Denitrification in alluvial wetlands in an urban landscape

Riparian wetlands have been shown to be effective "sinks" for nitrate N (NO3-), minimizing the downstream export of N to streams and coastal water bodies. However, the vast majority of riparian denitrification research has been in agricultural and forested watersheds, with relatively little work on riparian wetland function in urban watersheds. We investigated the variation and magnitude of denitrification in three constructed and two relict oxbow urban wetlands, and in two forested reference wetlands in the Baltimore metropolitan area. Denitrification rates in wetland sediments were measured with a 15N-enriched NO3- "push-pull" groundwater tracer method during the summer and winter of 2008. Mean denitrification rates did not differ among the wetland types and ranged from 147 +/- 29 microg N kg soil(-1) d(-1) in constructed stormwater wetlands to 100 +/- 11 microg N kg soil(-1) d(-1) in relict oxbows to 106 +/- 32 microg N kg soil(-1) d(-1) in forested reference wetlands. High denitrification rates were observed in both summer and winter, suggesting that these wetlands are sinks for NO3- year round. Comparison of denitrification rates with NO3- standing stocks in the wetland water column and stream NO3- loads indicated that mass removal of NO3- in urban wetland sediments by denitrification could be substantial. Our results suggest that urban wetlands have the potential to reduce NO3- in urban landscapes and should be considered as a means to manage N in urban watersheds.     

Nitrification and denitrification rates of Everglades wetland soils along a phosphorus-impacted gradient

Little information is available on the effect of phosphorus (P) enrichment on nitrogen (N) biogeochemical cycling in wetland soil. Of particular importance are the coupled nitrification-denitrification reactions that regulate the microbially mediated loss of N from wetland systems. Soils from the northern Florida Everglades have been affected by P loading from surface waters over the past 40 years. Elevated P levels have been show to have an effect on the size and activity of the microbial pool and a decrease in the N to P ratio of the microbial biomass. The objective of the study was to determine if P enrichment in soils affected microbial activities related to nitrification and denitrification in these flooded, peat soils. Potential nitrification rates of soil and detritus were determined using constantly stirred reactors under aerobic conditions while denitrification rates were determined from anaerobic incubations of slurry. Nitrification rates showed two distinct linear phases, a slower initial rate, signifying activity of nitrifiers present, followed by a sharp increase in the NH4+ conversion rate indicative of maximum potential rates. Initial rates of nitrification were highest in the surficial detrital layer decreasing with soil depth and did not correlate to soil total P. The potential rates of nitrification were 13 times greater than the initial rates. Potential denitrification rates were highest in the detritus and 0- to 10-cm soil interval with significantly lower values in the 10- to 30-cm soil interval, significantly correlated to total P of the soil. A significant (P < 0.01) relationship was seen between potential denitrification rates and soil total P suggesting an increased rate of N removal from P-enriched regions of the northern Everglades.     

Isotopic evidence of nitrate sources and denitrification in the Mississippi River, Illinois

Anthropogenic nitrate (NO3-) within the Mississippi-Atchafalaya River basin and discharge to the Gulf of Mexico has been linked to serious environmental problems. The sources of this NO3- have been estimated by others using mass balance methods; however, there is considerable uncertainty in these estimates. Part of the uncertainty is the degree of denitrification that the NO3- has undergone. The isotopic composition of NO3- in the Mississippi River adjacent to Illinois and tile drain (subsurface drain) discharge in agricultural areas of east-central Illinois was examined using N and O isotopes to help identify the major sources of NO3- and assess the degree of denitrification in the samples. The isotopic evidence suggests that most of the NO3- in the river is primarily derived from synthetic fertilizers and soil organic N, which is consistent with published estimates of N inputs to the Mississippi River. The 1:2 relationship between delta18O and delta15N also indicate that, depending on sample location and season, NO3- in the river and tile drains has undergone significant denitrification, ranging from about 0 to 55%. The majority of the denitrification appears to have occurred before discharge into the Mississippi River.     

