Use of tandem circulation wells to measure hydraulic conductivity without groundwater extraction

Conventional methods to measure the hydraulic conductivity of an aquifer on a relatively large scale (10-100 m) require extraction of significant quantities of groundwater. This can be expensive, and otherwise problematic, when investigating a contaminated aquifer. In this study, innovative approaches that make use of tandem circulation wells to measure hydraulic conductivity are proposed. These approaches measure conductivity on a relatively large scale, but do not require extraction of groundwater. Two basic approaches for using circulation wells to measure hydraulic conductivity are presented; one approach is based upon the dipole-flow test method, while the other approach relies on a tracer test to measure the flow of water between two recirculating wells. The approaches are tested in a relatively homogeneous and isotropic artificial aquifer, where the conductivities measured by both approaches are compared to each other and to the previously measured hydraulic conductivity of the aquifer. It was shown that both approaches have the potential to accurately measure horizontal and vertical hydraulic conductivity for a relatively large subsurface volume without the need to pump groundwater to the surface. Future work is recommended to evaluate the ability of these tandem circulation wells to accurately measure hydraulic conductivity when anisotropy and heterogeneity are greater than in the artificial aquifer used for these studies.     

Modelling the geochemical fate and transport of wastewater-derived phosphorus in contrasting groundwater systems

A 1D reactive transport model (RTM) is used to obtain a mechanistic understanding of the fate of phosphorus (P) in the saturated zone of two contrasting aquifer systems. We use the field data from two oxic, electron donor-poor, wastewater-impacted, sandy Canadian aquifers, (Cambridge and Muskoka sites) as an example of a calcareous and non-calcareous groundwater system, respectively, to validate our reaction network. After approximately 10 years of wastewater infiltration, P is effectively attenuated within the first 10 m down-gradient of the source mainly through fast sorption onto calcite and Fe oxides. Slow, kinetic sorption contributes further to P removal, while precipitation of phosphate minerals (strengite, hydroxyapatite) is quantitatively unimportant in the saturated zone. Nitrogen (N) dynamics are also considered, but nitrate behaves essentially as a conservative tracer in both systems. The model-predicted advancement of the P plume upon continued wastewater discharge at the calcareous site is in line with field observations. Model results suggest that, upon removal of the wastewater source, the P plume at both sites will persist for at least 20 years, owing to desorption of P from aquifer solids and the slow rate of P mineral precipitation. Sensitivity analyses for the non-calcareous scenario (Muskoka) illustrate the importance of the sorption capacity of the aquifer solids for P in modulating groundwater N:P ratios in oxic groundwater. The model simulations predict the breakthrough of groundwater with high P concentrations and low N:P ratios after 17 years at 20 m from the source for an aquifer with low sorption capacity (<0.02% w/w Fe(OH)(3)). In this type of system, denitrification plays a minor role in lowering the N:P ratios because it is limited by the availability of labile dissolved organic matter.     

Numerical simulation of a fine-grained denitrification layer for removing septic system nitrate from shallow groundwater

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. It has been proposed that adding labile carbon sources to septic distribution fields could enhance heterotrophic denitrification and thus reduce nitrate concentrations in shallow groundwater. In this study, a numerical model which solves for variably saturated flow and reactive transport of multiple species is employed to investigate the performance of a drain field design that incorporates a fine-grained denitrification layer. The hydrogeological scenario simulated is an unconfined sand aquifer. The model results suggest that the denitrification layer, supplemented with labile organic carbon, may be an effective means to eliminate nitrogen loading to shallow groundwater. It is also shown that in noncalcareous aquifers, the denitrification reaction may provide sufficient buffering capacity to maintain near neutral pH conditions beneath and down gradient of the drain field. Leaching of excess dissolved organic carbon (DOC) from the denitrification layer is problematic, and causes an anaerobic plume to develop in simulations where the water table is less than 5-6 m below ground surface; this anaerobic plume may lead to other down gradient changes in groundwater quality. A drain field and denitrification layer of smaller dimensions is shown to be just as effective for reducing nitrate, but has the benefit of reducing the excess DOC leached from the layer. This configuration will minimize the impact of wastewater disposal in areas where the water table is as shallow as 3.5 m.     

