The effect of biogas ebullition on ammonia emissions from animal manure-processing lagoons.

Various models have been developed to determine ammonia (NH3 ) emissions from animal manure-processing lagoons to enable relatively simple estimations of emissions. These models allow estimation of actual emissions without intensive field measurements or "one-size-fits-all" emission factors. Two mechanisms for lagoon NH3 emissions exist: (a) diffusive gas exchange from the water surface and (b) mass-flow (bubble transport) from NH3 contained within the ebullition gas bubble (as it rises to the surface) produced from anaerobic decomposition of organic matter. The purpose of this research is to determine whether gas ebullition appreciably affects NH3 emissions and therefore should be considered in emissions models. Specifically, NH3 mass-flow emissions were calculated and compared with calculated diffusive NH3 emissions. Mass-flow NH3 emissions were evaluated based on a two-film model, in connection with the acid dissociation constant of ammonium, to predict the degree of NH3 gas saturation within the bubbles. Average daily ammoniacal nitrogen concentration, pH, and measured biological gas production (ebullition) in conjunction with literature values for Henry's law constant were used to calculate emissions from NH3 saturation of ebullition gases. Ebullition enhancement of NH3 surface emissions due to increased turbulence was estimated from average lagoon ebullition rates and literature values of turbulence enhancement. Ebullition enhancement of NH3 surface emissions and ebullition mass-flow NH3 emissions was determined to be <10% and <0.052%, respectively, of total NH3 emissions. Therefore, because ebullition effects are small, they may be neglected when developing process models to estimate NH3 emissions from water surfaces of swine manure processing lagoons.

Classification of Nitrate Polluting Activities through Clustering of Isotope Mixing Model Outputs.

Apportionment of nitrate (NO) sources in surface water and classification of monitoring locations according to NO polluting activities may help implementation of water quality control measures. In this study, we (i) evaluated a Bayesian isotopic mixing model (stable isotope analysis in R [SIAR]) for NO source apportionment using 2 yr of δN-NO and δO-NO data from 29 locations within river basins in Flanders (Belgium) and five expert-defined NO polluting activities, (ii) used the NO source contributions as input to an unsupervised learning algorithm (k-means clustering) to reclassify sampling locations into NO polluting activities, and (iii) assessed if a decision tree model of physicochemical data could retrieve the isotope-based and expert-defined classifications. Based on the SIAR and δB results, manure/sewage was identified as a major NO source, whereas soil N, fertilizer NO, and NH in fertilizer and rain were intermediate sources and NO in precipitation was a minor source. The k-means clustering algorithm allowed classification of NO polluting activities that corresponded well to the expert-defined classifications. A decision tree model of physicochemical parameters allowed us to correctly classify 50 to 100% of the sampling locations as compared with the k-means clustering approach. We suggest that NO polluting activities can be identified via clustering of NO source contributions from samples representing an entire river basin. Classification of future monitoring locations into these classes could use decision tree models based on physicochemical data. The latter approach holds a substantial degree of uncertainty but provides more inherent information for dedicated abatement strategies than monitoring of NO concentrations alone.

Use of a Bayesian isotope mixing model to estimate proportional contributions of multiple nitrate sources in surface water.

To identify different NO(3)(-) sources in surface water and to estimate their proportional contribution to the nitrate mixture in surface water, a dual isotope and a Bayesian isotope mixing model have been applied for six different surface waters affected by agriculture, greenhouses in an agricultural area, and households. Annual mean δ(15)N-NO(3)(-) were between 8.0 and 19.4‰, while annual mean δ(18)O-NO(3)(-) were given by 4.5-30.7‰. SIAR was used to estimate the proportional contribution of five potential NO(3)(-) sources (NO(3)(-) in precipitation, NO(3)(-) fertilizer, NH(4)(+) in fertilizer and rain, soil N, and manure and sewage). SIAR showed that "manure and sewage" contributed highest, "soil N", "NO(3)(-) fertilizer" and "NH(4)(+) in fertilizer and rain" contributed middle, and "NO(3)(-) in precipitation" contributed least. The SIAR output can be considered as a "fingerprint" for the NO(3)(-) source contributions. However, the wide range of isotope values observed in surface water and of the NO(3)(-) sources limit its applicability.

Error assessment of nitrogen and oxygen isotope ratios of nitrate as determined via the bacterial denitrification method.

