Persistent elevated nitrate in a riparian zone aquifer

Streamside vegetated buffer strips (riparian zones) are often assumed to be zones of ground water nitrate (NO3(-)) attenuation. At a site in southwestern Ontario (Zorra site), detailed monitoring revealed that elevated NO3(-) -N (4-93 mg L(-1)) persisted throughout a 100-m-wide riparian floodplain. Typical of riparian zones, the site has a soil zone of recent river alluvium that is organic carbon (OC) rich (36 +/- 16 g kg(-1)). This material is underlain by an older glacial outwash aquifer with a much lower OC content (2.3 +/- 2.5 g kg(-1). Examination of NO3(-), Cl(-), SO4(2-), and dissolved organic carbon (DOC) concentrations; N/Cl ratios; and NO3(-) isotopic composition (delta15N and delta18O) provides evidence of four distinct NO3(-) source zones within the riparian environment. Denitrification occurs but is incomplete and is restricted to a narrow interval located within ~0.5 m of the alluvium-aquifer contact and to one zone (poultry manure compost zone) where elevated DOC persists from the source. In older ground water close to the river discharge point, denitrification remains insufficient to substantially deplete NO3(-). Overall, denitrification related specifically to the riparian environment is limited at this site. The persistence of NO3(-) in the aquifer at this site is a consequence of its Pleistocene age and resulting low OC content, in contrast to recent fluvial sediments in modern agricultural terrain, which, even if permeable, usually have zones enriched in labile OC. Thus, sediment age and origin are additional factors that should be considered when assessing the potential for riparian zone denitrification.     

Land management impacts on dairy-derived dissolved organic carbon in ground water

Dairy operations have the potential to elevate dissolved organic carbon (DOC) levels in ground water, where it may interact with organic and inorganic contaminants, fuel denitrification, and may present problems for drinking water treatment. Total and percent bioavailable DOC and total and carbon-specific trihalomethane (THM) formation potential (TTHMFP and STHMFP, respectively) were determined for shallow ground water samples from beneath a dairy farm in the San Joaquin Valley, California. Sixteen wells influenced by specific land management areas were sampled over 3 yr. Measured DOC concentrations were significantly elevated over the background as measured at an upgradient monitoring well, ranging from 13 to 55 mg L(-1) in wells downgradient from wastewater ponds, 8 to 30 mg L(-1) in corral wells, 5 to 12 mg L(-1) in tile drains, and 4 to 15 mg L(-1) in wells associated with manured fields. These DOC concentrations were at the upper range or greatly exceeded concentrations in most surface water bodies used as drinking water sources in California. DOC concentrations in individual wells varied by up to a factor of two over the duration of this study, indicating a dynamic system of sources and degradation. DOC bioavailability over 21 d ranged from 3 to 10%, comparable to surface water systems and demonstrating the potential for dairy-derived DOC to influence dissolved oxygen concentrations (nearly all wells were hypoxic to anoxic) and denitrification. TTHMFP measurements across all management units ranged from 141 to 1731 microg L(-1), well in excess of the maximum contaminant level of 80 microg L(-1) established by the Environmental Protection Agency. STHMFP measurements demonstrated over twofold variation ( approximately 4 to approximately 8 mmol total THM/mol DOC) across the management areas, indicating the dependence of reactivity on DOC composition. The results indicate that land management strongly controls the quantity and quality of DOC to reach shallow ground water and hence should be considered when managing ground water resources and in any efforts to mitigate contamination of ground water with carbon-based contaminants, such as pesticides and pharmaceuticals.     

In situ ground water denitrification in stratified, permeable soils underlying riparian wetlands

