Cattle excreta deposited on grazed grasslands are a major source of the greenhouse gas (GHG) nitrous oxide (N2O). Currently, many countries use the IPCC default emission factor (EF) of 2% to estimate excreta-derived N2O emissions. However, emissions can vary greatly depending on the type of excreta (dung or urine), soil type and timing of application. Therefore three experiments were conducted to quantify excreta-derived N2O emissions and their associated EFs, and to assess the effect of soil type, season of application and type of excreta on the magnitude of losses. Cattle dung, urine and artificial urine treatments were applied in spring, summer and autumn to three temperate grassland sites with varying soil and weather conditions. Nitrous oxide emissions were measured from the three experiments over 12months to generate annual N2O emission factors. The EFs from urine treated soil was greater (0.30-4.81% for real urine and 0.13-3.82% for synthetic urine) when compared with dung (-0.02-1.48%) treatments. Nitrous oxide emissions were driven by environmental conditions and could be predicted by rainfall and temperature before, and soil moisture deficit after application; highlighting the potential for a decision support tool to reduce N2O emissions by modifying grazing management based on these parameters. Emission factors varied seasonally with the highest EFs in autumn and were also dependent on soil type, with the lowest EFs observed from well-drained and the highest from imperfectly drained soil. The EFs averaged 0.31 and 1.18% for cattle dung and urine, respectively, both of which were considerably lower than the IPCC default value of 2%. These results support both lowering and disaggregating EFs by excreta type.

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Background: Measurements of carbohydrate-deficient transferrin (CDT) are used as markers of alcohol abuse. We developed a capillary zone electrophoresis (CZE) method aimed at improving accuracy of CDT testing. Methods: We studied 111 alcohol abusers with Alcohol Use Disorders Identification Test scores >11 and 50 teetotalers. CZE was performed with a P/ACE 5500, fused-silica capillaries, and a CEofix CDT reagent set. After iron saturation, sera were loaded by low-pressure injection, separated at 28 kV, and monitored at 214 nm. We identified the transferrin isoforms by migration times, treatment with 100 U/L neuraminidase, and immunosubtraction with anti-human transferrin and anti-C-reactive protein antibodies. We compared CZE results with current biological markers of alcohol abuse, including the %CDT turbidimetric immunoassay. Results: Migration times of the isoforms were identical in both populations. Asialotransferrin was missing in teetotalers but present in 92% of alcohol abusers. Disialotransferrin was higher in those who consumed excessive amounts of alcohol, whereas mean trisialotransferrin concentration was not affected by alcohol abuse. At cutoffs to maximize sensitivity and specificity, these values were 0.92 and 1 [mean ROC area (MRa), 0.96; 95% confidence interval (CI), 0.93–0.99] for asialotransferrin; 0.84 and 0.94 for the sum of asialo- + disialotransferrin (MRa, 0.94; 95% CI, 0.91–0.98); 0.79 and 0.94 for disialotransferrin (MRa, 0.89; 95% CI, 0.84–0.94); 0.62 and 0.53 for trisialotransferrin (MRa, 0.58; 95% CI, 0.49–0.68); 0.79 and 0.82 for a 3% %CDT; and 0.83 and 0.69 for a 2.6% cutoff (MRa, 0.87; 95% CI, 0.81–0.92). Current markers lack sensitivity (<0.65). Transferrins were not significantly correlated with serum enzymes and mean erythrocyte volume. Conclusions: CZE-isolated desialylated transferrin isoforms allowed differentiation between chronic alcohol abusers and teetotalers.

h i g h l i g h t sDicyandiamide (DCD) was encapsulated in glyoxal-crosslinked chitosan hydrogel beads. Chitosan delayed the release of nitrification inhibitor DCD in water and soil. DCD release was controlled by glyoxal polymerisation inside chitosan. The higher glyoxal polymerisation the more delayed DCD release in water or in soil. The higher glyoxal polymerisation the less DCD encapsulated in the beads. a r t i c l e i n f o b s t r a c tUsing chemical inhibitors to reduce soil nitrification decreases emissions of environmental damaging nitrate and nitrous oxide and improves nitrogen use efficiency in agricultural systems. The efficacy of nitrification inhibitors such as dicyandiamide (DCD) is limited in soil due to biodegradation. This study investigated if the persistence of DCD could be sustained in soil by slow release from a chitosan hydrogel. DCD was encapsulated in glyoxal-crosslinked chitosan beads where excess glyoxal was (i) partly removed (C beads) or (ii) allowed to dry (CG beads). The beads were tested in water and in soil. The beads contained two fractions of DCD: one which was quickly released in water, and one which was not. A large DCD fraction within C beads was readily available: 84% of total DCD bead content was released after 9 h immersion in water, while between 74% and 98% was released after 7 d in soil under low to high moisture conditions. A lower percentage of encapsulated DCD was readily released from CG beads: 19% after 9 h in water, and 33% after 7 d in soil under high rainfall conditions. Kinetic analysis indicated that the release in water occurred by quasi-Fickian diffusion. The results also suggest that DCD release was controlled by bead erosion and the leaching of glyoxal derivatives, predominantly a glyoxal-DCD adduct whose release was positively correlated with that of DCD (R 2 = 0.99, p 6 0.0001). Therefore, novel chitosan/glyoxal composite beads show a promising slow-release potential in soil for agrochemicals like DCD.