Currently, bacterial denitrification is becoming the accepted method for delta(15)N- and delta(18)O-NO(3)(-) determination. However, proper correction methods with international references (USGS32, USGS34 and USGS35) are needed. As a consequence, it is important to realize that the corrected isotope values are derived from a combination of several other measurements with associated uncertainties. Therefore, it is necessary to consider the propagated uncertainty on the final isotope value. This study demonstrates how to correctly estimate the uncertainty on corrected delta(15)N- and delta(18)O-NO(3)(-) values using a first-order Taylor series approximation. The bacterial denitrification method errors from 33 batches of 561 surface water samples varied from 0.2 to 2.1 per thousand for delta(15)N-NO(3)(-) and from 0.7 to 2.3 per thousand for delta(18)O-NO(3)(-), which is slightly wider than the machine error, which varied from 0.2 to 0.6 per thousand for delta(15)N-N(2)O and from 0.4 to 1.0 per thousand for delta(18)O-N(2)O. The overall uncertainties, which are composed of the machine error and the method error, for the 33 batches ranged from 0.3 to 2.2 per thousand for delta(15)N-NO(3)(-) and from 0.8 to 2.5 per thousand for delta(18)O-NO(3)(-). In addition, the mean corrected delta(15)N and delta(18)O values of 132 KNO(3)-IWS (internal working standard) measurements were computed as 8.4 +/- 1.0 per thousand and 25.1 +/- 2.0 per thousand, which is a slight underestimation for delta(15)N and overestimation for delta(18)O compared with the accepted values (delta(15)N = 9.9 +/- 0.3 per thousand and delta(18)O = 24.0 +/- 0.3 per thousand). The overall uncertainty of the bacterial denitrification method allows the use of this method for source identification of NO(3)(-).

Comparison of the silver nitrate and bacterial denitrification methods for the determination of nitrogen and oxygen isotope ratios of nitrate in surface water.

Nitrogen (N) and oxygen (O) isotope ratios of NO(3) (-) are often used to trace dominant NO(3) (-) pollution sources in water. Both the silver nitrate (AgNO(3)) method and the bacterial denitrification method are frequently used analytical techniques to determine delta(15)N- and delta(18)O-NO(3) (-) in aqueous samples. The AgNO(3) method is applicable for freshwater and requires a concentration of 100-200 micromol of NO(3) (-) for isotope determination. The bacterial denitrification method is applicable for seawater and freshwater and for KCl extracts of soils with a NO(3) (-) concentration as low as 1 micromol. We have carried out a thorough method comparison using 42 real surface water samples having a wide range of delta(15)N- and delta(18)O-NO(3) (-) values and NO(3) (-) concentrations. Various correction pairs using three international references and blanks were used to correct raw delta(15)N- and delta(18)O-NO(3) (-) values. No significant difference between the corrected data was observed when using various correction pairs for each analytical method. Both methods also showed excellent repeatability with high intraclass correlation coefficients (ICC). The ICC of the AgNO(3) method was 0.992 for delta(15)N and 0.970 for delta(18)O. The ICC of the bacterial denitrification method was 0.995 for delta(15)N and 0.954 for delta(18)O. Moreover, a positive linear relationship with a high correlation coefficient (r >or= 0.88) between the two methods was found for delta(15)N- and delta(18)O-NO(3) (-). The comparability of the methods was assessed by the Bland-Altman technique using 95% limits of agreement. The average difference between results obtained by the bacterial denitrification and the AgNO(3) method for delta(15)N was -1.5 per thousand with 95% limits of agreement -3.6 and +0.5 per thousand. For delta(18)O this was +2.0 per thousand, with 95% limits of agreement -3.3 and +7.3 per thousand. We found that for delta(15)N and for delta(18)O, 97% of the differences fell within these 95% limits of agreement. In conclusion, the AgNO(3) and the bacterial denitrification methods are highly correlated and statistically interchangeable.

Accumulation and fractionation of trace metals in a Tunisian calcareous soil amended with farmyard manure and municipal solid waste compost.

