In Situ DGT Sensing of Bioavailable Metal Fluxes to Improve Toxicity Predictions for Sediments.

An increased risk of adverse biological effects of metals in sediments may be accompanied by high labile metal fluxes as measured by the diffusive gradients in thin films (DGT) technique. To improve the usefulness of the DGT technique for sediment quality risk assessments, we used the simpler and more cost-effective piston DGTs rather than planar DGT probes to measure bioavailable metal fluxes in naturally contaminated sediments with widely varying composition (properties, metals and concentrations) and assessed their prediction of toxicity to amphipod reproduction in a flow-through microcosm. DGT pistons were deployed in sediments under different conditions, both in the field (in situ) and in the laboratory in sediment cores (lab-equilibrated) and in homogenized sediments (lab-homogenized). We demonstrated that the metal flux toxic units, DGTTU, measured in situ best predicted the magnitude of toxicity to amphipod reproduction. For sediments that had been highly disturbed before testing, DGTTU were less predictive for observed toxicity, but the copper flux alone (DGTTU-Cu) was effective, indicating copper was the primary cause of toxicity in these highly perturbed sediments. Overall, our study highlighted that the adverse effects induced by excessive bioavailable metals in contaminated sediments can be consistently sensed by the DGT pistons.

Evaluation of the Chelex-DGT technique for the measurement of rare earth elements in the porewater of estuarine and arine sediments.

This study describes the validation of a diffusive gradients in thin film (DGT) technique for determining lanthanide rare earth elements (REEs) and in situ measurements of REEs in sediment pore waters. Laboratory experiments demonstrated that Chelex-100 binding layers had uptake efficiencies ranging from 78.0% to 92.3% for all REEs. An eluent of 1 mol L-1 HNO3 was optimal with elution efficiencies >80% for all REEs. Mass versus time experiments confirmed that DGT uptake was linear for all REEs at pH 8.1, 6.6 and 3.9 over a period of 3-4 days. Diffusion coefficients (D) for all REEs were derived from these experiments using the slopes of the linear regressions. D values varied with pH but were generally similar to values reported previously. The Chelex-100 DGT technique from this study is highly sensitive for the measurement of REE concentrations with detection limits ranging from 1.8 to 45 ng L-1 based on 72 h deployments allowing measurements of natural trace REE levels. Chelex-100 DGT devices were deployed in estuarine and marine sediments over a period of 72 h and most REE porewater concentrations (50-10,410 ng L-1) were successfully measured. Individual depth profiles of REEs showed a complex response, with many peaks and troughs suggesting a high degree of sediment heterogeneity. Depth-averaged REE concentrations showed a typical zig-zag distribution, although patterns varied between sediment types, after the REEs were normalised using the Queensland Mud Composite shale reference. The Chelex-100 DGT technique therefore shows promise for REE measurements in sediments.

Oxidative Dissolution of Sulfide Minerals in Single and Mixed Sulfide Systems under Simulated Acid and Metalliferous Drainage Conditions.

Chalcopyrite, galena, and sphalerite commonly coexist with pyrite in sulfidic waste rocks. The aim of this work was to investigate their impact, potentially by galvanic interaction, on pyrite oxidation and acid generation rates under simulated acid and metalliferous drainage conditions. Kinetic leach column experiments using single-minerals and pyrite with one or two of the other sulfide minerals were carried out at realistic sulfide contents (total sulfide <5.2 wt % for mixed sulfide experiments), mimicking sulfidic waste rock conditions. Chalcopyrite was found to be most effective in limiting pyrite oxidation and acid generation with 77-95% reduction in pyrite oxidation over 72 weeks, delaying decrease in leachate pH. Sphalerite had the least impact with reduction of pyrite dissolution by 26% over 72 weeks, likely because of the large band gap and poor conductivity of sphalerite. Galena had a smaller impact than chalcopyrite on pyrite oxidation, despite their similar band gaps, possibly because of the greater extent of oxidation and the significantly reduced surface areas of galena (area reductions of >47% for galena vs <1.5% for chalcopyrite) over 72 weeks. The results are directly relevant to mine waste storage and confirm that the galvanic interaction plays a role in controlling acid generation in multisulfide waste even at low sulfide contents (several wt %) with small probabilities (≤0.23%) of direct contact between sulfide minerals in mixed sulfide experiments.