The ground water denitrification capacity of riparian zones in deep soils, where substantial ground water can flow through low-gradient stratified sediments, may affect watershed nitrogen export. We hypothesized that the vertical pattern of ground water denitrification in riparian hydric soils varies with geomorphic setting and follows expected subsurface carbon distribution (i.e., abrupt decline with depth in glacial outwash vs. negligible decline with depth in alluvium). We measured in situ ground water denitrification rates at three depths (65, 150, and 300 cm) within hydric soils at four riparian sites (two per setting) using a 15N-enriched nitrate "push-pull" method. No significant difference was found in the pattern and magnitude of denitrification when grouping sites by setting. At three sites there was no significant difference in denitrification among depths. Correlations of site characteristics with denitrification varied with depth. At 65 cm, ground water denitrification correlated with variables associated with the surface ecosystem (temperature, dissolved organic carbon). At deeper depths, rates were significantly higher closer to the stream where the subsoil often contains organically enriched deposits that indicate fluvial geomorphic processes. Mean rates ranged from 30 to 120 microg N kg(-1) d(-1) within 10 m versus <1 to 40 microg N kg(-1) d(-1) at >30 m from the stream. High denitrification rates observed in hydric soils, down to 3 m within 10 m of the stream in both alluvial and glacial outwash settings, argue for the importance of both settings in evaluating the significance of riparian wetlands in catchment-scale N dynamics.     

Changes in Labile Organic Carbon Fractions and Soil Enzyme Activities after Marshland Reclamation and Restoration in the Sanjiang Plain in Northeast China

The extensive reclamation of marshland into cropland has tremendously impacted the ecological environment of the Sanjiang Plain in northeast China. To understand the impacts of marshland reclamation and restoration on soil properties, we investigated the labile organic carbon fractions and the soil enzyme activities in an undisturbed marshland, a cultivated marshland and three marshlands that had been restored for 3, 6 and 12?years. Soil samples collected from the different management systems at a depth of 0-20?cm in July 2009 were analyzed for soil organic carbon (SOC), dissolved organic carbon (DOC), microbial biomass carbon (MBC) and easily degradable organic carbon. In addition, the activities of the invertase, β-glucosidase, urease and acid phosphatase were determined. These enzymes are involved in C, N and P cycling, respectively. Long-term cultivation resulted in decreased SOC, DOC, MBC, microbial quotient and C (invertase, β-glucosidase) and N-transforming (urease) enzyme activities compared with undisturbed marshland. After marshland restoration, the MBC and DOC concentrations and the soil invertase, β-glucosidase and urease activities increased. Soil DOC and MBC concentrations are probably the main factors responsible for the different invertase, β-glucosidase and urease activities. In addition, marshland restoration caused a significant increase in the microbial quotient, which reflects enhanced efficiency of organic substrate use by microbial biomass. Our observations demonstrated that soil quality recovered following marshland restoration. DOC, MBC and invertase, β-glucosidase and urease activities were sensitive for discriminating soil ecosystems under the different types of land use. Thus, these parameters should be considered to be indicators for detecting changes in soil quality and environmental impacts in marshlands.     

FOREST‐RIVER INTERACTIONS: INFLUENCE ON HYPORHEIC DISSOLVED ORGANIC CARBON CONCENTRATIONS IN A FLOODPLAIN TERRACE1

ABSTRACT: In large floodplain rivers, hyporheic (subsurface) flow‐paths transfer nutrients from productive riparian terraces to oligotrophic off‐channel habitats. Because dissolved organic carbon (DOC) fuels microbial processes and hyporheic microorganisms represent the first stage of retention and transformation of these nutrients, understanding DOC flux can provide information on the constraints of microbial metabolism in the hyporheic zone of rivers. We monitored hydrology, physicochemical indicators, and dissolved organic carbon (DOC) dynamics during low and high discharge periods in the hyporheic zone of a riparian terrace on the Queets River, Washington, to understand what processes control the supply of carbon to subsurface microbial communities. As discharge increased, terrace hyporheic flowpaths changed from parallel to focused, and the location of surface water inputs to the terrace shifted from the terrace edge to head. Overall, DOC concentrations decreased along hyporheic flowpaths; however, concentrations at points along the flowpaths varied with position along the head gradient and age of the overlying vegetation. We estimated that there is insufficient DOC in adverting surface water to support hyporheic microbial metabolism in this riparian terrace. These trends indicate that there are additional carbon sources to the subsurface water, and we conclude that DOC is leaching from overlying riparian soils within the forest patches. Thus, subsurface DOC concentrations reflect a balance between surface water inputs, metabolic uptake, and allochthonous inputs from forest soils.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Stabilization of composted organic matter after application to a humus-free sandy mining soil