A field plots experiment was carried out to assess the effects of repeated application of municipal solid waste compost in comparison to farmyard manure on the accumulation and distribution of trace metals, as well as organic carbon and nitrogen in Tunisian calcareous soil. Compared with untreated soil, the application of the two organic amendments significantly increased the organic carbon and nitrogen contents of the soil. Particle-size fractionations showed that carbon and nitrogen were mainly found to occur in the macro-organic matter fraction (80%). The two organic amendments significantly increased organic carbon in the macro-organic and mineral >150 microm fraction and the 150-50 microm fraction, as well as the organic nitrogen in 150-50 microm and macro-organic fraction. Compared with farmyard manure, municipal solid waste compost significantly increased total Cd, Cu, Pb and Zn contents in the topsoil. These trace metals were mainly present in the macro-organic matter fraction. Significant increases of Cu, Zn and Pb were detected in the 150-50 microm, <50 microm and macro-organic fractions after application of municipal solid waste compost. A significant increase of Cd content was only observed in the 150-50 microm fraction. The trace metals also showed different fractionation patterns when the BCR sequential extraction scheme was applied on untreated and compost-treated soil. The residual fraction was found to be the major fraction, especially for Cu, Cr, Ni and Zn. In contrast, Cd was mainly present in the acid-extractable and reducible fraction, whereas Pb was mainly associated with the reducible fraction.

Present limitations and future prospects of stable isotope methods for nitrate source identification in surface- and groundwater.

Nitrate (NO3(-)) contamination of surface- and groundwater is an environmental problem in many regions of the world with intensive agriculture and high population densities. Knowledge of the sources of NO3(-) contamination in water is important for better management of water quality. Stable nitrogen (delta15N) and oxygen (delta18O) isotope data of NO3(-) have been frequently used to identify NO3(-) sources in water. This review summarizes typical delta15N- and delta18O-NO3(-) ranges of known NO3(-) sources, interprets constraints and future outlooks to quantify NO3(-) sources, and describes three analytical techniques ("ion-exchange method", "bacterial denitrification method", and "cadmium reduction method") for delta15N- and delta18)O-NO3(-) determination. Isotopic data can provide evidence for the presence of dominant NO3(-) sources. However, quantification, including uncertainty assessment, is lacking when multiple NO3(-) sources are present. Moreover, fractionation processes are often ignored, but may largely constrain the accuracy of NO3(-) source identification. These problems can be overcome if (1) NO3(-) isotopic data are combined with co-migrating discriminators of NO3(-) sources (e.g. (11)B), which are not affected by transformation processes, (2) contributions of different NO3(-) sources can be quantified via linear mixing models (e.g. SIAR), and (3) precise, accurate and high throughput isotope analytical techniques become available.

Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils.

A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between 12CH4, 13CH4, and 12CH3D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per thousand in the delta13C value, with delta13C the relative 13C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.

On-line technique to determine the isotopic composition of total dissolved nitrogen.

A new on-line analytical setup for 15N measurements of total dissolved nitrogen (TDN) has been developed through the coupling of a high-temperature catalytic (Ce(IV)O2) oxidation furnace, a Cu reduction furnace, and an isotope ratio mass spectrometer. The detection limit for accurate delta15N measurements is 20 mg of N L-1. For N-containing compounds dissolved in water, a standard deviation on N concentration measurements of 0.2 mg of N L-1, independent of N concentration, has been found. Reproducibility on delta15N increased with increasing N concentration, with standard deviations varying from 0.8 to 0.1 per thousand in the range of 20-100 mg of N L-1. Salt matrixes, in which the N species might be dissolved, could influence the analysis capacity and continuity, mainly at concentrations above 0.1 M. To our knowledge, this system is the first successful on-line setup capable of performing routine delta15N and N concentration measurements of the TDN pool. Potential applications are large and are believed to result in an increased insight in N cycling and dissolved organic nitrogen behavior in terrestrial and aquatic ecosystems.

Assessment of temporal and spatial variation of nitrate removal in riparian zones.

The aim of this study was to monitor long-term temporal and spatial groundwater NO(3) (-) removal efficiencies in different riparian zones via a limited number of sampling wells. Groundwater NO(3) (-) concentrations were measured fortnightly or monthly over a period of two years using transects of ground water sampling wells. Depending on the level of the NO(3) (-) load (up to 120mgNL(-1) at the input side of the riparian zone a distance of 10 to 30m was needed to remove NO(3) (-) from the groundwater below 11.3mgNL(-1). Considering all seasons, the mixed vegetation and grass riparian site succeeded to remove groundwater NO(3) (-) efficiently (92-100% within a distance of 30m. The forested riparian zone removed 72-90% of the total NO(3) (-) input within a distance of 30m. Evidence emerged that NO(3) (-) could also be removed actively at depths up to 2m, due to the presence of organically enriched layers of alluvial deposits or roots. Our four dimensional approach (three dimensional space and time), in combination with a limited number of sampling wells, was shown to be a useful monitoring tool to assess the variability of NO(3) (-) removal in riparian zones.