Development and evaluation of a new colorimetric DGT technique for the 2D visualisation of labile phosphate in soils.

A new colorimetric technique for the measurement of labile phosphate in soils using the diffusive gradients in thin films (DGT) technique was developed in this study. This technique can determine the mass of phosphate accumulated on the precipitated Zr-oxide based binding gel by forming the blue colour following the standard molybdate-ascorbic acid method. The optimal reaction temperature and coloration time were 20 °C (room temperature) and 26 min. After determining a well-fitted calibration equation, the technique was able to measure phosphate concentration up to 2.5 mg/L for 24 h deployment with a detection limit of 10.1 µg/L. Two-dimensional quantitative visualisation of phosphate diffusion in three phosphorus (P) fertilised soils were obtained using the colorimetric technique. The results from the colorimetric DGT technique were compared to the elution DGT technique and Colwell P extraction. The DGT techniques (colorimetric and elution) and Colwell P measurements demonstrated similar patterns of phosphate diffusion in soil. Both DGT techniques showed similar phosphate concentration along the concentric rings around the fertiliser application. A new, convenient, and fast DGT colorimetric technique was developed, and successfully used to measure the distribution of potentially available phosphate in soils. The new technique is less laborious than current techniques as it does not require any pre-treatment of the binding gel layers or heating during scanning, thus providing faster results. Therefore, the technique may be more suitable for in-field applications and can be used to investigate the in situ diffusion of potentially available phosphate from fertilisers, and relate this to the plant uptake of P.

In situ, high-resolution measurement of labile phosphate in sediment porewater using the DET technique coupled with optimized imaging densitometry.

Obtaining two-dimensional distributions of reactive phosphorus in sediment porewater is very important for understanding fine-scale phosphorus mobilization and sequestration processes in sediments. In this study, the diffusive equilibrium in thin films (DET) measurement based on computer imaging densitometry (CID) was studied in detail with optimal conditions described. This study focuses on evaluating the two-dimensional colorimetric DET method coupled with CID (DET-CID method) for porewater labile phosphate measurements. The result shows that the red channel filter is the optimum channel for sensitivity to process the image. Additionally, staining time and temperature have great influence on the method, and 20 min staining time and ≥25 °C staining temperature were recommended. The minimum detection limit of labile phosphate of this method was 0.300 mg P/L, and the maximum detection limit could reach 50.00 mg P/L. The DET-CID technique can be used to measure labile phosphate in a wide range of acidic and alkaline water bodies (pH = 2-10 and water hardness from 0 to 2000 mg/L as CaCO3). The linear regression analysis shows that this technique presents very similar results compared with other two existing methods (R2 = 0.999). Our results would give insights into the precisely measurements of labile phosphate in field applications.

Hydrolysis of doped conducting polymers.

Conducting polymers display a range of interesting properties, from electrical conduction to tunable optical absorption and mechanical flexibility, to name but a few. Their properties arise from positive charges (carbocations) on their conjugated backbone that are stabilised by counterions doped in the polymer matrix. In this research we report hydrolysis of these carbocations when poly(3,4-ethylenedioxy thiophene) is exposed to 1 mM aqueous salt solutions. Remarkably, two classes of anion interactions are revealed; anions that oxidise PEDOT via a doping process, and those that facilitate the SN1 hydrolysis of the carbocation to create hydroxylated PEDOT. A pKa of 6.4 for the conjugate acid of the anion approximately marks the transition between chemical oxidation and hydrolysis. PEDOT can be cycled between hydrolysis and oxidation by alternating exposure to different salt solutions. This has ramifications for using doped conducting polymers in aqueous environments (such as sensing, energy storage and biomedical devices).

