-km digital elevation model for North America, and both runoff and population were estimated for each basin. Most of the basins (72% of the total) are smaller than 103 km2, and both runoff and population density are higher and more variable among small basins than among larger ones.While total load to the ocean can probably be adequately estimated from large systems only, analysis of the geographic distribution of nutrient loading requires consideration of the small basins, which can exhibit significant hydrologic and demographic heterogeneity between systems over their range even within the same geographic region. High-resolution regional and local analysis is necessary for environmental assessment and management. ?? Springer 2005.

Biogeochemistry↗

Dissolved inorganic nitrogen pools and surface flux under different brackish marsh vegetation types, common reed (Phragmites australis) and salt hay (Spartina patens)

The current expansion of Phragmites australis into the high marsh shortgrass (Spartina patens, Distichlis spicata) communities of eastern U.S. salt marshes provided an opportunity to identify the influence of vegetation types on pools and fluxes of dissolved inorganic nitrogen (DIN). Two brackish tidal marshes of the National Estuarine Research Reserve system were examined, Piermont Marsh of the Hudson River NERR in New York and Hog Island in the Jacques Coustaeu NERR of New Jersey. Pools of DIN in porewater and rates of DIN surface flux were compared in replicated pairs of recently-expanded P. australis and neighboring S. patens-dominated patches on the high marsh surface. Both marshes generally imported nitrate (NO3-) and exported ammonium (NH4+), such that overall DIN was exported. No differences in surface exchange of NO3- or NH4+ were observed between vegetation types. Depth-averaged porewater NH4+ concentrations over the entire growing season were 56% lower under P. australis than under S. patens (average 1.4 vs. 3.2 mg NH4+ L-1) with the most profound differences in November. Porewater profiles showed an accumulation of NH4+ at depth in S. patens and constant low concentrations in P. australis from the soil surface to 50 cm depth, with no significant differences in porewater salinity. Despite these profound differences in porewater, NH 4+ diffusion from soils of P. australis and S. patens were not measurably different, were similar to other published rates, and were well below estimated rates based on passive diffusion alone. Rapid adsorption and uptake by litter and microbes in surface soils of both communities may buffer NH4+ loss to flooding tides in both communities, thereby reducing the impact of P. australis invasion on NH4+ flux to flooding waters. ?? Springer 2005.

Biogeochemistry↗

Effects of watershed land use on nitrogen concentrations and δ 15 nitrogen in groundwater

Eutrophication is a major agent of change affecting freshwater, estuarine, and marine systems. It is largely driven by transportation of nitrogen from natural and anthropogenic sources. Research is needed to quantify this nitrogen delivery and to link the delivery to specific land-derived sources. In this study we measured nitrogen concentrations and δ 15 N values in seepage water entering three freshwater ponds and six estuaries on Cape Cod, Massachusetts and assessed how they varied with different types of land use. Nitrate concentrations and δ 15 N values in groundwater reflected land use in developed and pristine watersheds. In particular, watersheds with larger populations delivered larger nitrate loads with higher δ 15 N values to receiving waters. The enriched δ 15 N values confirmed nitrogen loading model results identifying wastewater contributions from septic tanks as the major N source. Furthermore, it was apparent that N coastal sources had a relatively larger impact on the N loads and isotopic signatures than did inland N sources further upstream in the watersheds. This finding suggests that management priorities could focus on coastal sources as a first course of action. This would require management constraints on a much smaller population.