Induction of enhanced methane oxidation in compost: temperature and moisture response.

Landfilling is one of the most common ways of municipal solid waste disposal. Degradation of organic waste produces CH(4) and other landfill gases that significantly contribute to global warming. However, before entering the atmosphere, part of the produced CH(4) can be oxidised while passing through the landfill cover. In the present study, the oxidation rate of CH(4) was studied with various types of compost as possible landfill cover. The influence of incubation time, moisture content and temperature on the CH(4) oxidation capacity of different types of compost was examined. It was observed that the influence of moisture content and temperature on methane oxidation is time-dependent. Maximum oxidation rates were observed at moisture contents ranging from 45% to 110% (dry weight basis), while the optimum temperature ranged from 15 to 30 degrees C.

Soil delta15N patterns in old-growth forests of southern Chile as integrator for N-cycling.

Old-growth forests of southern Chile represent an important reserve of temperate (rain) forests in the world. Wetter and colder forest ecosystems appear to be more efficient in conserving and recycling N such that mostly non-plant available N species are lost, which could be indicated by more depleted delta15N values of the soil and plants. Hydrological N loss from the old-growth forests in southern Chile occurs mainly via dissolved organic nitrogen and not via dissolved inorganic N. Forest disturbances (e.g. fire, clear-cutting or enhanced N deposition) cause (abrupt) changes in ecosystem N-cycling processes. In this study, we hypothesized that delta15N signatures of soil profiles under old-growth forests could be used as an integrator for ecosystem N-cycling, and changes of these delta15N profiles could be valuable to assess ecosystem resilience towards disturbances. Six old-growth forests were selected in the phytogeographical region of the Valdivian rain forest in southern Chile. One of the sites has been partly burned in February 2002. First, we observed that ecosystems with higher mean annual precipitation and lower mean annual temperature were relatively more depleted in 15N. Secondly, we found that a forest fire caused a 100-fold increase of the nitrate export and induced an enrichment of the soil delta15N signal in the upper 20 cm.

Nitrogen cycling through swine production systems: ammonia, dinitrogen, and nitrous oxide emissions.

Ammonia (NH(3)) emissions from animal systems have become a primary concern for all of livestock production. The purpose of this research was to establish the relationship of nitrogen (N) emissions to specific components of swine production systems and to determine accurate NH(3) emission factors appropriate for the regional climate, geography, and production systems. Micrometeorological instrumentation and gas sensors were placed over two lagoons in North Carolina during 1997-1999 to obtain information for determining ammonia emissions over extended periods and without interfering with the surrounding climate. Ammonia emissions varied diurnally and seasonally and were related to lagoon ammonium concentration, acidity, temperature, and wind turbulence. Conversion of significant quantities of ammonium NH(4)(+) to dinitrogen gas (N(2)) were measured in all lagoons with the emission rate largely dependent on NH(4)(+) concentration. Lagoon NH(4)(+) conversion to N(2) accounted for the largest loss component of the N entering the farm (43% as N(2)); however, small amounts of N(2)O were emitted from the lagoon (0.1%) and from field applications (0.05%) when effluent was applied nearby. In disagreement with previous and current estimates of NH(3) emissions from confined animal feeding operation (CAFO) systems, and invalidating current assumptions that most or all emissions are in the form of NH(3), we found much smaller NH(3) emissions from animal housing (7%), lagoons (8%), and fields (2%) using independent measurements of N transformation and transport. Nitrogen input and output in the production system were evaluated, and 95% of input N was accounted for as output N from the system.

Microbial biomass in a soil amended with different types of organic wastes.

Application of different types of organic wastes may have a marked effect on soil microbial biomass and its activity. The objective of this study was to quantify the amount of microbial biomass in a loamy-clayey soil, amended with different types of organic waste residues (composts of municipal solid waste of different ages, sewage sludge and farmyard manure) and incubated for 8 weeks at 25 degrees C and two-thirds of field capacity, using the fumigation-extraction method. Both microbial biomass-C and -N (BC and BN, respectively) appeared to be dependent on the type of organic waste residues, on their degree of stability, and on their chemical characteristics. In general, organic wastes increased the microbial biomass-C content in the soil and the microbial BC was positively correlated with the organic C content, the C/N, neutral detergent fibre/N (NDF/N) and acid detergent fibre/N (ADF/ N) ratios. The microbial biomass content decreased according to the period of incubation, especially when the compost used was immature. The microbial biomass-N was positively correlated with the total N and percentage of hemicellulose. The microbial biomass-C was linearly related with the microbial biomass-N and the ratio BC/BN was exponentially related with the BC.