Collateral geochemical impacts of agricultural nitrogen enrichment from 1963 to 1985: a southern Wisconsin ground water depth profile

In this study, we used chlorofluorocarbon (CFC) age-dating to investigate the geochemistry of N enrichment within a bedrock aquifer depth profile beneath a south central Wisconsin agricultural landscape. Measurement of N(2)O and excess N(2) allowed us to reconstruct the total NO(3)(-) and total nitrogen (TN) leached to ground water and was essential for tracing the separate influences of soil nitrification and ground water denitrification in the collateral geochemical chronology. We identify four geochemical impacts due to a steady ground water N enrichment trajectory (39 +/- 2.2 micromol L(-1) yr(-1), r(2) = 0.96) over two decades (1963-1985) of rapidly escalating N use. First, as a by-product of soil nitrification, N(2)O entered ground water at a stable (r(2) = 0.99) mole ratio of 0.24 +/- 0.007 mole% (N(2)O-N/NO(3)-N). The gathering of excess N(2)O in ground water is a potential concern relative to greenhouse gas emissions and stratospheric ozone depletion after it discharges to surface water. Second, excess N(2) measurements revealed that NO(3)(-) was a prominent, mobile, labile electron acceptor comparable in importance to O(2.) Denitrification transformed 36 +/- 15 mole% (mol mol(-1) x 100) of the total N within the profile to N(2) gas, delaying exceedance of the NO(3)(-) drinking water standard by approximately 6 yr. Third, soil acids produced from nitrification substantially increased the concentrations of major, dolomitic ions (Ca, Mg, HCO(3)(-)) in ground water relative to pre-enrichment conditions. By 1985, concentrations approximately doubled; by 2006, CFC age-date projections suggest concentrations may have tripled. Finally, the nitrification induced mobilization of Ca may have caused a co-release of P from Ca-rich soil surfaces. Dissolved P increased from an approximate background value of 0.02 mg L(-1) in 1963 to 0.07 mg L(-1) in 1985. The CFC age-date projections suggest the concentration could have reached 0.11 mg L(-1) in ground water recharge by 2006. These results highlight an intersection of the N and P cycles potentially important for managing the quality of ground water discharged to surface water.     

Denitrification potential in urban riparian zones

Denitrification, the anaerobic microbial conversion of nitrate (NO3-) to nitrogen (N) gases, is an important process contributing to the ability of riparian zones to function as "sinks" for NO3- in watersheds. There has been little analysis of riparian zones in urban watersheds despite concerns about high NO3- concentrations in many urban streams. Vegetation and soils in urban ecosystems are often highly disturbed, and few studies have examined microbial processes like denitrification in these ecosystems. In this study, we measured denitrification potential and a suite of related microbial parameters (microbial biomass carbon [C] and N content, potential net N mineralization and nitrification, soil inorganic N pools) in four rural and four urban riparian zones in the Baltimore, MD metropolitan area. Two of the riparian zones were forested and two had herbaceous vegetation in each land use context. There were few differences between urban and rural and herbaceous and forest riparian zones, but variability was much higher in urban than rural sites. There were strong positive relationships between soil moisture and organic matter content and denitrification potential. Given the importance of surface runoff in urban watersheds, the high denitrification potential of the surface soils that we observed suggests that if surface runoff can be channeled through areas with high denitrification potential (e.g., stormwater detention basins with wetland vegetation), these areas could function as important NO3- sinks in urban watersheds.     

Selenium stable isotope investigation into selenium biogeochemical cycling in a lacustrine environment: Sweitzer Lake, Colorado

We present a comprehensive set of Se concentration and isotope ratio data collected over a 3-yr period from dissolved, sediment-hosted, and organically bound Se in a Se-contaminated lake and littoral wetland. Median isotope ratios of these various pools of Se spanned a narrow isotopic range (delta80/76Se(SRM-3149)) = 1.14-2.40 per thousand). Selenium (VI) reduction in the sediments is an important process in this system, but its isotopic impact is muted by the lack of direct contact between surface waters and reduction sites within sediments. This indicates that using Se isotope data as an indicator of microbial or abiotic Se oxyanion reduction is not effective in this or other similar systems. Isotopic data suggest that most Se(IV) in the lake originates from oxidation of organically bound Se rather than directly through Se(VI) reduction. Mobilization of Se(VI) from bedrock involves only a slight isotopic shift. Temporally constant isotopic differences observed in Se(VI) from two catchment areas suggest the potential for tracing Se(VI) from different source areas. Phytoplankton isotope ratios are close to those of the water, with a small depletion in heavy isotopes (0.56 per thousand). Fish tissues nearly match the phytoplankton, being only slightly depleted in the heavier isotopes. This suggests the potential for Se isotopes as migration indicators. Volatile, presumably methylated Se was isotopically very close to median values for phytoplankton and macrophytes, indicating a lack of isotopic fractionation during methylation.     