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Excessive nitrate (NO) concentration in groundwater raises health and environmental issues that must be addressed by all European Union (EU) member states under the Nitrates Directive and the Water Framework Directive. The identification of NO sources is critical to efficiently control or reverse NO contamination that affects many aquifers. In that respect, the use of stable isotope ratios N/N and O/O in NO (expressed as δN-NO and δO-NO, respectively) has long shown its value. However, limitations exist in complex environments where multiple nitrogen (N) sources coexist. This two-year study explores a method for improved NO source investigation in a shallow unconfined aquifer with mixed N inputs and a long established NO problem. In this tillage-dominated area of free-draining soil and subsoil, suspected NO sources were diffuse applications of artificial fertiliser and organic point sources (septic tanks and farmyards). Bearing in mind that artificial diffuse sources were ubiquitous, groundwater samples were first classified according to a combination of two indicators relevant of point source contamination: presence/absence of organic point sources (i.e. septic tank and/or farmyard) near sampling wells and exceedance/non-exceedance of a contamination threshold value for sodium (Na) in groundwater. This classification identified three contamination groups: agricultural diffuse source but no point source (D+P-), agricultural diffuse and point source (D+P+) and agricultural diffuse but point source occurrence ambiguous (D+P±). Thereafter δN-NO and δO-NO data were superimposed on the classification. As δN-NO was plotted against δO-NO, comparisons were made between the different contamination groups. Overall, both δ variables were significantly and positively correlated (p < 0.0001, r = 0.599, slope of 0.5), which was indicative of denitrification. An inspection of the contamination groups revealed that denitrification did not occur in the absence of point source contamination (group D+P-). In fact, strong significant denitrification lines occurred only in the D+P+ and D+P± groups (p < 0.0001, r > 0.6, 0.53 ≤ slope ≤ 0.76), i.e. where point source contamination was characterised or suspected. These lines originated from the 2-6‰ range for δN-NO, which suggests that i) NO contamination was dominated by an agricultural diffuse N source (most likely the large organic matter pool that has incorporated N-depleted nitrogen from artificial fertiliser in agricultural soils and whose nitrification is stimulated by ploughing and fertilisation) rather than point sources and ii) denitrification was possibly favoured by high dissolved organic content (DOC) from point sources. Combining contamination indicators and a large stable isotope dataset collected over a large study area could therefore improve our understanding of the NO contamination processes in groundwater for better land use management. We hypothesise that in future research, additional contamination indicators (e.g. pharmaceutical molecules) could also be combined to...

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Nitrification inhibitors are used in agriculture for the purpose of decreasing nitrogen (N) losses, by limiting the microbially mediated oxidation of ammonium (NH 4 + ) to nitrate (NO 3 − ). Successful inhibition of nitrification has been shown in numerous studies, but the extent to which inhibitors affect other N transformations in soil is largely unknown. In the present study, cattle slurry was applied to microcosms of three different grassland soils, with or without the nitrification inhibitor dicyandiamide (DCD). A solution containing NH 4 + and NO 3 − , labelled with 15 N either on the NH 4 + or the NO 3 − part, was mixed with the slurry before application. Gross N transformation rates were estimated using a 15 N tracing model. In all three soils, DCD significantly inhibited gross autotrophic nitrification, by 79-90%. Gross mineralization of recalcitrant organic N increased significantly with DCD addition in two soils, whereas gross heterotrophic nitrification from the same pool decreased with DCD addition in two soils. Fungal to bacterial ratios were not significantly affected by DCD addition. Total gross mineralization and immobilization increased significantly across the three soils when DCD was used, which suggests that DCD can cause non-target effects on soil N mineralization-immobilization turnover.