The use of mining substrates for recultivation purposes is limited due to their low organic matter (OM) contents. In a 1-yr laboratory experiment we evaluated the stabilization of biowaste compost added to a humus-free sandy mining soil to examine the suitability of compost amendment for the formation of stable soil organic matter (SOM). The stabilization process was characterized by measuring enrichment of OM and nitrogen in particle size fractions obtained after dispersion with different amounts of energy (ultrasonication and shaking in water), carbon mineralization, and amount of dissolved organic carbon (DOC). During the experiment, 17.1% of the organic carbon (OC) was mineralized. Organic carbon enrichment in the < 20-micron particle size fraction at the beginning of the experiment was in the range of natural soils with similar texture. Within 12 mo, a distinct OC redistribution from coarse into fine fractions was found with both dispersion methods. The accumulation of OC was more pronounced for the size separates obtained by ultrasonication, where the carbon distribution between 0.45- to 20-micron particle size fractions increased from 30% at the beginning to 71% at the end of the experiment. Dissolved organic carbon contents ranged between 50 and 68 g kg-1 OC and decreased during the incubation. In conclusion, the exponential decrease of carbon mineralization and the OC enrichment in the fine particle size fractions both indicated a distinct OM stabilization in the mining soil.     

In situ treatment of metals in contaminated soils with phytate

Batch experiments were conducted to evaluate the ability of various forms of phytate, the hexaphosphoric form of myo-inositol (IP6), to immobilize U, Ni, and other inorganic contaminants in soils and sediments. A Ca-phytate precipitate (Ca(n)-IP6), dodeca sodium-phytate (Na12-IP6), and hydroxyapatite (HA) were added to contaminated soil at rates of 0, 10, 25, and 50 g kg(-1) and equilibrated in 0.001 M CaCl2. The samples were then centrifuged, the solution pH was measured, and the supernatants were filtered prior to analysis for dissolved organic carbon (DOC), U, Ni, P, and other inorganic contaminants, such as As, Cr, Se, and Pb. The residual sediments were air-dried prior to characterization by analytical electron microscopy and extraction with the Toxicity Characteristic Leaching Procedure (TCLP). The solubility of several metals (e.g., U, Pb, Cu) increased with increasing Na12-IP6 when compared with the nonamended control. In some cases immobilization was observed at the lowest Na12-IP6 application rate (10 g kg(-1)) with an increase in solubility observed at the higher rates, demonstrating the importance of metal to ligand ratio. In contrast, Ca(n)-IP6 and HA decreased the solubility of U, Ni, Al, Pb, Ba, Co, Mn, and Zn. For example, soluble U decreased from 2242 to 76 microg kg(-1) and Ni from 58 to 9.6 mg kg with the Ca(n)-IP6 addition, similar to the results observed for HA. Arsenic and Se solubility increased for HA and both forms of IP6, but to a much greater degree for Na12-IP6, suggesting that the increase in pH observed for HA and Na12-IP6, combined with added competition from PO4 and IP6 for sorption sites, resulted in the release of sorbed oxyanion contaminants. The analytical electron microscopy results indicated that metals such as U and Ni were closely associated with secondary Al-rich precipitates in the HA-treated soils, rather than unreacted HA. The analytical electron microscopy results were less definitive for the Ca(n)-IP6-treated soil, although the residual P-containing material was enriched in Al, with lesser amounts of U and Ni.     

Decreased carbon and nutrient input to boreal lakes from particulate organic matter following riparian clear-cutting

The plankton communities of oligotrophic Canadian Shield lakes are strongly regulated by the allochthonous supply of total phosphorus (TP) and dissolved organic carbon (DOC), a proportion of both of which originate from particulate organic matter. Although decreased inputs of allochthonous leaf litter have been documented for small streams whose riparian forests have been removed, no such data exist for boreal lakes. Through estimates of airborne litter input from forested and clear-cut shorelines and laboratory measurements of concentrations released from leaf leachate, we determined that riparian deforestation resulted in reductions of DOC from 17.8 to 0.4 g/m shoreline/yr and of TP from 2.9 to 0.3 g/m shoreline/yr. Previous predictive models indicate that such reductions may be substantial enough to decrease basic metabolic processes of lake plankton communities by as much as 9% in primary production and 17% in respiration.     