Mechanisms of nutrient attenuation in a subsurface flow riparian wetland

Riparian wetlands are transition zones between terrestrial and aquatic environments that have the potential to serve as nutrient filters for surface and ground water due to their topographic location. We investigated a riparian wetland that had been receiving intermittent inputs of NO3- and PO4(3-) during storm runoff events to determine the mechanisms of nutrient attenuation in the wetland soils. Few studies have shown whether infrequent pulses of NO3- are sufficient to maintain substantial denitrifying communities. Denitrification rates were highest at the upstream side of the wetland where nutrient-rich runoff first enters the wetland (17-58 microg N2O-N kg soil(-1) h(-1)) and decreased further into the wetland. Carbon limitation for denitrification was minor in the wetland soils. Samples not amended with dextrose had 75% of the denitrification rate of samples with excess dextrose C. Phosphate sorption isotherms suggested that the wetland soils had a high capacity for P retention. The calculated soil PO4(3-) concentration that would yield an equilibrium aqueous P04(3-) concentration of 0.05 mg P L(-1) was found to be 100 times greater than the soil PO4(3-) concentration at the time of sampling. This indicated that the wetland could retain a large additional mass of PO4(3-) without increasing the dissolved P04(3-) concentrations above USEPA recommended levels for lentic waters. These results demonstrated that denitrification can be substantial in systems receiving pulsed NO3- inputs and that sorption could account for extensive PO4(3-) attenuation observed at this site.     

Tracing nitrate transport and environmental impact from intensive swine farming using delta nitrogen-15

Natural-abundance delta15N showed that nitrate generated from commercial land application of swine (Sus scrofa domesticus) waste within a North Carolina Coastal Plain catchment was being discharged to surface waters by ground water passing beneath the sprayfields and adjacent riparian buffers. This was significant because intensive swine farms in North Carolina are considered non-discharge operations, and riparian buffers with minimum widths of 7.6 m (25 ft) are the primary regulatory control on ground water export of nitrate from these operations. This study shows that such buffers are not always adequate to prevent discharge of concentrated nitrate in ground water from commercial swine farms in the Mid-Atlantic Coastal Plain, and that additional measures are required to ensure non-discharge conditions. The median delta15N-total N of liquids in site swine waste lagoons was +15.4 +/- 0.2% vs. atmospheric nitrogen. The median delta15N-NO3 values of shallow ground water beneath and adjacent to site sprayfields, a stream draining sprayfields, and waters up to 1.5 km downstream were + 15.3 +/- 0.2 to + 15.4 +/- 0.2%. Seasonal and spatial isotopic variations in lagoons and well waters were greatly homogenized during ground water transport and discharge to streams. Neither denitrification nor losses of ammonia during spraying significantly altered the bulk ground water delta15N signal being delivered to streams. The lagoons were sources of chloride and potassium enrichment, and shallow ground water showed strong correlation between nitrate N, potassium, and chloride. The 15N-enriched nitrate in ground water beneath swine waste sprayfields can thus be successfully traced during transport and discharge into nearby surface waters.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

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.     

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.     