Effects of macrophytes and external carbon sources on nitrate removal from groundwater in constructed wetlands

Several microcosm wetlands unplanted and planted with five macrophytes (Phragmites australis, Commelina communis, Penniserum purpureum, Ipomoea aquatica, and Pistia stratiotes) were employed to remove nitrate from groundwater at a concentration of 21-47 mg NO3-N/l. In the absence of external carbon, nitrate removal rates ranged from 0.63 to 1.26 g NO3-N/m2/day for planted wetlands. Planted wetlands exhibited significantly greater nitrate removal than unplanted wetlands (P<0.01), indicating that macrophytes are essential to efficient nitrate removal. Additionally, a wetland planted with Penniserum showed consistently higher nitrate removal than those planted with the other four macrophytes, suggesting that macrophytes present species-specific nitrate removal efficiency possibly depending on their ability to produce carbon for denitrification. Although adding external carbon to the influent improved nitrate removal, a significant fraction of the added carbon was lost via microbial oxidation in the wetlands. Planting a wetland with macrophytes with high productivity may be an economic way for removing nitrate from groundwater. According to the harvest result, 4-11% of nitrogen removed by the planted wetland was due to vegetation uptake, and 89-96% was due to denitrification.     

Analytical solutions for flow fields near continuous wall reactive barriers

Permeable reactive barriers (PRBs) are widely applied for in-situ remediation of contaminant plumes transported by groundwater. Besides the goal of a sufficient contaminant remediation inside the reactive cell (residence time) the width of plume intercepted by a PRB is of critical concern. A 2-dimensional analytical approach is applied to determine the flow fields towards rectangular PRBs of the continuous wall (CW) configuration with and without impermeable side walls (but yet no funnel). The approach is based on the conformal mapping technique and assumes a homogeneous aquifer with a uniform ambient flow field. The hydraulic conductivity of the reactive material is furthermore assumed to exceed the conductivity of the aquifer by at least one order of magnitude as to neglect the hydraulic gradient across the reactor. The flow fields are analyzed regarding the widths and shapes of the respective capture zones as functions of the dimensions (aspect ratio) of the reactive cell and the ambient groundwater flow direction. Presented are an improved characterization of the advantages of impermeable side walls, a convenient approach to improved hydraulic design (including basic cost-optimization) and new concepts for monitoring CW PRBs. Water level data from a CW PRB at the Seneca Army Depot site, NY, are used for field demonstration.     

Field test of a cross-injection scheme for stimulating in situ denitrification near a municipal water supply well

A pilot-scale test of an in situ denitrification scheme was undertaken to assess an adaptation of the nutrient injection wall (NIW) technology for treating a deep (30-40 m) nitrate contamination problem (N-NO(-)(3) ~ 10-12 mg/L). The adaptation is called the Cross-Injection Scheme (CIS). It duplicates the NIW method without a wall; wells are installed and operated directly in the aquifer and high-flux zones of the aquifer are preferentially targeted for treatment. The test was conducted on the site of a municipal water supply well field, with the supply well pumping between 15-80 m(3)/h. Acetate was periodically injected into the aquifer between an injection-extraction well pair positioned across the normal direction of flow. The injected pulses were then permitted to move with the water toward the municipal wells, providing a carbon supply to drive the desired denitrification. The fate of nitrate, nitrite, acetate and sulphate were monitored at multilevel wells located between the injection location and the municipal wells. The acetate pulsing interval was approximately weekly (9 h injections), so that the system was operating passively 95% of the time. Previous work on the site has established that the highest solute fluxes were associated with a 1-3 m thick zone about 35 m below surface. This zone was found to respond to the acetate additions as a function of the municipal pumping rate and the carbon-to-nitrogen ratio (i.e., determined by the injected acetate concentration). Initially, acetate was injected just below the theoretical stoichiometric requirement for complete denitrification and nitrate disappearance was accompanied by nitrite production. Increasing the C:N ratio (doubling the acetate injection concentration) increased the removal of nitrate and diminished the occurrence of nitrite. Slowing the municipal pumping rate, with a C:N ratio of 1.2-1.6, resulted in complete nitrate attenuation with no nitrite production and no sulfate reduction. The experiment demonstrated that the CIS injection scheme is a viable option for the treatment of nitrate contamination in situ near high-capacity wells.     