Modeling and simulation of oxygen-limited partial nitritation in a membrane-assisted bioreactor (MBR).

Combination of a partial nitritation process and an anaerobic ammonium oxidation process for the treatment of sludge reject water has some general cost-efficient advantages compared to nitrification-denitrification. The integrated process features two-stage autotrophic conversion of ammonium via nitrite to dinitrogen gas with lower demand for oxygen and no external carbon requirement. A nitrifying membrane-assisted bioreactor (MBR) for the treatment of sludge reject water was operated under continuous aeration at low dissolved oxygen (DO) concentrations with the purpose of generating nitrite accumulation. Microfiltration was applied to allow a high sludge retention time (SRT), resulting in a stable partial nitritation process. During start-up of the MBR, oxygen-limited conditions were induced by increasing the ammonium loading rate and decreasing the oxygen transfer. At a loading rate of 0.9 kg N m(-3) d(-1) and an oxygen concentration below 0.1 mg DO L(-1), conversion to nitrite was close to 50% of the incoming ammonium, thereby yielding an optimal effluent within the stoichiometric requirements for subsequent anaerobic ammonium oxidation. A mathematical model for ammonium oxidation to nitrite and nitrite oxidation to nitrate was developed to describe the oxygen-limited partial nitritation process within the MBR. The model was calibrated with in situ determinations of kinetic parameters for microbial growth, reflecting the intrinsic characteristics of the ammonium oxidizing growth system at limited oxygen availability and high sludge age. The oxygen transfer coefficient (K(L)a) and the ammonium-loading rate were shown to be the appropriate operational variables to describe the experimental data accurately. The validated model was used for further steady state simulation under different operational conditions of hydraulic retention time (HRT), K(L)a, temperature and SRT, with the intention to support optimized process design. Simulation results indicated that stable nitrite production from sludge reject water was feasible with this process even at a relatively low temperature of 20 degrees C with HRT down to 0.25 days.

Stable carbon isotope analysis of different tissues of beef animals in relation to their diet.

As part of a larger experiment, 31 young bulls, divided into three groups, were given different diets containing either C(3) plants or a combination of C(3) and C(4) plant-based feeds in three feeding periods before slaughter. Variation in the proportion of C(4) plant material in the diets was made by including or not maize or maize-derived ingredients, whereas the other dietary constituents were from C(3) plants. Analysis of stable carbon isotope ratios (delta(13)C value) was performed on different tissues taken at slaughter: blood, plasma, liver, kidney fat, hair, muscle and ruminal contents. Blood and plasma samples were also taken at the beginning of each period. A highly significant difference was found in the delta(13)C values of blood and plasma samples taken from animals that had received a diet of only C(3) plants or with 59% C(4) material for 70 days. The delta(13)C values of all different samples taken at slaughter were highly significantly different between the three feeding groups that had received diets with 0, 13.5 or 35% C(4) material for on average 137, 139 and 83 days, respectively. For the three groups, samples of hair, muscle, plasma, whole blood and liver were significantly enriched in (13)C compared with the diet (except for liver in one group), whereas kidney fat was significantly depleted. The proportion of C(4) plant material could be accurately estimated from the delta(13)C values of different tissue samples. Stable carbon analysis of different tissues from beef animals can be used to trace back diets containing variable proportions of C(3) and C(4) plant material.

Relationship between soil organic C degradability and the evolution of the delta13C signature in profiles under permanent grassland.