Massachusetts↗

NO gas loss from biologically crusted soils in Canyonlands National Park, Utah

In this study, we examined N gas loss as nitric oxide (NO) from N-fixing biologically crusted soils in Canyonlands National Park, Utah. We hypothesized that NO gas loss would increase with increasing N fixation potential of the biologically crusted soil. NO fluxes were measured from biologically crusted soils with three levels of N fixation potential (Scytonema-Nostoc-Collema spp. (dark)>Scytonema-Nostoc-Microcoleus spp. (medium)>Microcoleus spp. (light)) from soil cores and field chambers. In both cores and field chambers there was a significant effect of crust type on NO fluxes, but this was highly dependent on season. NO fluxes from field chambers increased with increasing N fixation potential of the biologically crusted soils (dark>medium>light) in the summer months, with no differences in the spring and autumn. Soil chlorophyllasis Type a content (an index of N fixation potential), percent N, and temperature explained 40% of the variability in NO fluxes from our field sites. Estimates of annual NO loss from dark and light crusts was 0.04-0.16 and 0.02-0.11-N/ha/year. Overall, NO gas loss accounts for approximately 3-7% of the N inputs via N fixation in dark and light biologically crusted soils. Land use practices have drastically altered biological soil crusts communities over the past century. Livestock grazing and intensive recreational use of public lands has resulted in a large scale conversion of dark cyanolichen crusts to light cyanobacterial crusts. As a result, changes in biologically crusted soils in arid and semi-arid regions of the western US may subsequently impact regional NO loss. ?? Springer 2005.

Biogeochemistry↗

Impacts of biological soil crust disturbance and composition on C and N loss from water erosion

In this study, we conducted rainfall simulation experiments in a cool desert ecosystem to examine the role of biological soil crust disturbance and composition on dissolved and sediment C and N losses. We compared runoff and sediment C and N losses from intact late-successional dark cyanolichen crusts (intact) to both trampled dark crusts (trampled) and dark crusts where the top 1 cm of the soil surface was removed (scraped). In a second experiment, we compared C and N losses in runoff and sediments in early-successional light cyanobacterial crusts (light) to that of intact late-successional dark cyanolichen crusts (dark). A relatively high rainfall intensity of approximately 38 mm per 10-min period was used to ensure that at least some runoff was generated from all plots. Losses of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and ammonium (NH 4+ ) were significantly higher from trampled plots as compared to scraped and intact plots. Sediment C and N losses, which made up more than 98% of total nutrient losses in all treatments, were more than 4-fold higher from trampled plots relative to intact plots (sediment C g/m2, intact = 0.74, trampled = 3.47; sediment N g/m2, intact = 0.06, trampled = 0.28). In light crusts, DOC loss was higher relative to dark crusts, but no differences were observed in dissolved N. Higher sediment loss in light crusts relative to dark crusts resulted in 5-fold higher loss of sediment-bound C and N. Total C flux (sediment + dissolved) was on the order of 0.9 and 7.9 g/m2 for dark and light crusts, respectively. Sediment N concentration in the first minutes after runoff from light crusts was 3-fold higher than the percent N of the top 1 cm of soil, suggesting that even short-term runoff events may have a high potential for N loss due to the movement of sediments highly enriched in N. Total N loss from dark crusts was an order of magnitude lower than light crusts (dark = 0.06 g N/m2, light = 0.63 g/m2). Overall, our results from the small plot scale (0.5 m2) suggest that C and N losses are much lower from intact late-successional cyanolichen crusts as compared to recently disturbed or early-successional light cyanobacterial crusts. ?? Springer 2006.

Biogeochemistry↗

Effect of reduced winter precipitation and increased temperature on watershed solute flux, 1988-2002, Northern Michigan

