Combining stable isotopes with contamination indicators: A method for improved investigation of nitrate sources and dynamics in aquifers with mixed nitrogen inputs.

Excessive nitrate (NO3−) 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 NO3− sources is critical to efficiently control or reverse NO3− contamination that affects many aquifers. In that respect, the use of stable isotope ratios 15N/14N and 18O/16O in NO3− (expressed as δ15N-NO3− and δ18O-NO3−, 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 NO3− source investigation in a shallow unconfined aquifer with mixed N inputs and a long established NO3− problem. In this tillage-dominated area of free-draining soil and subsoil, suspected NO3− 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 δ15N-NO3− and δ18O-NO3− data were superimposed on the classification. As δ15N-NO3− was plotted against δ18O-NO3−, comparisons were made between the different contamination groups. Overall, both δ variables were significantly and positively correlated (p 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 δ15N-NO3−, which suggests that i) NO3− contamination was dominated by an agricultural diffuse N source (most likely the large organic matter pool that has incorporated 15N-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 NO3− 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 disentangle NO3− contamination from animal and human wastes

Slow delivery of a nitrification inhibitor (dicyandiamide) to soil using a biodegradable hydrogel of chitosan

Using 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 (R2 = 0.99, p ⩽ 0.0001). Therefore, novel chitosan/glyoxal composite beads show a promising slow-release potential in soil for agrochemicals like DCD

Amendment of cattle slurry with the nitrification inhibitor dicyandiamide during storage: A new effective and practical N2O mitigation measure for landspreading

Large quantities of organic manures and soiled water are generated by cattle housing every year. These organic wastes are stored until soil conditions are suitable for landspreading or there is a crop requirement for nutrients. After land application, some nitrogen (N) is lost through the direct emission of nitrous oxide (N2O), a powerful greenhouse gas (GHG) produced by nitrification and partial denitrification of mineral N. The objective of this research was to investigate whether N2O losses could be mitigated after applying cattle slurry pre-mixed with the nitrification inhibitor dicyandiamide (DCD) during anaerobic storage. Contrary to our initial hypothesis, DCD mixed with slurry did not degrade for up to six months post amendment during an incubation study. These results highlight the feasibility of amending cattle slurry with DCD directly into slurry tanks any time before land application. This incubation experiment also showed that a slow release of DCD in slurry could be achieved if the amendment used was beads of a chitosan xerogel impregnated with DCD. A field study revealed that slurry application to grassland plots can cause large N2O emissions under wet and mild conditions when ammonia emissions are expected to be low. Slurry incubated with DCD for six month was effective at significantly (P < 0.01) decreasing N2O net cumulative emissions, which were 88% lower than in the slurry treatment with no DCD. The addition of DCD to slurry also reduced the fraction of N2O in the total GHG net cumulative emissions from 52% down to just 10%. Mixing slurry with DCD during storage could therefore offer farmers a cost-effective, practical, mitigation alternative to DCD broadcast application for the reduction of agricultural N losses