Identification and reliability of microbial aerobic respiration and denitrification kinetics using a single-well push-pull field test

Methods to derive reaction rates of microbial processes are important since these processes are determining many chemical reactions influencing groundwater quality. Thereby, it is not only important to derive the parameters, but also to have a firm idea about the reliability with which these are determined. Analysis of residuals, sensitivity analyses and analysis of joint confidence intervals provide an interesting tool for this purpose. The method is illustrated in this paper using a push-pull test designed to derive aerobic respiration and denitrification. Therefore, a test solution containing dissolved oxygen and nitrate as reactive tracer and bromide as non-reactive tracer was injected in organic matter rich sediment. Afterwards, this test solution was extracted and water quality was monitored. ReacTrans, a finite-difference, axial-symmetric groundwater flow and solute transport model was developed to simulate the test and derive hydraulic, solute transport and chemical parameters. Aerobic respiration and denitrification were simulated with Michaelis-Menten kinetics. Maximum reaction rates (10.4 and 2.4 mmol/ld for aerobic respiration and denitrification respectively) and Michaelis constants (0.14 and 0.1 mmol/l for aerobic respiration and denitrification respectively) were determined. The reliability with which these parameters are derived is indicated by analysis of residuals, sensitivities and joint confidence intervals. This shows that the Michaelis-Menten parameters can be derived reliable with a push-pull test, whereas the test is insensitive to effective porosity and hydraulic conductivity. Because of the small scale of the test, longitudinal dispersivity was very small and therefore unidentifiable.     

Evaluation of groundwater flow patterns around a dual-screened groundwater circulation well

Dual-screened groundwater circulation wells (GCWs) can be used to remove contaminant mass and to mix reagents in situ. GCWs are so named because they force water in a circular pattern between injection and extraction screens. The radial extent, flux and direction of the effective flow of this circulation cell are difficult to measure or predict. The objective of this study is to develop a robust protocol for assessing GCW performance. To accomplish this, groundwater flow patterns surrounding a GCW are assessed using a suite of tools and data, including: hydraulic head, in situ flow velocity, measured hydraulic conductivity data from core samples, chemical tracer tests, contaminant distribution data, and numerical flow and transport models. The hydraulic head data show patterns that are consistent with pumping on a dual-screened well, however, many of the observed changes are smaller than expected. In situ thermal perturbation flow sensors successfully measured horizontal flow, but vertical flow could not be determined with sufficient accuracy to be useful in mapping flow patterns. Two types of chemical tracer tests were utilized at the site and showed that much of the flow occurs within a few meters of the GCW. Flow patterns were also assessed based on changes in contaminant (trichloroethylene, TCE) concentrations over time. The TCE data clearly showed treated water moving away from the GCW at shallow and intermediate depths, but the circulation of that water back to the well, except very close to the well, was less clear. Detailed vertical and horizontal hydraulic conductivities were measured on 0.3 m-long sections from a continuous core from the GCW installation borehole. The measured vertical and horizontal hydraulic conductivity data were used to construct numerical flow and transport models, the results of which were compared to the head, velocity and concentration data. Taken together, the field data and modeling present a fairly consistent picture of flow and transport around the GCW. However, the time and expense associated with conducting all of those tests would be prohibitive for most sites. As a consequence, a sequential protocol for GCW characterization is presented here in which the number of tools used can be adjusted to meet the needs of individual sites. While not perfect, we believe that this approach represents the most efficient means for evaluating GCW performance.     

Measurements of groundwater velocity in discrete rock fractures

Estimating groundwater velocity in fracture networks using a Darcy or cubic law calculation is complicated by the wide distribution of fracture aperture often found in these systems and by the difficulty in measuring hydraulic head in discrete fracture features. Although difficult to conduct in a fractured rock setting, the point dilution method can be utilized to collect direct measurements of groundwater velocity in individual fractures. To compare measured against calculated velocities, more than 100 point dilution experiments were conducted within a 35 x 35 m area of a single fracture and in discrete fracture features within a fracture network at a larger scale. The dilution experiments were conducted by isolating a fracture feature in a borehole, measuring the hydraulic aperture, and measuring the decay of an injected tracer due to the advective groundwater flux across the fracture. Groundwater velocity was estimated using the hydraulic aperture and the rate of decay of the injected tracer. Estimates of the local hydraulic gradient were calculated via the cubic law using the velocity estimate and the hydraulic aperture. The results of the tests conducted in the single fracture show variable (1 to 33 m/day) but on average higher velocities in comparison to that measured during a natural gradient tracer experiment conducted previously (in which the effects of matrix diffusion were accounted for) and to that which would be calculated using the cubic law. Based on these results, it was determined that the best estimate of the average groundwater velocity, at the scale of the measurement area used for the cubic law calculations, could only be obtained using the largest apertures in the aperture distribution. Variability of the velocity measurements was also observed over time. Increases in velocity were attributed to the effect of rainfall although concurrent increases in hydraulic gradient were not detected (likely within the tolerance of the measuring devices). The groundwater velocities measured in the fracture network varied over a wider range than at the scale of the single fracture (from 2 to 388 m/day). No correlation, however, was observed between the size of the fracture aperture and measured velocity.     