Since 1987 we have studied weekly change in winter (December-April) precipitation, snowpack, snowmelt, soil water, and stream water solute flux in a small (176-ha) Northern Michigan watershed vegetated by 65-85 year-old northern hardwoods. Our primary study objective was to quantify the effect of change in winter temperature and precipitation on watershed hydrology and solute flux. During the study winter runoff was correlated with precipitation, and forest soils beneath the snowpack remained unfrozen. Winter air temperature and soil temperature beneath the snowpack increased while precipitation and snowmelt declined. Atmospheric inputs declined for H+, NO 3- , NH 4+ , dissolved inorganic nitrogen (DIN), and SO 42- . Replicated plot-level results, which could not be directly extrapolated to the watershed scale, showed 90% of atmospheric DIN input was retained in surface shallow (<15 cm deep) soils while SO 42- flux increased 70% and dissolved organic carbon (DOC) 30-fold. Most stream water base cation (C B), HCO 3- , and Cl- concentrations declined with increased stream water discharge, K+, NO 3- , and SO 42- remained unchanged, and DOC and dissolved organic nitrogen (DON) increased. Winter stream water solute outputs declined or were unchanged with time except for NO 3- and DOC which increased. DOC and DIN outputs were correlated with the percentage of winter runoff and stream discharge that occurred when subsurface flow at the plot-level was shallow (<25 cm beneath Oi). Study results suggest that the percentage of annual runoff occurring as shallow lateral subsurface flow may be a major factor regulating solute outputs and concentrations in snowmelt-dominated ecosystems. ?? Springer 2006.

Biogeochemistry↗

Tracing sources of streamwater sulfate during snowmelt using S and O isotope ratios of sulfate and 35S activity

The biogeochemical cycling of sulfur (S) was studied during the 2000 snowmelt at Sleepers River Research Watershed in northeastern Vermont, USA using a hydrochemical and multi-isotope approach. The snowpack and 10 streams of varying size and land use were sampled for analysis of anions, dissolved organic carbon (DOC), 35 S activity, and δ 34 S and δ 18 O values of sulfate. At one of the streams, δ 18 O values of water also were measured. Apportionment of sulfur derived from atmospheric and mineral sources based on their distinct δ 34 S values was possible for 7 of the 10 streams. Although mineral S generally dominated, atmospheric-derived S contributions exceeded 50% in several of the streams at peak snowmelt and averaged 41% overall. However, most of this atmospheric sulfur was not from the melting snowpack; the direct contribution of atmospheric sulfate to streamwater sulfate was constrained by 35 S mass balance to a maximum of 7%. Rather, the main source of atmospheric sulfur in streamwater was atmospheric sulfate deposited months to years earlier that had microbially cycled through the soil organic sulfur pool. This atmospheric/pedospheric sulfate (pedogenic sulfate formed from atmospheric sulfate) source is revealed by δ 18 O values of streamwater sulfate that remained constant and significantly lower than those of atmospheric sulfate throughout the melt period, as well as streamwater 35 S ages of hundreds of days. Our results indicate that the response of streamwater sulfate to changes in atmospheric deposition will be mediated by sulfate retention in the soil.

Vermont↗

Solute sources in stream water during consecutive fall storms in a northern hardwood forest watershed: A combined hydrological, chemical and isotopic approach

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO 3 − (δ 15 N and δ 18 O) and SO 4 2− (δ 34 S and δ 18 O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14–18, 18.5 mm; Storm 2: Sept. 21–24, 33 mm; Storm 3: Sept. 27–29, 42.9 mm; Storm 4: Oct. 16–21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in C b (sum of base cations), Si, NO 3 − , and SO 4 2− , DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO 4 2− and NO 3 − . There was a strong inverse relationship between SO 4 2− concentrations and δ 34 S values suggesting the importance of S biogeochemical redox processes in contributing to SO 4 2− export. The isotopic composition of NO 3 − in stream water indicated that this N had been microbially processed. Linkages between SO 4 2− and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO 3 − suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change.

Biogeochemistry↗

Soil respiration in the cold desert environment of the Colorado Plateau (USA): Abiotic regulators and thresholds