DGT and selective extractions reveal differences in arsenic and antimony uptake by the white icicle radish (Raphanus sativus).

Increasing soil contamination of arsenic (As) and antimony (Sb) is posing a serious concern to human health. Due to insufficient studies on Sb, the biogeochemical behaviour and plant uptake of Sb are assumed to be similar to that of As. As part of extensive research unravelling As and Sb biogeochemistry and plant uptake, the diffusive gradients in thin films (DGT) technique and sequential extraction procedure (SEP) were applied to evaluate As and Sb uptake by the white icicle radish (Raphanus sativus) cultivated in diluted cattle dip soils contaminated with As only and diluted mining soils contaminated with both As and Sb under agricultural conditions. Labile As and Sb in these soils measured by DGT (CDGT), soil solution (Csol), and SEP (CSEP-labile), were compared with As and Sb bioaccumulation in R. sativus tissues. Regardless of contamination sources and measurement techniques, the results showed that As was consistently more labile than Sb although total As concentrations in two soil types were lower than total Sb. Labile As in cattle dip soils was higher than that in mining soils, although there were no significant differences in soil As concentrations. The analysis of R. sativus tissues revealed that the overall As bioaccumulation was 4.5-fold higher than for Sb, and that As translocation to shoots was limited. In contrast, considerable Sb translocation to shoots was observed. The As and Sb bioaccumulation were strongly correlated with their CSEP-labile, CDGT, and Csol (R2 = 0.87-0.99), demonstrating the effectiveness of these techniques in predicting As and Sb in the white icicle radish. Compared with the cherry bell radish previously studied, the white icicle radish exhibited higher bioaccumulation factors (BAF) for Sb, but lower BAF for As, and lower translocation of As and Sb to shoots, providing understanding of how As and Sb are accumulated by radish cultivars.

A new colorimetric DET technique for determining mm-resolution sulfide porewater distributions and allowing improved interpretation of iron(II) co-distributions.

Measurement of sulfide in pore waters is critical for understanding biogeochemical processes, especially within coastal sediments. Here we report the development of a new colorimetric DET (diffusive equilibration in thin films) technique for determining mm-resolution, two-dimensional sulfide distributions in sediment pore waters. This colorimetric sulfide DET method was based on the standard spectrophotometric methylene blue assay, but modified to allow quantitation of sulfide by computer imaging densitometry. The method detection and effective upper measurement limits of the optimised technique were 3.7 and 1000 µmol L-1, respectively. The optimised sulfide DET method was combined with the colorimetric iron(II) DET method to obtain co-distributions in coastal seagrass (Zostera muelleri) colonised sediment under light and dark conditions. In the dark, seagrass sediments were more reduced than in the light, with large areas being dominated by high porewater sulfide concentrations. These co-distributions were compared with those obtained using the previously described DET-DGT (diffusive gradients in thin films) method for measuring iron(II) and sulfide co-distributions. There was less overlap of iron(II) and sulfide distributions using the sulfide DET as the two DET methods are influenced most by the later hours of deployment, whereas the sulfide-DGT measurement integrates concentrations over the whole deployment period. Overlap was most apparent in very dynamic sediment zones, such as burrow wall sediments.

Comparison of DET, DGT and conventional porewater extractions for determining nutrient profiles and cycling in stream sediments.