Water quality dynamics and hydrology in nitrate loaded riparian zones in the Netherlands

Riparian zones are known to function as buffers, reducing non-point source pollution from agricultural land to streams. In the Netherlands, riparian zones are subject to high nitrogen inputs. We combined hydrological, chemical and soil profile data with groundwater modelling to evaluate whether chronically N loaded riparian zones were still mitigating diffuse nitrate fluxes. Hydraulic parameters and water quality were monitored over 2 years in 50 piezometres in a forested and grassland riparian zone. Average nitrate loadings were high in the forested zone with 87 g NO(3)(-)-N m(-2) y(-1) and significantly lower in the grassland zone with 15 g NO(3)(-)-N m(-2) y(-1). Groundwater from a second aquifer diluted the nitrate loaded agricultural runoff. Biological N removal however occurred in both riparian zones, the grassland zone removed about 63% of the incoming nitrate load, whereas in the forested zone clear symptoms of saturation were visible and only 38% of the nitrate load was removed.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

Denitrification in the river estuaries of the northern Baltic Sea

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.     

Use of vegetable oil in a pilot-scale denitrifying barrier

Nitrate in drinking water is a hazard to both humans and animals. Contaminated water can cause methemoglobinemia and may pose a cancer risk. Permeable barriers containing innocuous oils, which stimulate denitrification, can remove nitrate from flowing groundwater. For this study, a sand tank (1.1 x 2.0 x 0.085 m in size) containing sand was used as a one-dimensional open-top scale model of an aquifer. A meter-long area near the center of the tank contained sand coated with soybean oil. This region served as a permeable denitrifying barrier. Water containing 20 mg l(-1) nitrate-N was pumped through the barrier at a high flow rate, 1112 l week(-1), for 30 weeks. During the 30-week study, the barrier removed 39% of the total nitrate-N present in the water. The barrier was most efficient during the first 10 weeks of the study when almost all of the nitrate and nitrogen was removed. Efficiency declined with time so that by week 30 almost no nitrate was removed by the system. Nitrite levels in the effluent water remained low throughout the study. Barriers could be used to protect groundwater from nitrate contamination or for the in situ treatment of contaminated water. At the low flow rates that exist in most aquifers, such barriers should be effective at removing nitrate from groundwater for a much longer period of time.     

Combined use of field and laboratory testing to predict preferred flow paths in an heterogeneous aquifer

Elevated nitrate concentrations within a municipal water supply aquifer led to pilot testing of a field-scale, in situ denitrification technology based on carbon substrate injections. In advance of the pilot test, detailed characterization of the site was undertaken. The aquifer consisted of complex, discontinuous and interstratified silt, sand and gravel units, similar to other well studied aquifers of glaciofluvial origin, 15-40 m deep. Laboratory and field tests, including a conservative tracer test, a pumping test, a borehole flowmeter test, grain-size analysis of drill cuttings and core material, and permeameter testing performed on core samples, were performed on the most productive depth range (27-40 m), and the results were compared. The velocity profiles derived from the tracer tests served as the basis for comparison with other methods. The spatial variation in K, based on grain-size analysis, using the Hazen method, were poorly correlated with the breakthrough data. Trends in relative hydraulic conductivity (K/K(avg)) from permeameter testing compared somewhat better. However, the trends in transient drawdown with depth, measured in multilevel sampling points, corresponded particularly well with those of solute mass flux. Estimates of absolute K, based on standard pumping test analysis of the multilevel drawdown data, were inversely correlated with the tracer test data. The inverse nature of the correlation was attributed to assumptions in the transient drawdown packages that were inconsistent with the variable diffusivities encountered at the scale of the measurements. Collectively, the data showed that despite a relatively low variability in K within the aquifer under study (within a factor of 3), water and solute mass fluxes were concentrated in discrete intervals that could be targeted for later bioremediation.     