Upland disturbance affects headwater stream nutrients and suspended sediments during baseflow and stormflow

Because catchment characteristics determine sediment and nutrient inputs to streams, upland disturbance can affect stream chemistry. Catchments at the Fort Benning Military Installation (near Columbus, Georgia) experience a range of upland disturbance intensities due to spatial variability in the intensity of military training. We used this disturbance gradient to investigate the effects of upland soil and vegetation disturbance on stream chemistry. During baseflow, mean total suspended sediment (TSS) concentration and mean inorganic suspended sediment (ISS) concentration increased with catchment disturbance intensity (TSS: R2= 0.7, p = 0.005, range = 4.0-10.1 mg L(-1); ISS: R2= 0.71, p = 0.004, range = 2.04-7.3 mg L(-1)); dissolved organic carbon (DOC) concentration (R2= 0.79, p = 0.001, range = 1.5-4.1 mg L(-1)) and soluble reactive phosphorus (SRP) concentration (R2= 0.75, p = 0.008, range = 1.9-6.2 microg L(-1)) decreased with increasing disturbance intensity; and ammonia (NH4+), nitrate (NO3-), and dissolved inorganic nitrogen (DIN) concentrations were unrelated to disturbance intensity. The increase in TSS and ISS during storms was positively correlated with disturbance (R2= 0.78 and 0.78, p = 0.01 and 0.01, respectively); mean maximum change in SRP during storms increased with disturbance (r = 0.7, p = 0.04); and mean maximum change in NO3- during storms was marginally correlated with disturbance (r = 0.58, p = 0.06). Soil characteristics were significant predictors of baseflow DOC, SRP, and Ca2+, but were not correlated with suspended sediment fractions, any nitrogen species, or pH. Despite the largely intact riparian zones of these headwater streams, upland soil and vegetation disturbances had clear effects on stream chemistry during baseflow and stormflow conditions.     

Geochemical partitioning of copper, lead, and zinc in benthic, estuarine sediment profiles

The geochemical partitioning of copper (Cu), lead (Pb), and zinc (Zn) was examined in benthic sediment profiles (0- to 20-cm depth interval) composed of relatively coarse (65-90% sand-sized particles), noncohesive, suboxic material (Eh +120 to +260 mV). Total Cu, Pb, and Zn concentrations ranged from 8.3 to 194, 16.3 to 74.8, and 30.1 to 220 mg/kg, respectively, and were related to vertical trends in sediment texture. The observed distribution coefficients describing solid-solution partitioning were in the range of 100 to 1000 L/kg. The geochemical partitioning of solid-phase Cu, Pb, and Zn between six operationally defined fractions was examined with a sequential extraction scheme. The association of Cu, Pb, and Zn with amorphous oxides, crystalline oxides, and organic matter was linearly dependent on the abundance of each respective phase. For retention by amorphous oxide minerals, the observed stoichiometry ranged from 5.2 to 23.7 mg/g for Cu, 12.8 to 21.5 mg/g for Pb, and 23.1 to 85.7 mg/g for Zn. Corresponding values for association with crystalline oxides were an order of magnitude less than those for amorphous oxides, indicating a lesser affinity of trace metals for crystalline oxides. The stoichiometric relationships describing association with organic matter ranged from 17.6 to 54.0 mg/g for Cu, 6.1 to 9.6 mg/g for Pb, and 6.4 to 16.4 mg/g for Zn. The results from this study provide an insight into processes controlling trace metal partitioning in coarse-textured, suboxic, estuarine sediments.     

Spatial and Seasonal Variation of Dissolved Organic Carbon (DOC) Concentrations in Irish Streams: Importance of Soil and Topography Characteristics