Denitrification in anaerobic lagoons used to treat swine wastewater

Anaerobic lagoons are commonly used for the treatment of swine wastewater. Although these lagoons were once thought to be relatively simple, their physical, chemical, and biological processes are very complex. This study of anaerobic lagoons had two objectives: (i) to quantify denitrification enzyme activity (DEA) and (ii) to evaluate the influence of lagoon characteristics on the DEA. The DEA was measured by the acetylene inhibition method. Wastewater samples and physical and chemical measurements were taken from the wastewater column of nine anaerobic swine lagoons from May 2006 to May 2009. These lagoons were typical for anaerobic swine lagoons in the Carolinas relative to their size, operation, and chemical and physical characteristics. Their mean value for DEA was 87 mg N2O-N m(-3) d(-1). In a lagoon with 2-m depth, this rate of DEA would be compatible with 1.74 kg N ha(-1) d(-1) When nonlimiting nitrate was added, the highest DEA was compatible with 4.38 kg N ha(-1) d(-1) loss. Using stepwise regression for this treatment, the lagoon characteristics (i.e., soluble organic carbon, total nitrogen, temperature, and NO3-N) provided a final step model R2 of 0.69. Nitrous oxide from incomplete denitrification was not a significant part of the system nitrogen balance. Although alternate pathways of denitrification may exist within or beneath the wastewater column, this paper documents the lack of sufficient denitrification enzyme activity within the wastewater column of these anaerobic lagoons to support large N2 gas losses via classical nitrification and denitrification.     

A method to quantitatively trap volatilized organoselenides for stable selenium isotope analysis

If volatile organoselenides are to be analyzed for their stable Se isotope composition to elucidate sources and formation processes, organoselenides need to be trapped quantitatively to avoid artificial Se isotope fractionation. We developed an efficient trap of organoselenides to be used in microcosms designed to determine the Se isotope fractionation by microbial transformation of inorganic Se to volatile organoselenides. The recoveries of volatilized dimethyldiselenide (DMDSe) from aqueous standard solutions by activated charcoal and alkaline peroxide solution with subsequent freeze-drying and purification via a cation exchange resin were tested. Microcosm experiments with the Se-methylating fungus in a growth medium were conducted, and tightness of the microcosm was assessed by comparing mass balances of total Se of the fungus, medium, and trapped organoselenides with the supplied Se mass. At the end of the experiment, we calculated δSe values of the whole microcosm and compared them with the δSe value of supplied Se(IV) and Se(VI). Our results demonstrated that activated charcoal cannot be used for quantitative trapping of organoselenides because generally <64% of the outgassed DMDSe were recovered. The mean recovery of Se volatilized from an aqueous DMDSe standard trapped in alkaline peroxide, in contrast, was 96 ± 11% (SD) after 2 h ( = 4). The mass balances of total Se in microcosm experiments with alkaline peroxide traps run for 11 to 15 d were 96 ± 15 and 102 ± 2.4% for Se(IV) and Se(VI) ( = 3), respectively. The mass-weighted mean δSe values for the Se(IV) and Se(VI) batch experiments were -0.31 ± 0.05‰ ( = 3) and -0.76 ± 0.07‰ ( = 3), compared with -0.20 ± 0.10‰ and -0.69 ± 0.10‰ in the supplied Se oxyanions, respectively. We conclude that the alkaline peroxide trap can reliably be used to determine the Se isotope composition of organoselenides.     

Evaluation of nitrate nitrogen fluxes from a tile-drained watershed in central Iowa

Nitrate N fluxes from tile-drained watersheds have been implicated in water quality studies of the Mississippi River basin, but actual NO3-N loads from small watersheds during long periods are poorly documented. We evaluated discharge and NO3-N fluxes passing the outlet of an Iowa watershed (5134 ha) and two of its tile-drained subbasins (493 and 863 ha) from mid-1992 through 2000. The cumulative NO3-N load from the catchment was 168 kg ha(-1), and 176 and 229 kg ha(-1) from the subbasins. The outlet had greater total discharge (1831 mm) and smaller flow-weighted mean NO3-N concentration (9.2 mg L(-1)) than the subbasins, while the larger subbasin had greater discharge (1712 vs. 1559 mm) and mean NO3-N concentration (13.4 vs. 11.3 mg L(-1)) than the smaller subbasin. Concentrations exceeding 10 mg L(-1) were common, but least frequent at the outlet. Nitrate N was generally not diluted by large flows, except during 1993 flooding. The outlet showed smaller NO3-N concentrations at low flows. Relationships between discharge and NO3-N flux showed log-log slopes near 1.0 for the subbasins, and 1.2 for the outlet, considering autocorrelation and measurement-error effects. We estimated denitrification of subbasin NO3-N fluxes in a hypothetical wetland using published data. Assuming that temperature and NO3-N supply could limit denitrification, then about 20% of the NO3-N would have been denitrified by a wetland constructed to meet USDA-approved criteria. The low efficiency results from the seasonal timing and NO3-N content of large flows. Therefore, agricultural and wetland best management practices (BMPs) are needed to achieve water quality goals in tile-drained watersheds.     