Determining inorganic nutrient profiles to support understanding of nitrogen transformations in stream sediments is challenging, due to nitrification and denitrification being confined to particular conditions in potentially heterogeneous sediment influenced by benthic microalgae, rooted aquatic plants and/or diel light cycles. The diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques allow in situ determination of porewater concentration profiles, and distributions for some solutes. In this study, DGT, DET and conventional porewater extraction (sectioning and centrifugation) methods were compared for ammonium and nitrate in stream sediments under light and dark conditions. Two-dimensional distributions of Fe(ii) and PO4-P were also provided to indicate the degree of spatial and temporal heterogeneity in sediment porewater, which can explain the sources and sinks of ammonium at various depths in the sediments. Although the conventional porewater extraction method consistently measured higher NH4-N concentrations than the DGT and DET techniques, the study showed that the DET measurements were the most reliable indicator of porewater NH4-N concentrations, with the DGT data being usefully supplementary. However, a large proportion of the NO3-N concentrations measured by DGT and DET were close to or below the method detection limits. Therefore, further development of these techniques is required to reduce the blanks and detection limits to allow natural low sediment porewater NO3-N concentrations to be accurately monitored using DGT and DET. The study indicated that benthic microalgae had direct and indirect influences on porewater nutrient distributions over light-dark cycles. Overall, DGT and DET techniques can be useful for monitoring porewater nutrient concentrations and profiles and for determining how biological processes drive changes in sediment nutrient concentrations and distributions.

Removing ammonium from water and wastewater using cost-effective adsorbents: A review.

Ammonium is an important nutrient in primary production; however, high ammonium loads can cause eutrophication of natural waterways, contributing to undesirable changes in water quality and ecosystem structure. While ammonium pollution comes from diffuse agricultural sources, making control difficult, industrial or municipal point sources such as wastewater treatment plants also contribute significantly to overall ammonium pollution. These latter sources can be targeted more readily to control ammonium release into water systems. To assist policy makers and researchers in understanding the diversity of treatment options and the best option for their circumstance, this paper produces a comprehensive review of existing treatment options for ammonium removal with a particular focus on those technologies which offer the highest rates of removal and cost-effectiveness. Ion exchange and adsorption material methods are simple to apply, cost-effective, environmentally friendly technologies which are quite efficient at removing ammonium from treated water. The review presents a list of adsorbents from the literature, their adsorption capacities and other parameters needed for ammonium removal. Further, the preparation of adsorbents with high ammonium removal capacities and new adsorbents is discussed in the context of their relative cost, removal efficiencies, and limitations. Efficient, cost-effective, and environmental friendly adsorbents for the removal of ammonium on a large scale for commercial or water treatment plants are provided. In addition, future perspectives on removing ammonium using adsorbents are presented.

Diffusive Gradients in Thin Films Reveals Differences in Antimony and Arsenic Mobility in a Contaminated Wetland Sediment during an Oxic-Anoxic Transition.

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).

Development and evaluation of a new diffusive gradients in thin-films technique for measuring organotin compounds in coastal sediment pore water.

Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10-8 and 1.6 ×10-5ngcm2s-1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.

Comparing in situ colorimetric DET and DGT techniques with ex situ core slicing and centrifugation for measuring ferrous iron and dissolved sulfide in coastal sediment pore waters.

In productive coastal sediments the separation between different biogeochemical zones (e.g. oxic, iron(III)-reducing and sulfate-reducing) may be on the scale of millimetres. Conventional measurement techniques simply cannot resolve changes in pore water solute concentrations over such small distances. The diffusive equilibration in thin films (DET) and the diffusive gradients in thin films (DGT) techniques allow in situ determination of pore water solute concentration profiles with one-dimensional profiles and/or two-dimensional distributions on the millimetre scale. Here we compare measurements of pore water iron(II) and sulfide using conventional core sampling (slicing and centrifugation) and colorimetric DET-DGT techniques. DET-DGT samplers were deployed within replicate sediment cores from three different sites, which were processed by slicing and centrifugation following retrieval of the samplers, so that the measurements were approximately co-located. Iron(II) concentrations were determined by DET at all three sites (0.3-262 µmol L-1), while dissolved sulfide was consistently measured by DGT at one site only (0.003-112 µmol L-1). Pore water concentrations of iron(II) and sulfide determined conventionally following pore water extraction (iron(II); 0.4-88 µmol L-1 and sulfide; 0.05-36 µmol L-1), were systematically lower than the colorimetric DET and DGT measurements in the same sample. This underestimation was most likely due to the mixing of sediment from different biogeochemical zones during pore water extraction, which resulted in the precipitation of iron(II) and sulfide. This study shows that conventional pore water extraction methods can be unreliable for the determination of redox-active solutes due to artefacts associated with pore water mixing.