Dissolved organic carbon (DOC) concentrations have increased in many sites in Europe and North America in recent decades. High DOC concentrations can damage the structure and functions of aquatic ecosystems by influencing water chemistry. This study investigated the spatial and seasonal variation of DOC concentrations in Irish streams across 55 sites at seven time occasions over 1 year (2006/2007). The DOC concentrations ranged from 0.9 to 25.9 mg/L with a mean value of 6.8 and a median value of 5.7 mg/L and varied significantly over the course of the year. The DOC concentrations from late winter (February: 5.2 ± 3.0 mg/L across 55 sites) and early spring (April: 4.5 ± 3.5 mg/L) had significantly lower DOC concentrations than autumn (October: mean 8.3 ± 5.6 mg/L) and early winter (December: 8.3 ± 5.1 mg/L). The DOC production sources (e.g., litterfall) or the accumulation of DOC over dry periods might be the driving factor of seasonal change in Irish stream DOC concentrations. Analysis of data using stepwise multiple linear regression techniques identified the topographic index (TI, an indication of saturation-excess runoff potential) and soil conditions (organic carbon content and soil drainage characteristics) as key factors in controlling DOC spatial variation in different seasons. The TI and soil carbon content (e.g., soil organic carbon; peat occurrence) are positively related to DOC concentrations, while well-drained soils are negatively related to DOC concentrations. The knowledge of spatial and seasonal variation of DOC concentrations in streams and their drivers are essential for optimum riverine water resources management.     

Mitigation of shallow groundwater nitrate in a poorly drained riparian area and adjacent cropland

Riparian ecosystems, through their unique position in the agricultural landscape and ability to influence nutrient cycles, can potentially reduce NO3 loading to surface and ground waters. The purpose of this study was to determine the fate of NO3 in shallow groundwater moving along a lateral flowpath from a grass seed cropping system through an undisturbed mixed-species herbaceous riparian area. Soil A (30-45 cm) and C horizon (135-150 cm) NO3, dissolved oxygen, and nitrous oxide concentrations were significantly higher in the cropping system than the adjacent riparian area. Nitrate concentrations in both horizons of the riparian soil were consistently at or below 0.05 mg N L(-1) while cropping system concentrations ranged from 1 to 12 mg N L(-1). Chloride data suggested that NO3 dilution occurred from recharge by precipitation. However, a sharp decrease in NO3/Cl ratios as water moved into the riparian area indicated that additional dilution of NO3 concentrations was unlikely. Riparian area A horizon soil water had higher dissolved organic carbon than the cropping system and when the riparian soil became saturated, available electron acceptors (O2, NO3) were rapidly reduced. Dissolved inorganic carbon was significantly higher in the riparian area than the cropping system for both horizons indicating high biological activity. Carbon limitation in the cropping system may have led to microbial respiration using primarily O2 and to a lesser degree NO3. Within 6 m of the riparian/cropping system transition, NO3 was virtually undetectable.     

Nitrate removal in a riparian wetland of the Appalachian Valley and Ridge physiographic province

Riparian zones within the Appalachian Valley and Ridge physiographic province are often characterized by localized variability in soil moisture and organic carbon content, as well as variability in the distribution of soils formed from alluvial and colluvial processes. These sources of variability may significantly influence denitrification rates. This investigation studied the attenuation of nitrate (NO3- -N) as wastewater effluent flowed through the shallow ground water of a forested headwater riparian zone within the Appalachian Valley and Ridge physiographic province. Ground water flow and NO3- -N measurements indicated that NO3- -N discharged to the riparian zone preferentially flowed through the A and B horizons of depressional wetlands located in relic meander scars, with NO3- -N decreasing from > 12 to < 0.5 mg L(-1). Denitrification enzyme activity (DEA) attributable to riparian zone location, soil horizon, and NO3- -N amendments was also determined. Mean DEA in saturated soils attained values as high as 210 microg N kg(-1) h(-1), and was significantly higher than in unsaturated soils, regardless of horizon (p < 0.001). Denitrification enzyme activity in the shallow A horizon of wetland soils was significantly higher (p < 0.001) than in deeper soils. Significant stimulation of DEA (p = 0.027) by N03- -N amendments occurred only in the meander scar soils receiving low NO3- -N (<3.6 mg L(-1)) concentrations. Significant denitrification of high NO3- -N ground water can occur in riparian wetland soils, but DEA is dependent upon localized differences in the degree of soil saturation and organic carbon content.     