Transport and fate of nitrate in headwater agricultural streams in Illinois

Nitrogen inputs to the Gulf of Mexico have increased during recent decades and agricultural regions in the upper Midwest, such as those in Illinois, are a major source of N to the Mississippi River. How strongly denitrification affects the transport of nitrate (NO(3)-N) in Illinois streams has not been directly assessed. We used the nutrient spiraling model to assess the role of in-stream denitrification in affecting the concentration and downstream transport of NO(3)-N in five headwater streams in agricultural areas of east-central Illinois. Denitrification in stream sediments was measured approximately monthly from April 2001 through January 2002. Denitrification rates tended to be high (up to 15 mg N m(-2) h(-1)), but the concentration of NO(3)-N in the streams was also high (>7 mg N L(-1)). Uptake velocities for NO(3)-N (uptake rate/concentration) were lower than reported for undisturbed streams, indicating that denitrification was not an efficient N sink relative to the concentration of NO(3)-N in the water column. Denitrification uptake lengths (the average distance NO(3)-N travels before being denitrified) were long and indicated that denitrification in the streambed did not affect the transport of NO(3)-N. Loss rates for NO(3)-N in the streams were <5% d(-1) except during periods of low discharge and low NO(3)-N concentration, which occurred only in late summer and early autumn. Annually, most NO(3)-N in these headwater sites appeared to be exported to downstream water bodies rather than denitrified, suggesting previous estimates of N losses through in-stream denitrification may have been overestimated.     

Denitrification as a nitrogen removal mechanism in a Vermont peatland

Atmospheric deposition of nitrogenous compounds to ombrotrophic peatlands (i.e., those that have peat layers higher than their surroundings and receive nutrients and minerals exclusively by precipitation) has the potential to significantly alter ecosystem functioning. This study utilized the acetylene inhibition technique to estimate the relative importance of denitrification in nitrogen removal from a primarily ombrotrophic peatland, in an attempt to estimate the threat of increased nitrogen loadings to these areas. Estimates of mean rates of denitrification ranged from -2.76 to 84.0 ng N(2)O-N cm(-3) h(-1) (equivalent to -150 to 4800 microg N(2)O-N m(-2) h(-1)) using an ex situ core technique and from -8.30 to 5.98 microg N(2)O-N m(-2) h(-1) using an in situ chamber technique. Core rates may have been elevated over natural field levels due to effects of disturbance on substrate availability, and chamber rates may have been low due to diffusional constraints on acetylene and N(2)O. Net nitrification was also measured in an attempt to evaluate this process as a source of nitrate for denitrifiers. The low rates of net nitrification measured, in combination with the low rates of in situ denitrification and the very low amounts of free nitrate measured in this peatland, suggests that inorganic N turnover in this wetland is low. Results showed that nitrate was a limiting factor for denitrification in this peatland, with mean rates from nitrate-amended cores ranging from 13.1 to 260 ng N(2)O-N cm(-3) h(-1), and it is expected that increases in nitrogen loadings will increase denitrification rates in this ecosystem.     

Selenium stable isotope ratios in California agricultural drainage water management systems

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se-affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow-through wetland reveal small isotopic contrasts (mean difference 0.7%) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(0), respectively. For the integrated on-farm drainage management sites, evaporite salts were slightly (approximately 0.6%) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4%) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments.     

