Towards a global interpretation of dual nitrate isotopes in surface waters

Modern anthropogenic activities have significantly increased nitrate (NO3-) concentrations in surface waters. Stable isotopes (delta N-15 and delta O-18) in NO3- offer a tool to deconvolute some of the human-made changes in the nitrogen cycle. They are often graphically illustrated on a template designed to identify different sources of NO3- and denitrification. In the two decades since this template was developed, delta N-1(5)- and delta O-1(8)-NO3- have been measured in a variety of ecosystems and through the nitrogen cycle. However, its interpretation is often fuzzy or complex. This default is no longer helpful because it does not describe surface water ecosystems well and biases researchers towards denitrification as the NO3- removal pathway, even in well oxygenated systems where denitrification is likely to have little to no influence on the nitrogen cycle. We propose a different scheme to encourage a better understanding of the nitrogen cycle and interpretation of NO3- isotopes. We use a mechanistic understanding of NO3- formation to place bounds on the oxygen isotope axis and provide a means to adjust for different environmental water isotope values, so data from multiple sites and times of year can be appropriately compared. We demonstrate that any interpretation of our example datasets (Canada, Kenya, United Kingdom) show clear evidence of denitrification or a mixture of NO3- sources simply because many data points fall outside of arbitrary boxes which cannot be supported once the range of potential delta O-1(8)-NO(3)(- )values has been considered.Modern anthropogenic activities have significantly increased nitrate (NO3-) concentrations in surface waters. Stable isotopes (delta N-15 and delta O-18) in NO3- offer a tool to deconvolute some of the human-made changes in the nitrogen cycle. They are often graphically illustrated on a template designed to identify different sources of NO3- and denitrification. In the two decades since this template was developed, delta N-1(5)- and delta O-1(8)-NO3- have been measured in a variety of ecosystems and through the nitrogen cycle. However, its interpretation is often fuzzy or complex. This default is no longer helpful because it does not describe surface water ecosystems well and biases researchers towards denitrification as the NO3- removal pathway, even in well oxygenated systems where denitrification is likely to have little to no influence on the nitrogen cycle. We propose a different scheme to encourage a better understanding of the nitrogen cycle and interpretation of NO3- isotopes. We use a mechanistic understanding of NO3- formation to place bounds on the oxygen isotope axis and provide a means to adjust for different environmental water isotope values, so data from multiple sites and times of year can be appropriately compared. We demonstrate that any interpretation of our example datasets (Canada, Kenya, United Kingdom) show clear evidence of denitrification or a mixture of NO3- sources simply because many data points fall outside of arbitrary boxes which cannot be supported once the range of potential delta O-1(8)-NO(3)(- )values has been considered.A

Hydrological assessment and monitoring of wetlands

The physical and chemical characteristics which favour wetland plant communities, primarily high soil water levels and anaerobic soil chemistry, are related directly to the hydrology/hydrogeology of the wetland and often its surrounding catchment. Appreciation and successful management of a wetland therefore almost always requires an understanding of its hydrological functioning, including the influences on hydrological functioning which often lie beyond the designated boundary of the sit

A deconvolutional Bayesian mixing model approach for river basin sediment source apportionment

Increasing complexity in human-environment interactions at multiple watershed scales presents major challenges to sediment source apportionment data acquisition and analysis. Herein, we present a step-change in the application of Bayesian mixing models: Deconvolutional-MixSIAR (D-MIXSIAR) to underpin sustainable management of soil and sediment. This new mixing model approach allows users to directly account for the 'structural hierarchy' of a river basin in terms of sub-watershed distribution. It works by deconvoluting apportionment data derived for multiple nodes along the stream-river network where sources are stratified by sub-watershed. Source and mixture samples were collected from two watersheds that represented (i) a longitudinal mixed agricultural watershed in the south west of England which had a distinct upper and lower zone related to topography and (ii) a distributed mixed agricultural and forested watershed in the mid-hills of Nepal with two distinct sub-watersheds. In the former, geochemical fingerprints were based upon weathering profiles and anthropogenic soil amendments. In the latter compound-specific stable isotope markers based on soil vegetation cover were applied. Mixing model posterior distributions of proportional sediment source contributions differed when sources were pooled across the watersheds (pooled-MixSIAR) compared to those where source terms were stratified by sub-watershed and the outputs deconvoluted (D-MixSIAR). In the first example, the stratified source data and the deconvolutional approach provided greater distinction between pasture and cultivated topsoil source signatures resulting in a different posterior distribution to non-deconvolutional model (conventional approaches over-estimated the contribution of cultivated land to downstream sediment by 2 to 5 times). In the second example, the deconvolutional model elucidated a large input of sediment delivered from a small tributary resulting in differences in the reported contribution of a discrete mixed forest source. Overall D-MixSIAR model posterior distributions had lower (by ca 25-50%) uncertainty and quicker model run times. In both cases, the structured, deconvoluted output cohered more closely with field observations and local knowledge underpinning the need for closer attention to hierarchy in source and mixture terms in river basin source apportionment. Soil erosion and siltation challenge the energy-food-water-environment nexus. This new tool for source apportionment offers wider application across complex environmental systems affected by natural and human-induced change and the lessons learned are relevant to source apportionment applications in other disciplines

Is phosphate δ¹⁸O any good for ecosystem science?