Decomposition is central to understanding ecosystem carbon exchange and nutrient-release processes. Unlike mesic ecosystems, which have been extensively studied, xeric landscapes have received little attention; as a result, abiotic soil-respiration regulatory processes are poorly understood in xeric environments. To provide a more complete and quantitative understanding about how abiotic factors influence soil respiration in xeric ecosystems, we conducted soil- respiration and decomposition-cloth measurements in the cold desert of southeast Utah. Our study evaluated when and to what extent soil texture, moisture, temperature, organic carbon, and nitrogen influence soil respiration and examined whether the inverse-texture hypothesis applies to decomposition. Within our study site, the effect of texture on moisture, as described by the inverse texture hypothesis, was evident, but its effect on decomposition was not. Our results show temperature and moisture to be the dominant abiotic controls of soil respiration. Specifically, temporal offsets in temperature and moisture conditions appear to have a strong control on soil respiration, with the highest fluxes occurring in spring when temperature and moisture were favorable. These temporal offsets resulted in decomposition rates that were controlled by soil moisture and temperature thresholds. The highest fluxes of CO 2 occurred when soil temperature was between 10 and 16 °C and volumetric soil moisture was greater than 10%. Decomposition-cloth results, which integrate decomposition processes across several months, support the soil-respiration results and further illustrate the seasonal patterns of high respiration rates during spring and low rates during summer and fall. Results from this study suggest that the parameters used to predict soil respiration in mesic ecosystems likely do not apply in cold-desert environments.

Utah↗

Does biofilm contribute to diel cycling of Zn in High Ore Creek, Montana?

Concentrations of metals cycle daily in the water column of some mining-impacted streams in the Rocky Mountains of the western USA. We hypothesized that biofilm in High Ore Creek, Montana, USA, sorbs and releases Zn on a diel cycle, and this uptake-and-release cycle controls the total and dissolved (0.45-μm filtered) Zn concentrations. We collected water samples from three sites (upstream, middle and downstream at 0, 350 and 650 m, respectively) along a 650-m reach of High Ore Creek during a 47-h period in August 2002 and from the upstream and downstream sites during a 24-h period in August 2003; we also collected biofilm samples at these sites. In 2002 and 2003, total and dissolved Zn concentrations did not exhibit a diel cycle at the upstream sampling site, which was ~30 m downstream from a settling pond through which the creek flows. However, total and dissolved Zn concentrations exhibited a diel cycle at the middle and downstream sampling sites, with the highest Zn concentrations occurring at dawn and the lowest Zn concentrations occurring during late afternoon (>2-fold range of concentrations at the downstream site). Based on (1) concentrations of Zn in biofilm at the three sites and (2) results of streamside experiments that demonstrated Zn uptake and release by naïve biofilm during the light and dark hours of a photocycle, respectively, we conclude that Zn uptake in photosynthetic biofilms could contribute a large percentage to the cycling of Zn concentrations in the water column in High Ore Creek.

Montana↗

Soluble reactive phosphorus transport and retention in tropical, rainforest streams draining a volcanic and geothermally active landscape in Costa Rica.: Long-term concentration patterns, pore water environment and response to ENSO events

Soluble reactive phosphorus (SRP) transport/retention was determined at four sites in three rainforest streams draining La Selva Biological Station, Costa Rica. La Selva is located at the base of the last remaining intact rainforest transect from 30 m above sea level to 3000 m along the entire Caribbean slope of Central America. Steam SRP levels can be naturally high there due to regional, geothermal groundwater discharged at ambient temperature. Monitoring since 1988 has revealed distinctive long-term differences in background SRP and total P (TP) for three streams in close proximity, and identified the impact of ENSO (El Nino Southern Oscillation) events on SRP-enriched reaches. Mean interannual SRP concentrations (?? standard deviation) were 89 ?? 53??g/l in the Salto (1988-1996), 21 ?? 39??g/l in the Pantano (1988-1998), and 26 ?? 35??g/l in the Sabalo (1988-1996). After January, 1997 the separate upland-lowland contributions to discharge and SRP load were determined monthly in the Salto. SRP in Upper Salto was low (19 ?? 8??g/l, 1997-2002) until enriched at the upland-lowland transition by regional groundwater. Mean SRP concentration in Lower Salto (108 ?? 104??g/l) was typically highest February-April, the driest months, and lowest July-September, the wettest. SRP concentration was positively correlated to the inverse of discharge in Lower Salto when ENSO data were omitted (1992 and 1998-1999), but not in the Upper Salto, Pantano, or Sabalo. TP was positively correlated to the inverse of discharge in all three streams when ENSO data were omitted. High SRP springs and seeps along the Lower Salto contributed 36% of discharge but 85% of SRP export 1997-2001. Annual SRP flux from the total Salto watershed (1997-2001) averaged 2.9 kg/ha year, but only 0.6 kg/ha year from the Upper Salto. A dye tracer injection showed that pore water environments were distinctly different between Upper and Lower Salto. Upper Salto had high surface water-pore water exchange, high dissolved oxygen, low SRP, and low conductivity similar to surface water, and Lower Salto had low surface water-pore water exchange, low dissolved oxygen, high SRP, and high conductivity reflecting geothermal groundwater influence. SRP export from the Salto was controlled by regional groundwater transfer, which in similar volcanic settings could be a significant P source. However, ENSO events modified the SRP concentration in the Salto suggesting that long-term monitoring is required to understand underlying SRP dynamics and P flux to downstream communities. ?? 2006 Springer Science+Business Media, Inc.

