Toward In-Field Determination of Nitrate Concentrations Via Diffusive Gradients in Thin Films-Incorporation of Reductants and Color Reagents.

Diffusive gradients in thin films (DGTs) have been established as useful tools for the determination of nitrate, phosphate, trace metals, and organic concentrations. General use of DGTs, however, is limited by the subsequent requirement for laboratory analysis. To increase the uptake of DGT as a tool for routine monitoring by nonspecialists, not researchers alone, methods for in-field analysis are required. Incorporation of color reagents into the binding layer, or as the binding layer, could enable the easy and accurate determination of analyte concentrations in-field. Here, we sought to develop a chitosan-stabilized silver nanoparticle (AuNP) suspension liquid-binding layer which developed color on exposure to nitrite, combined with an Fe(0)-impregnated poly-2-acrylamido-2-methyl-1-propanesulfonic acid/acrylamide copolymer hydrogel [Fe(0)-p(AMPS/AMA)] for the reduction of nitrate. The AuNP-chitosan suspension was housed in a 3D designed and printed DGT base, with a volume of 2 mL, for use with the standard DGT solution probe caps. A dialysis membrane with a molecular weight cutoff of <15 kDa was used, as part of the material diffusion layer, to ensure that the AuNP-chitosan did not diffuse through to the bulk solution. This synthesized AuNP-chitosan provided quantitative nitrite concentrations (0 to 1000 mg L-1) and masses (145 µg) in laboratory-based color development studies. An Fe(III)-impregnated poly-2-acrylamido-2-methyl-1-propanesulfonic acid/acrylamide copolymer hydrogel [Fe(III)-p(AMPS/AMA)] was developed (10% AMPS, and 90% AMA), which was treated with NaBH4 to form an Fe(0)-p(AMPS/AMA) hydrogel. The Fe(0)-p(AMPS/AMA) hydrogel quantitatively reduced nitrate to nitrite. The total nitrite mass produced was ∼110 µg, from nitrate. The diffusional characteristics of nitrite and nitrate through the Fe(III)-p(AMPS/AMA) and dialysis membrane were 1.40 × 10-5 and 1.40 × 10-5 and 5.05 × 10-6 and 5.15 × 10-6 cm2 s-1 at 25 °C respectively. The Fe(0)-hydrogel and AuNP-chitosan suspension operated successfully in laboratory tests individually; however, the combined AuNP-chitosan suspension and Fe(0)-hydrogel DGT did not provide quantitative nitrate concentrations. Further research is required to improve the reaction rate of the AuNP-chitosan nitrite-binding layer, to meet the requirement of rapid binding to operate as a DGT.

The temperature and flow dependence of nitrate concentration and load estimates based on diffusive gradients in thin films.

Concentrations determined using diffusive gradients in thin films (DGT) have been used to derive time-averaged loads in streams and rivers. However, DGT provide time-weighted average concentrations that assume the independence of concentration and flow. Additionally, dynamic and coordinated changes in temperature, flow, and concentration are potential sources of bias in concentration and load calculations. We modeled scenarios in which temperature and flow were correlated to varying degrees with concentration and evaluated the consequences for DGT concentration and load calculations. As the correlation between solution flow and concentration moved toward 1 and -1, the load determined by DGT either overestimated or underestimated the actual load by as much as 30%. In DGT-based load estimates, the degree of potential bias should be assessed, and the concentration-flow relation should be characterized. As the correlation of analyte concentration and temperature approached 1 and -1, the deviation of the concentration determined by DGT from the actual concentration increased. In most cases, this bias was < 2%; however, if the changes in concentration and temperature were large (∼10 mg L-1 and ∼10 °C), the bias exceeded 5%. Concentration and temperature are unlikely to be perfectly or strongly correlated or anti-correlated in natural systems and thus should not affect the accuracy of DGT concentration calculations in most circumstances. The more solution temperature, flow, and concentration were uncorrelated, the closer DGT-derived concentration and load were to the actual solution concentration and load.

Development of bromide-selective Diffusive Gradients in Thin-Films for the measurement of average flow rate of streams.