Applications and implications of direct groundwater velocity measurement at the centimetre scale

Three projects involving point velocity probes (PVPs) illustrate the advantages of direct groundwater velocity measurements. In the first, a glacial till and outwash aquifer was characterized using conventional methods and multilevel PVPs for designing a bioremediation program. The PVPs revealed a highly conductive zone that dominated the transport of injected substances. These findings were later confirmed with a natural gradient tracer test. In the second, PVPs were used to map a groundwater velocity field around a dipole recirculation well. The PVPs showed higher than expected velocities near the well, assuming homogeneity in the aquifer, leading to improved representations of the aquifer heterogeneity in a 3D flow model, and an improved match between the modelled and experimental tracer breakthrough curves. In the third study, PVPs detected subtle changes in aquifer permeability downgradient of a biostimulation experiment. The changes were apparently reversible once the oxygen source was depleted, but in locations where the oxygen source lingered, velocities remained low. PVPs can be a useful addition to the hydrogeologist's toolbox, because they can be constructed inexpensively, they provide data in support of models, and they can provide information on flow in unprecedented detail.     

Importance of considering intraborehole flow in solute transport modeling under highly dynamic flow conditions

Correct interpretation of tracer test data is critical for understanding transport processes in the subsurface. This task can be greatly complicated by the presence of intraborehole flows in a highly dynamic flow environment. At a new tracer test site (Hanford IFRC) a dynamic flow field created by changes in the stage of the adjacent Columbia River, coupled with a heterogeneous hydraulic conductivity distribution, leads to considerable variations in vertical hydraulic gradients. These variations, in turn, create intraborehole flows in fully-screened (6.5m) observation wells with frequently alternating upward and downward movement. This phenomenon, in conjunction with a highly permeable aquifer formation and small horizontal hydraulic gradients, makes modeling analysis and model calibration a formidable challenge. Groundwater head data alone were insufficient to define the flow model boundary conditions, and the movement of the tracer was highly sensitive to the dynamics of the flow field. This study shows that model calibration can be significantly improved by explicitly considering (a) dynamic flow model boundary conditions and (b) intraborehole flow. The findings from this study underscore the difficulties in interpreting tracer tests and understanding solute transport under highly dynamic flow conditions.     

复合介质渗透反应格栅去除地下水中的氨氮

针对受低浓度氨氮污染的地下水,实验筛选组合了不同的反应介质,利用串联的多介质填充柱模拟渗透反应格栅,通过物理吸附及生物硝化-反硝化作用来实现氮的去除。结果表明,在进水氨氮浓度为10 mg/L、流速为0.5 m/d的条件下,模拟柱对氨氮的去除率达到98%以上,且不会出现亚硝酸盐及硝酸盐浓度的升高。水体经过释氧柱后溶解氧由2mg/L升高至10 mg/L以上,表明释氧材料可提供硝化细菌所需的好氧环境。好氧柱中填充易于生物挂膜的生物陶粒及对氨氮有较强吸附能力的沸石,二者联用通过生物硝化-物理吸附协同作用实现对氨氮的去除,其中生物作用实现的氨氮去除量占总去除量的50%左右。后续厌氧反应柱填充海绵铁除氧并利用松树皮颗粒作为碳源,创造反硝化菌生长条件,硝酸盐氮浓度可由10 mg/L降低至5 mg/L以下,实现对好氧反应阶段所产生的硝酸盐的去除,避免了地下水的二次污染。     

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.     

Denitrification in cypress swamp within the Atchafalaya River Basin, Louisiana

Nitrogen has been implicated as a major cause of hypoxia in shallow water along the Louisiana/Texas, USA coasts. Excess nitrogen (mainly nitrate) from Mississippi and Atchafalaya River drainage basins may drive the onset and duration of hypoxia in the northern Gulf of Mexico. Restoring and enhancing denitrification have been proposed to reduce and control coastal hypoxia and improve water quality in the Mississippi River Basin. Sediments were collected from six baldcypress restoration sites within the Atchafalaya River Basin, Louisiana, USA. The acetylene blockage technique was used to measure background and potential sediment denitrification rates. Denitrification fluxes were measured before nitrate addition (background rates) and after nitrate addition of 100mgNl(-1) (potential denitrification) at three seasonal temperatures. Background denitrification was low across all cypress swamp sites ranging from 0.9 to 8.8, 0.6 to 28.5 and 8.8 to 47.5g N evolved ha(-1)d(-1) at water/sediment column temperatures of 8, 22 and 30 degrees C, respectively. After nitrate addition, temperature had a significant effect on sediment denitrification potential. Maximum rates measured at 8, 22 and 30 degrees C were approximately 250-260, 550 and 970gNha(-1)d(-1), respectively. Most of the added nitrate in water columns, incubated at 8 degrees C, was removed after 65d compared to 32d and 17d at 22 and 30 degrees C, respectively. These results indicate cypress swamps have the potential to assimilate and process elevated levels of floodwater nitrate with denitrification being a major removal mechanism.