Biogeochemistry↗

Soluble reactive phosphorus (SRP) transport and retention in tropical, rain forest streams draining a volcanic landscape in Costa Rica: In situ SRP amendment to streams and laboratory studies

Soluble reactive phosphorus (SRP) transport/retention was determined in two rain forest streams (Salto, Pantano) draining La Selva Biological Station, Costa Rica. There, SRP levels can be naturally high due to groundwater enriched by geothermal activity within the surfically dormant volcanic landscape, and subsequently discharged at ambient temperature. Combined field and laboratory approaches simulated high but natural geothermal SRP input with the objective of estimating the magnitude of amended SRP retention within high and low SRP settings and determining the underlying mechanisms of SRP retention. First, we examined short-term SRP retention/transport using combined SRP-conservative tracer additions at high natural in situ concentrations. Second, we attempted to observe a DIN response during SRP amendment as an indicator of biological uptake. Third, we determined SRP release/retention using laboratory sediment assays under control and biologically inhibited conditions. Short-term in situ tracer-SRP additions indicated retention in both naturally high and low SRP reaches. Retention of added SRP mass in Upper Salto (low SRP) was 17% (7.5 mg-P m-2 h-1), and 20% (10.9 mg-P m-2 h -1) in Lower Salto (high SRP). No DIN response in either nitrate or ammonium was observed. Laboratory assays using fresh Lower Salto sediments indicated SRP release (15.4 ?? 5.9 ??g-P g dry wt.-1 h -1), when incubated in filter sterilized Salto water at ambient P concentration, but retention when incubated in filter sterilized river water amended to 2.0 mg SRP l-1 (233.2 ?? 5.8 ??g-P g dry wt. -1 h-1). SRP uptake/release was similar in both control- and biocide-treated sediments indicating predominantly abiotic retention. High SRP retention even under biologically saturated conditions, absence of a DIN response to amendment, patterns of desorption following amendment, and similar patterns of retention and release under control and biologically inhibited conditions all indicated predominantly abiotic P flux. ?? 2006 Springer Science+Business Media, Inc.

Biogeochemistry↗

Factors controlling soil water and stream water aluminum concentrations after a clearcut in a forested watershed with calcium-poor soils