Diffusive Gradients in Thin-Films (DGT) have traditionally been used to measure time-weighted average concentration in water. We tested whether Br--DGT in combination with the trace-dilution flow rate method, could be used as a new approach for measuring water flow rate. A novel bromide selective DGT based on the Purolite Bromide Plus anion exchange resin (Br--DGT) was developed, which provided environmental bromide concentrations comparable to grab samples. The Br--DGT provided quantitative bromide concentrations at a range of pH, competing ion concentrations, and in synthetic natural solution. The uptake efficiency was 95.7 ± 3.4%, and the elution efficiency was 95.5 ± 4.7%. The absorption maximum/saturation point of each binding disk was 0.684 ± 0.001 mg. Bromide adsorption to the binding layer was linear to 44.1% of the total binding capacity, 0.302 mg. The determined diffusion coefficient through the agarose cross-linked polyacrylamide (APA) hydrogels was 1.05 × 10-5 cm2 s-1 at 17.9 °C, temperature corrected to 25 °C was 1.29 × 10-5 cm2 s-1. DGT flow rates were between -14.7 and 6.50% of the flow independently monitored flow rate (weir). In comparison, grab sample flow rates diverged by 5.52 to 58.9% from the weir flow rate.

Utility of 'Diffusive Gradients in Thin-Films' for the measurement of nitrate removal performance of denitrifying bioreactors.

The increase in environmental nutrient availability as a result of human activities has necessitated the development of mitigation strategies for nutrient removal, such as nitrate. Current methods for determining the efficiency of different mitigation strategies required measurement of changes in nitrate concentrations, however, these methods can be expensive or do not account fully for the temporal variability of nitrate concentration. This study evaluated the utility of Diffusive Gradients in Thins-Films (DGT) for determining nitrate removal in two denitrifying bioreactors, and compared DGT performance to traditional approaches for determining performance, including high and low frequency water grab sampling. The binding layer was produced using the Purolite® A520E anion exchange resin. The uptake and elution efficiencies were 98.8% and 93.4% respectively. DGTs of three material diffusion layer thicknesses were placed in piezometers along longitudinal transects, to enable calculation of the diffusive boundary layer and provide replicates. These were removed after 16, 24 and 36 h, and the accumulated nitrate masses were extracted and quantified to calculate nitrate concentration. Concentrations were subsequently utilised to calculate nitrate removal rates in both bioreactors. Grab samples were taken at 30 and 60 min intervals over those periods, nitrate concentrations were also measured to determine nitrate removal. DGTs provided nitrate removal rates at bioreactor site one (controlled flow, wastewater treatment) of 14.83-30.75 g N m-3 d-1, and 1.22-3.63 g N m-3 d-1 at site two (variable flow, agricultural run-off). DGT determined nitrate concentrations and removal rates were in strong accordance with high frequency grab sampling, but data collection via DGTs was considerably easier. Utilising DGTs for the measurement of bioreactor performance overcame many of the challenges associated with high frequency grab sampling, and other methods, such as accounting for temporal variation in nitrate concentration and reduced analytical requirements.

A comment on scaling methane emissions from vegetation and grazing ruminants in New Zealand.

Keppler et al. (2006, Nature 439, 187-191) showed that plants produce methane (CH4) in aerobic environments, leading Lowe (2006, Nature 439, 148-149) to postulate that in countries such as New Zealand, where grazed pastures have replaced forests, the forests could have produced as much CH4 as the ruminants currently grazing these areas. Estimating CH4 emissions from up to 85 million ruminants in New Zealand is challenging and, for completeness, the capacity of forest and pastoral soils to oxidise CH4 should be included. On average, the CH4 emission rate of grazing ruminants is estimated to be 9.6 ± 2.6 g m-2 year-1 (±standard deviation), six times the corresponding estimate for an indigenous forest canopy (1.6 ± 1.1 g m-2 year-1). The forest's soil is estimated to oxidise 0.9 ± 0.2 g m-2 year-1 more CH4 than representative soils beneath grazed pasture. Taking into account plant and animal sources and the soil's oxidative capacity, the net CH4 emission rates of forest and grazed ecosystems are 0.6 ± 1.1 and 9.8 ± 2.6 g m-2 year-1, respectively.