The isotopic composition of oxygen in phosphate (δ¹⁸OP) could be a useful tool for understanding ecosystem nutrient cycling and tracing aquatic phosphorus (P) pollution. This is based on evidence that P pollution sources impart distinct δ¹⁸OP signatures and that biological P turnover shifts δ¹⁸OP signatures towards a temperature-dependent equilibrium with the surrounding water (δ¹⁸OH2O). Here we present our experiences around the practical and quantitative limitations to using δ¹⁸OP across terrestrial-aquatic landscapes. A core part of this work was to evaluate whether δ¹⁸OP could distinguish agricultural PO4³¯ sources by measuring the integrated δ¹⁸OP composition and P speciation of contrasting inorganic fertilisers (compound v rock) and soil types (sands, loams, clays). We measured differences in the δ¹⁸OP composition between both soil and fertiliser types. Integrating these values into a catchment-scale mixing model indicated that diffuse ‘agriculture’ δ¹⁸OP signatures could span from 18 – 25 ‰, and are influenced by both fertiliser type and the time between application and leaching. These findings demonstrate the limits of using δ¹⁸OP as a tracer in unconstrained systems, and that overcoming these limits requires addressing uncertainties around sample processing and equilibrium fractionation

The significance of colloids in the transport of pesticides through Chalk

Agrochemical contamination in groundwater poses a significant long term threat to water quality and is of concern for legislators, water utilities and consumers alike. In the dual porosity, dual permeability aquifers such as the Chalk aquifer, movement of pesticides and their metabolites through the unsaturated zone to groundwater is generally considered to be through one of two pathways; a rapid by-pass flow and a slower ‘piston-flow’ route via the rock matrix. However, the dissolved form or ‘colloidal species’ in which pesticides move within the water body is poorly understood. Following heavy rainfall, very high peaks in pesticide concentration have been observed in shallow Chalk aquifers. These concentrations might be well explained by colloidal transport of pesticides. We have sampled a Chalk groundwater beneath a deep (30 m) unsaturated zone known to be contaminated with the pesticide diuron. Using a tangential flow filtration technique we have produced colloidal fractions from 0.45 μm to 1 kDa. In addition, we have applied agricultural grade diuron to a typical Chalk soil and created a soil water suspension which was also subsequently fractionated using the same filtration system. The deep groundwater sample showed no evidence of association between colloidal material and pesticide concentration. In comparison, despite some evidence of particle trapping or sorption to the filters, the soil water clearly showed an association between the < 0.45 μm and < 0.1 μm colloidal fractions which displayed significantly higher pesticide concentrations than the unfiltered sample. Degradation products were also observed and found to behave in a similar manner to the parent compound. Although relatively large colloids can be generated in the Chalk soil zone, it appears transport to depth in a colloidal-bound form does not occur. Comparison with other field and monitoring studies suggests that rapid by-pass flow is unlikely to occur beneath 4–5 m. Therefore, shallow groundwaters are most at risk from rapid transport of high concentrations of pesticide–colloidal complexes. The presence of a deep unsaturated zone will mean that most of the colloidal–complexes will be filtered by the narrow Chalk pores and the majority of pesticide transport will occur in a ‘dissolved’ form through the more gradual ‘piston-flow’ route

δ¹⁸O as a tracer of PO₄³¯ losses from agricultural landscapes

Accurately tracing the sources and fate of excess PO₄³¯ in waterways is necessary for sustainable catchment management. The natural abundance isotopic composition of O in PO₄³¯ (δ¹⁸OP) is a promising tracer of point source pollution, but its ability to track diffuse agricultural pollution is unclear. We tested the hypothesis that δ¹⁸OP could distinguish between agricultural PO₄³¯ sources by measuring the integrated δ¹⁸OP composition and P speciation of contrasting inorganic fertilisers (compound v rock) and soil textures (sand, loam, clay). δ¹⁸OP composition differed between the three soil textures sampled across six working livestock farms: sandy soils had lower overall δ¹⁸OP values (21 ± 1 ‰) than the loams (23 ± 1 ‰), which corresponded with a smaller, but more readily leachable, PO₄³¯ pool. Fertilisers had greater δ¹⁸OP variability (~8‰) driven by both fertiliser type and manufacturing year. Upscaling these values showed that ‘agricultural soil leaching’ δ¹⁸OP signatures could span from 18 – 25 ‰, and are influenced by both fertiliser type and the time between application and leaching. These findings emphasise the potential of δ¹⁸OP to untangle soil-fertiliser P dynamics under controlled conditions, but that its use to trace catchment-scale agricultural PO₄³¯ losses is limited by uncertainties in soil biological P cycling and its associated isotopic fractionation

Integrated time-lapse geoelectrical imaging of wetland hydrological processes

Wetlands provide crucial habitats, are critical in the global carbon cycle, and act as key biogeochemical and hydrological buffers. The effectiveness of these services is mainly controlled by hydrological processes, which can be highly variable both spatially and temporally due to structural complexity and seasonality. Spatial analysis of 2-D geoelectrical monitoring data integrated into the interpretation of conventional hydrological data has been implemented to provide a detailed understanding of hydrological processes in a riparian wetland. A two-layered hydrological system was observed in the peat. In the lower part of the peat, upwelling of deeper groundwater from underlying deposits was considered the driver for a 30% increase in peat resistivity during Winter/Spring. In Spring/Summer there was a 60% decrease in resistivity in the near-surface peats due to plant transpiration and/or microbial activity. Water exchange between the layers only appeared to be initiated following large drops in the encircling surface water stage. For the first time, we demonstrated that automated interpretation of geoelectrical data can be used to quantify ground movement in the vertical direction. Here, we applied this method to quantify shrink-swell of expandable soils, affecting hydrological parameters, such as, porosity and permeability. This study shows that an integrated interpretation of hydrological and geophysical data can significantly improve the understanding of wetland hydrological processes. Potentially, this approach can provide the basis for the evaluation of ecosystem services and may aid in the optimization of wetland management strategies