Natural uranium and thorium distributions in podzolized soils and native blueberry

Plant uptake of radionuclides is one of many vectors for introduction of contaminants into the human food chain. Thus, it is critical to understand soil-plant relationships that control nuclide bioavailability. Our objectives in this study were to (i) determine the extent of U and Th uptake and cycling by blueberry (Vaccinium pallidum Aiton) in native habitat and (ii) identify the soil properties and processes that contribute most to U and Th bioavailability in this system. We collected composite samples of plant leaves and stems, and samples from surface (AE) horizons and from the upper part of the Bs horizon at two sites. Concentration ratios (CRs) for U and Th were calculated for all plant tissues, using both the AE and Bs horizons as the base. Soil concentrations of U ranged from 16 to 25 microg g(-1), with a mean of 21.1 microg g(-1). Soil concentrations of Th ranged from 14 to 97 microg g(-1), with a mean of 41.8 microg g(-1). Mean U concentrations were 8.65 x 10(-3) microg g(-1) in leaf tissue, and 7.95 x 10(-3) microg g(-1) in stem tissue. Mean Th concentrations were 1.59 x 10(-1) microg g(-1) in leaf tissue, and 9.10 x 10(-2) microg g(-1) in stem tissue. Blueberry plants are cycling both U and Th in this system, with Th cycling occurring to a greater extent than U. In addition, Th was translocated preferentially to plant leaves while U concentrations showed little preferential translocation. Uranium uptake, however, seemed more sensitive than Th uptake to soil properties.     

Potential adverse effects of applying phosphate amendments to immobilize soil contaminants

Seven-day batch equilibrium experiments were conducted to measure the efficacy of four phosphate amendments (trisodium trimetaphosphate [TP3], dodecasodium phytate [Na-IP6], precipitated calcium phytate [Ca-IP6], and hydroxyapatite [HA]) for immobilizing Ni and U in organic-rich sediment. Using the eight-step modified Miller's sequential extraction procedure and the USEPA's Toxicity Characteristic Leaching Procedure, the effect of these amendments on the distribution of Ni and U was assessed. Relative to unamended controls, equilibrium aqueous-phase U concentrations were lower following HA and Ca-IP6 additions but higher following TP3 and Na-IP6 amendments, whereas aqueous Ni concentrations were not decreased only in the Na-IP6 amended treatment relative to the control. The poor rates of contaminant immobilization following TP3 and Na-IP6 amendments correlate with the dispersion of organic matter and organo-mineral colloids, which probably contain sorbed U and Ni. While all amendments shifted the U distribution toward more recalcitrant soil fractions, Ni was redistributed to more labile soil fractions. This study cautions that the addition of orthophosphates and organophosphates as contaminant immobilizing amendments may in fact have adverse effects, especially in high-organic soils. Particular attention is warranted at sites with mixed contaminants with varying geochemical behaviors.     

Differences in Dissolved Organic Carbon and Nitrogen Responses to Storm‐Event and Ground‐Water Conditions in a Forested,Glaciated Watershed in Western New York1

Abstract: Differences in the storm‐event responses of dissolved organic carbon (DOC) and nitrogen (DON) in streamflow and ground water were evaluated for a glaciated forested watershed in western New York. Eight to ten storm events with varying rainfall amounts, intensities, and antecedent moisture conditions were studied for three catchments (1.6, 3.4, and 696 ha) over a three‐year period (2003‐2005). Concentrations of DOC in streamflow exiting the catchments were significantly higher for storm events following a dry period, whereas no similar response was observed for DON. Highest DON concentrations in streamflow were typically associated with storm events following wet antecedent moisture conditions. In addition to antecedent moisture conditions, DOC concentrations were also positively correlated with precipitation amounts, while DON did not reveal a consistent pattern. Streamwater and ground‐water concentrations of DOC during storm events were also strongly correlated with riparian ground‐water depths but a similar relationship was not observed for DON. Ground‐water DON concentrations were also more variable than DOC. We hypothesized that the differences in DOC and DON responses stemmed from the differences in catchment sources of these solutes. This study suggests that while DOC and DON are intrinsically linked as components of dissolved organic matter, their dynamics and exports from watersheds may be regulated by a different set of mechanisms and factors. Identifying these differences is critical for developing more reliable and robust models for transport of dissolved organic matter.     