A modified DGT technique for the simultaneous measurement of dissolved inorganic nitrogen and phosphorus in freshwaters.

A modified diffusive gradients in thin films (DGT) technique uses both a mixed binding layer (PrCH and A520E resins for NH4-N and NO3-N, respectively) and multiple binding layers (Metsorb binding layer for PO4-P overlying the mixed binding layer) for the simultaneous measurement of dissolved inorganic nitrogen (nitrate and ammonium) and phosphate in freshwater (INP-DGT). High uptake and elution efficiencies were determined for a mixed (PrCH/A520E) binding gel for dissolved inorganic nitrogen and an agarose-based Metsorb binding layer for PO4-P. Diffusion coefficients (D) obtained from DGT time-series experiments (conductivity 180 µS cm-1) for NH4-N, NO3-N and PO4-P agreed well with those measured using individual DGT techniques in previous studies, but were characterised over a wider range of ionic strengths here. D for NO3-N and PO4-P were constant over a range of ionic strengths (between 100 and 800 µS cm-1) while the diffusion coefficient for NH4-N decreased with increasing ionic strength, as reported previously. The measurement of NH4-N, NO3-N and PO4-P using the INP-DGT was independent of pH (3.5-8.5) and quantitative over varying ionic strength ranges (up to 0.004 mol L-1 NaCl for NH4-N, up to 0.014 mol L-1 NaCl for NO3-N and over 0.1 mol L-1 NaCl for PO4-P) for a 24 h deployment time. Performance of INP-DGT in synthetic freshwaters with differing conductivity indicated the three nutrients were affected differently, with NH4-N measurements being most sensitive. Representative performance was determined for NO3-N (90-330 µS cm-1) and PO4-P (all tested conductivities) over a 72 h deployment period and for NH4-N (<330 µS cm-1) over a 24 h deployment period. Field validations showed that the ratios of INP-DGT concentrations to the average concentrations from grab samples were generally between 0.80 and 1.13 over 24 and 48 h deployment periods. To ensure the representative performance of INP-DGT for all three nutrients, the conductivity should not exceed 400 µS cm-1 and deployment times should be no longer than 24 h. The results of this study have demonstrated that INP-DGT could provide a cost-effective monitoring technique for measuring time-weighted average concentrations of dissolved inorganic nutrients in many freshwaters.

Evaluation of the DGT technique for selective measurement of aluminium and trace metal concentrations in an acid drainage-impacted coastal waterway.

The performance of DGT-Chelex, DGT-Metsorb and DGT-MBL (Chelex-Metsorb mixed binding layer) with open and restricted diffusive layers for trace metal (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and oxyanion (As, Mo, Sb, V) measurements, was evaluated in four natural waters with different pH (range 3.29-7.81). In moderately acidic (pH ≈ 5) and circumneutral (pH ≈ 6.3) waters, all three binding layers measured relatively similar concentrations of Al, while in more alkaline waters (pH ≈ 8) DGT-MBL measured higher concentrations than the other two binding layers. The measurements of DGT-Chelex and DGT-MBL for Co, Cu, Ni, Pb and Zn, and DGT-Metsorb and DGT-MBL for As, Sb and V were within 82-119% and not statistically different (p > 0.05) over the pH range 5-8. Mn measurements by DGT-Chelex and DGT-MBL were quite similar (95%) at pH 6.3, while DGT-MBL measured higher concentrations than DGT-Chelex at other pHs. The ratios of measured concentrations with different diffusive layers (Crestricted/Copen) were between 0.78 and 1.12 for all binding layers and no statistical differences (p > 0.05) were observed, except for Al at pH 7.81 and Cu at pH 6.28. DGT-MBL was comparable to DGT-Chelex for the measurement of most trace metals, and to DGT-Metsorb for the measurement of most oxyanions, over the pH range 5.05-7.81. Overall, DGT-MBL is superior to the other tested binding layers because it can simultaneously measure cations and anions, and accurately measure dissolved Al, across the greatest range of environmental conditions.