The 24 ha Dry Creek watershed in the Catskill Mountains of southeastern New York State USA was clearcut during the winter of 1996-1997. The interactions among acidity, nitrate (NO3- ), aluminum (Al), and calcium (Ca2+) in streamwater, soil water, and groundwater were evaluated to determine how they affected the speciation, solubility, and concentrations of Al after the harvest. Watershed soils were characterized by low base saturation, high exchangeable Al concentrations, and low exchangeable base cation concentrations prior to the harvest. Mean streamwater NO3- concentration was about 20 ??mol l-1 for the 3 years before the harvest, increased sharply after the harvest, and peaked at 1,309 ??mol l -1 about 5 months after the harvest. Nitrate and inorganic monomeric aluminum (Alim) export increased by 4-fold during the first year after the harvest. Alim mobilization is of concern because it is toxic to some fish species and can inhibit the uptake of Ca2+ by tree roots. Organic complexation appeared to control Al solubility in the O horizon while ion exchange and possibly equilibrium with imogolite appeared to control Al solubility in the B horizon. Alim and NO3- concentrations were strongly correlated in B-horizon soil water after the clearcut (r2 = 0.96), especially at NO3- concentrations greater than 100 ??mol l-1. Groundwater entering the stream from perennial springs contained high concentrations of base cations and low concentrations of NO3- which mixed with acidic, high Alim soil water and decreased the concentration of Alim in streamwater after the harvest. Five years after the harvest soil water NO 3- concentrations had dropped below preharvest levels as the demand for nitrogen by regenerating vegetation increased, but groundwater NO3- concentrations remained elevated because groundwater has a longer residence time. As a result streamwater NO3- concentrations had not fallen below preharvest levels, even during the growing season, 5 years after the harvest because of the contribution of groundwater to the stream. Streamwater NO3- and Alim concentrations increased more than reported in previous forest harvesting studies and the recovery was slower likely because the watershed has experienced several decades of acid deposition that has depleted initially base-poor soils of exchangeable base cations and caused long-term acidification of the soil. ?? 2007 Springer Science+Business Media B.V.

Biogeochemistry↗

Decomposition of soil organic matter from boreal black spruce forest: Environmental and chemical controls

Black spruce forests are a dominant covertype in the boreal forest region, and they inhabit landscapes that span a wide range of hydrologic and thermal conditions. These forests often have large stores of soil organic carbon. Recent increases in temperature at northern latitudes may be stimulating decomposition rates of this soil carbon. It is unclear, however, how changes in environmental conditions influence decomposition in these systems, and if substrate controls of decomposition vary with hydrologic and thermal regime. We addressed these issues by investigating the effects of temperature, moisture, and organic matter chemical characteristics on decomposition of fibric soil horizons from three black spruce forest sites. The sites varied in drainage and permafrost, and included a “Well Drained” site where permafrost was absent, and “Moderately well Drained” and “Poorly Drained” sites where permafrost was present at about 0.5 m depth. Samples collected from each site were incubated at five different moisture contents (2, 25, 50, 75, and 100% saturation) and two different temperatures (10°C and 20°C) in a full factorial design for two months. Organic matter chemistry was analyzed using pyrolysis gas chromatography-mass spectrometry prior to incubation, and after incubation on soils held at 20°C, 50% saturation. Mean cumulative mineralization, normalized to initial carbon content, ranged from 0.2% to 4.7%, and was dependent on temperature, moisture, and site. The effect of temperature on mineralization was significantly influenced by moisture content, as mineralization was greatest at 20°C and 50–75% saturation. While the relative effects of temperature and moisture were similar for all soils, mineralization rates were significantly greater for samples from the “Well Drained” site compared to the other sites. Variations in the relative abundances of polysaccharide-derivatives and compounds of undetermined source (such as toluene, phenol, 4-methyl phenol, and several unidentifiable compounds) could account for approximately 44% of the variation in mineralization across all sites under ideal temperature and moisture conditions. Based on our results, changes in temperature and moisture likely have similar, additive effects on in situ soil organic matter (SOM) decomposition across a wide range of black spruce forest systems, while variations in SOM chemistry can lead to significant differences in decomposition rates within and among forest sites.