The main objective of this research was to investigate to what extent the potential C dynamics of soil organic matter (SOM) are related to the degree of 13C enrichment with increasing depth in soil profiles under permanent grassland. The evolution of the C content and the 13C natural abundance (delta13C value) of SOM were investigated in three soil profiles (0-40 cm depth) under permanent grassland of varying texture (a loamy sand, a loam and a clay loam soil). The delta13C value of the SOM showed a gradual increase with increasing depth and decreasing C content in the profiles, ranging from 1.9 per thousand (loamy sand soil), 2.9 per thousand (clay loam soil) and 4 per thousand (loam soil) in relation to the delta13C value of SOM at the surface. The relationship between the 13C enrichment and total organic C content at different depths in the profiles (down to 40 cm depth in the loam and clay loam soil, down to 25 cm depth in the loamy sand soil) could be well described by the Rayleigh equation. The enrichment factors epsilon, associated with the Rayleigh approximation of the data, ranged from -1.57 per thousand (clay loam soil) to -1.64 per thousand (loamy sand soil) and -1.91 per thousand (loam soil). The potential C dynamics in four depth intervals from the profiles (0-10, 10-20, 20-30 and 30-40 cm depth) were determined by means of an incubation experiment. The C decomposition rate constants from the four sampling depths in the profiles showed a significant, positive correlation (y = 0.21x + 0.018, R(2) = 0.66, p < 0.005) with the corresponding Deltadelta13C values (change of the delta13C value per depth increment). A better correlation was obtained when only the data from the upper 20 cm in the profiles (y = 0.21x + 0.019, R(2) = 0.78, p < 0.05) were considered. These results suggest that the Deltadelta13C values in the surface layers of profiles under permanent grassland may serve as an indicator of the potential degradability or the stability of the SOM (in terms of C decomposition rate constants).

Quantifying nitrate retention processes in a riparian buffer zone using the natural abundance of 15N in NO3-.

Quantifying the relative importance of denitrification and plant uptake to groundwater nitrate retention in riparian zones may lead to methods optimising the construction of riparian zones for water pollution control. The natural abundance of 15N in NO3- has been shown to be an interesting tool for providing insights into the NO3- retention processes occurring in riparian zones. In this study, 15N isotope fractionation (variation in delta15N of the residual NO3-) due to denitrification and due to plant uptake was measured in anaerobic soil slurries at different temperatures (5, 10 and 15 degrees C) and in hydroponic systems with different plant species (Lolium perenne L., Urtica dioica L. and Epilobium hirsutum L.). It was found that temperature had no significant effect on isotope fractionation during denitrification, which resulted in a 15N enrichment factor epsilonD of -22.5 +/- 0.6 per thousand. On the other hand, nitrate uptake by plants resulted in 15N isotope fractionation, but was independent of plant species, leading to a 15N enrichment factor epsilonP of -4.4 +/- 0.3 per thousand. By relating these two laboratory-defined enrichment factors to a field enrichment factor for groundwater nitrate retention during the growing season (epsilonR = -15.5 +/- 1.0 per thousand ), the contribution of denitrification and plant uptake to groundwater nitrate retention could be calculated. The relative importance of denitrification and plant uptake to groundwater nitrate retention in the riparian buffer zone was 49 and 51% during spring, 53 and 47% during summer, and 75 and 25% during autumn. During wintertime, high micropore dissolved organic carbon (DOC) concentrations and low redox potentials due to decomposition of the highly productive riparian vegetation probably resulted in a higher denitrification rate and favoured other nitrate retention processes such as nitrate immobilisation or dissimilatory nitrate reduction to ammonium (DNRA). This could have biased the 15N isotope fractionation and led to a low 15N enrichment factor for groundwater nitrate retention during wintertime (-6.2 +/- 0.9 per thousand ). In contradiction to what many other studies suggest, it is possible that due to plant decomposition during the winter period other nitrate transformation processes compete with denitrification.

Simulation model for gas diffusion and methane oxidation in landfill cover soils.

Landfill cover soils oxidize a considerable fraction of the methane produced by landfilled waste. Despite many efforts this oxidation is still poorly quantified. In order to reduce the uncertainties associated with methane oxidation in landfill cover soils, a simulation model was developed that incorporates Stefan-Maxwell diffusion, methane oxidation, and methanotrophic growth. The growth model was calibrated to laboratory data from an earlier study. There was an excellent agreement between the model and the experimental data. Therefore, the model is highly applicable to laboratory column studies, but it has not been validated with field data. A sensitivity analysis showed that the model is most sensitive to the parameter expressing the maximum attainable methanotrophic activity of the soil. Temperature and soil moisture are predicted to be the environmental factors affecting the methane oxidizing capacity of a landfill cover soil the most. Once validated with field data, the model will enable a year-round estimate of the methane oxidizing capacity of a landfill cover soil.