Nitrite formation and nitrous oxide emissions as affected by reclaimed effluent application

The effect of irrigation with reclaimed effluent (RE) (after secondary treatment) on the mechanisms and rates of nitrite formation, N2O emissions, and N mineralization is not well known. Grumosol (Chromoxerert) soil was incubated for 10 to 14 d with fresh water (FW) and RE treated with 15NO3- and 15NH4+ to provide a better insight on N transformations in RE-irrigated soil. Nitrite levels in RE-irrigated soil were one order of magnitude higher than in FW- irrigated soil and ranged between 15 to 30 mg N kg(-1) soil. Higher levels of NO2- were observed at a moisture content of 60% than at 70% and 40% w/w. Nitrite levels were also higher when RE was applied to a relatively dry Grumosol (20% w/w) than at subsequent applications of RE to soil at 40% w/w. Isotopic labeling indicated that the majority of NO2 was formed via nitrification. The amount of N2O emitted from RE-treated Grumosol was double the amount emitted from FW treatments at 60% w/w. Nitrification was responsible for about 42% of the emissions. The N20 emission from the RE-treated bulk soil (passing a 9.5-mm sieve) was more than double the amount formed in large aggregates (4.76-9.5 mm in diameter). No dinitrogen was detected under the experimental conditions. Results indicate that irrigation with secondary RE stimulates nitrification, which may enhance NO3 leaching losses. This could possibly be a consequence of long-term exposure of the nitrifier population to RE irrigation. Average gross nitrification rate estimates were 11.3 and 15.8 mg N kg(-1) soil d(-1) for FW- and RE-irrigated bulk soils, respectively. Average gross mineralization rate estimates were about 3 mg N kg(-1) soil d(-1) for the two water types.     

Nitrous oxide emissions from wastewater treatment and water reclamation plants in southern California

Nitrous oxide (N?O) is a long-lived and potent greenhouse gas produced during microbial nitrification and denitrification. In developed countries, centralized water reclamation plants often use these processes for N removal before effluent is used for irrigation or discharged to surface water, thus making this treatment a potentially large source of N?O in urban areas. In the arid but densely populated southwestern United States, water reclamation for irrigation is an important alternative to long-distance water importation. We measured N?O concentrations and fluxes from several wastewater treatment processes in urban southern California. We found that N removal during water reclamation may lead to in situ N?O emission rates that are three or more times greater than traditional treatment processes (C oxidation only). In the water reclamation plants tested, N?O production was a greater percentage of total N removed (1.2%) than traditional treatment processes (C oxidation only) (0.4%). We also measured stable isotope ratios (δN and δO) of emitted N?O and found distinct δN signatures of N?O from denitrification (0.0 ± 4.0 ‰) and nitrification reactors (-24.5 ± 2.2 ‰), respectively. These isotope data confirm that both nitrification and denitrification contribute to N?O emissions within the same treatment plant. Our estimates indicate that N?O emissions from biological N removal for water reclamation may be several orders of magnitude greater than N?O emissions from agricultural activities in highly urbanized southern California. Our results suggest that wastewater treatment that includes biological nitrogen removal can significantly increase urban N?O emissions.     

Seasonal dynamics of denitrification along topohydrosequences in three different riparian wetlands

We investigated the seasonal patterns of denitrification rates and potentials in soil profiles along the topohydrosequence formed at the upland-wetland interface in three riparian wetlands with different vegetation cover (i.e., forest, understory vegetation, and grass). Denitrification was measured using the acetylene inhibition method on soil cores and slurries, which provided a means of comparing the relative activity of this process in different locations. We evaluated, on a seasonal basis, the respective importance of the vegetative cover and the hydromorphic gradient as factors limiting denitrification. Regardless of the season, vegetation type, or lateral position along each topohydrosequence in the riparian wetlands, strong significant gradients of both in situ and potential denitrification rates were measured within a soil profile. Results confirm that the upper organic soil horizon is the most active, when in contact with the ground water. In deeper soil horizons, denitrification activity was low (from 0.004 to 0.5 mg N kg(-1) dry soil d(-1)), but contributed significantly to the reduction of ground water NO3- load along the riparian ground water flowpath (from 9.32 to 0.98 mg NO3-N L(-1)). Along the soil topohydrosequence, the denitrifying community of the upper soil horizons did not vary significantly on a seasonal basis despite the large seasonal ground water fluctuations. Along each topohydrosequence, the denitrification-limiting factor gradually shifted from anaerobiosis to NO3- supply. In situ denitrification rates in the forested, understory vegetation and grass sites were not significantly different. This result emphasizes the importance of the topography of the valley rather than the vegetation cover in controlling denitrification activity in riparian wetlands.