Antimony and arsenic exhibit contrasting spatial distributions in the sediment and vegetation of a contaminated wetland.

Antimony is a priority environmental contaminant that is relatively poorly studied compared to other trace metal(loid)s. In particular, the behaviour of antimony in wetland sediments, where anaerobic conditions often dominate, has received considerably less attention compared to well-drained terrestrial soil environments. Here we report the results of a spatial assessment of antimony in the sediments and vegetation of a freshwater wetland exposed to stibnite tailings for the past forty years. The concentration of antimony in the sediment decreased rapidly with distance from the tailings deposit, from a maximum of ∼22,000 mg kg-1 to ∼1000 mg kg-1 at a distance of ∼150 m. In contrast, arsenic was distributed more evenly across the wetland, indicating that it was more mobile under the prevailing hypoxic/anoxic conditions. Less clear trends were observed in the tissues of wetland plants, with the concentrations of antimony in waterlilies (2.5-195 mg kg-1) showing no clear trends with distance from the tailings deposit, and no correlation with sediment concentrations. Sedges and Melaleuca sp. trees had lower antimony concentrations (<25 mg kg-1 and 5 mg kg-1, respectively) compared to waterlilies, but showed a non-significant trend of higher concentrations closer to the tailings. For all vegetation types sampled, antimony concentrations were consistently lower than arsenic concentrations (Sb:As = 0.27-0.31), despite higher concentrations of antimony in the sediment. Overall, the results of this study highlight clear differences in the behaviour of antimony and arsenic in freshwater wetlands, which should be considered during the management and remediation of such sites.

"Diffusive Gradients in Thin Films" Techniques Provide Representative Time-Weighted Average Measurements of Inorganic Nutrients in Dynamic Freshwater Systems.

Nutrient concentrations in freshwater are highly variable over time, with changes driven by weather events, anthropogenic sources, modifications to catchment hydrology or habitats, and internal biogeochemical processes. Measuring infrequently collected grab samples is unlikely to adequately represent nutrient concentrations in such dynamic systems. In contrast, in situ passive sampling techniques, such as the "diffusive gradients in thin films" (DGT) technique, provide time-weighted average analyte concentrations over the entire deployment time. A pair of recently developed DGT techniques for nitrate (A520E-DGT) and ammonium (PrCH-DGT), as well as the Metsorb-DGT technique for phosphate, were used to monitor inorganic nutrients in different freshwater systems (i.e., streams and wetlands) with a range of environmental values and that were affected by different catchment types. Measurements of grab samples collected frequently (1-2 times daily, 8-10 a.m. and 2-4 p.m.) showed that concentrations of NH4-N and NO3-N changed dramatically in most of the studied freshwater systems over short time scales, while there were only relatively small fluctuations in PO4-P. The DGT measurements were highly representative in comparison with the average nutrient concentrations obtained from daily grab samples over short-term (24 h) and long-term (72 h) deployments. The ratios of DGT-labile concentrations to the average concentrations from grab samples were between 1.00 and 1.12 over the studied deployment periods. The results of this study confirmed that DGT measurements provided a reliable and robust method for monitoring NH4-N, NO3-N, and PO4-P in a diverse range of dynamic freshwater systems.

Determining time-weighted average concentrations of nitrate and ammonium in freshwaters using DGT with ion exchange membrane-based binding layers.