Biogeochemistry↗

Groundwater nutrient concentrations near an incised midwestern stream: Effects of floodplain lithology and land management

It has been recognized that subsurface lithology plays an important role in controlling nutrient cycling and transport in riparian zones. In Iowa and adjacent states, the majority of alluvium preserved in small and moderate sized valleys consists of Holocene-age organic-rich, and fine-grained loam. In this paper, we describe and evaluate spatial and temporal patterns of lithology and groundwater nutrient concentrations at a riparian well transect across Walnut Creek at the Neal Smith National Wildlife Refuge in Jasper County, Iowa. Land treatment on one side of the stream reduced the grass cover to bare ground and allowed assessment of the effects of land management on nutrient concentrations. Results indicated that groundwater in Holocene alluvium is very nutrient rich with background concentrations of nitrogen, phosphorus and dissolved organic carbon that exceed many environmentally sensitive criteria. Average concentrations of ammonium exceeded 1 mg/l in several wells under grass cover whereas nitrate concentrations exceeded 20 mg/l in wells under bare ground. Phosphate concentrations ranged from 0.1 to 1.3 mg/l and DOC concentrations exceeded 5 mg/l in many wells. Denitrification, channel incision, land management and geologic age of alluvium were found to contribute to variable nutrient loading patterns at the site. Study results indicated that riparian zones of incised streams downcutting through nutrient-rich Holocene alluvium can potentially be a significant source of nutrient loadings to streams. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗

Nitrogen attenuation in the Connecticut River, northeastern USA; a comparison of mass balance and N2 production modeling approaches

Two methods were used to measure in-stream nitrogen loss in the Connecticut River during studies conducted in April and August 2005. A mass balance on nitrogen inputs and output for two study reaches (55 and 66 km), at spring high flow and at summer low flow, was computed on the basis of total nitrogen concentrations and measured river discharges in the Connecticut River and its tributaries. In a 10.3 km subreach of the northern 66 km reach, concentrations of dissolved N2 were also measured during summer low flow and compared to modeled N2 concentrations (based on temperature and atmospheric gas exchange rates) to determine the measured "excess" N2 that indicates denitrification. Mass balance results showed no in-stream nitrogen loss in either reach during April 2005, and no nitrogen loss in the southern 55 km study reach during August 2005. In the northern 66 km reach during August 2005, however, nitrogen output was 18% less than the total nitrogen inputs to the reach. N2 sampling results gave an estimated rate of N2 production that would remove 3.3% of the nitrogen load in the river over the 10.3 km northern sub-reach. The nitrogen losses measured in the northern reach in August 2005 may represent an approximate upper limit for nitrogen attenuation in the Connecticut River because denitrification processes are most active during warm summer temperatures and because the study was performed during the annual low-flow period when total nitrogen loads are small. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗

Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation

The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/ 40Ca ratios (expressed as ??44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root-soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (??44Ca ???-3.95???). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least ??44Ca values and leaf litter the greatest. An approximately 2??? difference in ??44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗

Changes in the character of DOC in streams during storms in two Midwestern watersheds with contrasting land uses

Dissolved organic carbon (DOC) dynamics in streams is important, yet few studies focus on DOC dynamics in Midwestern streams during storms. In this study, stream DOC dynamics during storms in two Midwestern watersheds with contrasting land uses, the change in character of stream DOC during storms, and the usability of DOC as a hydrologic tracer in artificially drained landscapes of the Midwest are investigated. Major cation/DOC concentrations, and DOC specific UV absorbance (SUVA) and fluorescence index (FI) were monitored at 2-4 h intervals during three spring storms. Although DOC is less aromatic in the mixed land use watershed than in the agricultural watershed, land use has little impact on stream DOC concentration during storms. For both watersheds, DOC concentration follows discharge, and SUVA and FI values indicate an increase in stream DOC aromaticity and lignin content during storms. The comparison of DOC/major cation flushing dynamics indicates that DOC is mainly exported via overland flow/macropore flow. In both watersheds, the increase in DOC concentration in the streams during storms corresponds to a shift in the source of DOC from DOC originating from mineral soil layers of the soil profile at baseflow, to DOC originating from surficial soil layers richer in aromatic substances and lignin during storms. Results also suggest that DOC, SUVA and FI could be used as hydrologic tracers in artificially drained landscapes of the Midwest. These results underscore the importance of sampling streams for DOC during high flow periods in order to understand the fate of DOC in streams. ?? 2008 Springer Science+Business Media B.V.

Biogeochemistry↗