Accumulation, distribution, and toxicity of copper in sediments of catfish ponds receiving periodic copper sulfate applications

Copper sulfate (CuSO4) is applied periodically to commercial channel catfish (Ictalurus panctatus) ponds as an algicide or parasiticide. Current understanding of the chemistry of copper in soil-water systems suggests that copper may accumulate in pond sediments, although the forms and potential bioavailability of copper in catfish pond sediments are not known. This study investigated the accumulation and distribution of copper in the sediment of catfish ponds receiving periodic additions of CuSO4.5H2O. All ponds were constructed in Sharkey (very-fine, smectitic, thermic Chromic Epiaquert) soil. Nine 0.40-ha ponds received 59 applications of 2.27 kg CuSO4.5H2O per application per pond over 3 yr; no CuSO4.5H2O applications were made to nine additional ponds. Total Cu concentration in the sediments of CuSO4.5H2O-amended catfish ponds (172.5 mg kg(-1)) was four to five times higher than that in the sediments of nonamended ponds (36.1 mg kg(-1)). Copper accumulated in catfish pond sediments at a rate of 41 microg kg(-1) dry sediment for each 1 kg ha(-1) of CuSO4. 5H2O applied to ponds. Copper in the sediments of amended ponds was mainly in the organic matter-bound (30.7%), carbonate-bound (31.8%), and amorphous iron oxide-bound (22.1%) fractions with a considerable fraction (3.4%; 3 to 8 mg kg(-1)) in soluble and exchangeable fractions. This indicates that Cu accumulates differentially in various fractions, with proportionally greater initial accumulation in potentially bioavailable forms. However, toxicity bioassays with amphipods (Hyallela azteca) and common cattail (Typha latifolia L.) indicated that the effect of exposure to amended or nonamended pond sediments was not different.     

GROWTH INHIBITION OF HYDRILLA VERTICILLATA BY SELECTED LAKE SEDIMENT EXTRACTS1

ABSTRACT: Sediments were investigated from two Florida lakes that have not been infested with the submersed, perennial, noxious plant Hydrilla verticillata. Aqueous extracts of the peat-like sediments from these lakes were shown to inhibit the growth of Hydrilla verticillata in laboratory systems. The extracts have substantial concentrations of organic carbon and iron. The apparent molecular weight of the inhibitory fraction is between 2,000 and 10,000, based upon ultrafiltration studies. Hydrilla growth was about 35 percent relative to control for a partially purified fraction at a level of 0.4 ppm organic carbon. Growth was measured as change in biomass (wet and dry) over a one-week period. The inhibitory material was highly fluorescent, dark brown, and inhibitory activity was lost after passage over an anion-exchange column (Cellex-D).     

Immobilization of nickel and other metals in contaminated sediments by hydroxyapatite addition

Batch experiments were conducted to evaluate the ability of hydroxyapatte (HA) to reduce the solubility of metals, including the primary contaminants of concern, Ni and U, from contaminated sediments located on the Department of Energy's Savannah River Site, near Aiken, SC. Hydroxyapatitie was added to the sediments at application rates of 0, 5, 15.8, and 50 g kg-1. After equilibrating in either 0.02 M KCl or 0.01 M CaCl2, the samples were centrifuged and the supernatants filtered prior to metal, dissolved organic C, and PO4 analyses. The treated soils were then air-dried and changes in solid-phase metal distribution were evaluated using sequential extractions and electron-based microanalysis techniques. Hydroxyapatite was effective at reducing the solubility of U and, to a lesser degree, Ni. Hydroxyapatite was also effective in reducing the solubility of Al, Ba, Cd, Co, Mn, and Pb. Sequential extractions indicate that HA transfers such metals from more chemically labile forms, such as the water-soluble and exchangeable fractions, by altering solid-phase speciation in favor of secondary phosphate precipitates. Hydroxyapatite effectiveness was somewhat reduced in the presence of soluble organics that likely increased contaminant metal solubility through complexation. Arsenic and Cr solubility increased with HA addition, suggesting that the increase in pH and competition from PO4 reduced sorption of oxyanion contaminants. Energy dispersive x-ray (EDXA) analysis conducted in the transmission electron microscope (TEM) confirmed that HA amendment sequesters U, Ni, Pb, and possibly other contaminant metals in association with secondary Al-phosphates.