Commercially-available AMI-7001 anion exchange and CMI-7000 cation exchange membranes were utilised as binding layers for DGT measurements of NO3-N and NH4-N in freshwaters. These ion exchange membranes are easier to prepare and handle than DGT binding layers consisting of hydrogels cast with ion exchange resins. The membranes showed good uptake and elution efficiencies for both NO3-N and NH4-N. The membrane-based DGTs are suitable for pH 3.5-8.5 and ionic strength ranges (0.0001-0.014 and 0.0003-0.012 mol L-1 as NaCl for the AMI-7001 and CMI-7000 membrane, respectively) typical of most natural freshwaters. The binding membranes had high intrinsic binding capacities for NO3-N and NH4-N of 911 ± 88 µg and 3512 ± 51 µg, respectively. Interferences from the major competing ions for membrane-based DGTs are similar to DGTs employing resin-based binding layers but with slightly different selectivity. This different selectivity means that the two DGT types can be used in different types of freshwaters. The laboratory and field experiments demonstrated that AMI-DGT and CMI-DGT can be an alternative to A520E-DGT and PrCH-DGT for measuring NO3-N and NH4-N, respectively, as (i) membrane-based DGT have a consistent composition, (ii) avoid the use of toxic chemicals, (iii) provided highly representative results (CDGT : CSOLN between 0.81 and 1.3), and (iv) agreed with resin-based DGTs to within 85-120%.

Decomposition of jellyfish carrion in situ: Short-term impacts on infauna, benthic nutrient fluxes and sediment redox conditions.

Jellyfish often form blooms that persist for weeks to months before they collapse en masse, resulting in the sudden release of large amounts of organic matter to the environment. This study investigated the biogeochemical and ecological effects of the decomposition of jellyfish in a shallow coastal lagoon in New South Wales, Australia. Catostylus mosaicus carrion was added to the surface of shallow sub-tidal sediments and biogeochemical parameters and macrofaunal abundance immediately below the jellyfish carrion were measured over three days. Sediment plots without jellyfish served as controls. Sediment oxygen demand and carbon and nitrogen efflux increased by up to 60-fold in the jellyfish plots, compared to control plots, and dissolved organic nutrient fluxes were more sustained than in previous studies due to the use of fresh rather than frozen biomass. The decomposing jellyfish progressively altered sediment redox conditions, indicated by an increase in porewater iron (II) and sulfide concentrations measured by high-resolution in situ diffusive samplers. Abundance of some macrofaunal taxa in the jellyfish plots decreased relative to controls, however, the abundance of a carnivorous gastropod, which was presumably feeding on the carrion, increased in the jellyfish plots. While jellyfish carrion may be a food source for some macrofauna, low oxygen conditions coupled with the accumulation of toxic dissolved sulfides in the near-surface sediments may explain the overall change in the macroinfaunal community.

Development and evaluation of the diffusive gradients in thin films technique for measuring nitrate in freshwaters.

A new diffusive gradients in thin films (DGT) technique, using Purolite A520E anion exchange resin, was developed and evaluated for the measurement of NO3N in freshwaters. Purolite A520E had a very high uptake efficiency (>98%) and elution efficiency (82.7% with 2 mol L(-1) NaCl as eluent) for NO3N. The 24 h mass vs. time validation experiments had excellent linearity (R(2) ≥ 0.997) and the intrinsic capacity of the binding layer for NO3N was 849 ± 24 µg. NO3N uptake was quantitative over a pH (3.5-8.5) range typical of most natural freshwaters. Several anions competed with NO3N to produce a lower effective binding capacity for NO3N in the following order of selectivity, Cl(-) > HCO3(-) > SO4(2-) > H2PO4(-), although NO3N measurements were quantitative at ionic strengths 0.0001-0.008 mol L(-1) as NaCl. NO2N did not adversely affect determination of NO3N at typical concentrations. Field deployments of DGT samplers with varying diffusive layer thicknesses validated the use of the technique in situ, allowed calculation of the diffusive boundary layer and accurate measurement of NO3N (CDGT/CSOLN 1.03-1.04). Reproducibility of the technique during field deployments was good (relative standard deviation < 3.2%). Limits of detection of A520E-DGT for NO3N were 13.15 µg L(-1) and 7.52 µg L(-1) (equivalent to 0.94 and 0.54 µmol L(-1)) based on 24 h and 48 h deployments, respectively. A520E-DGT determined NO3N concentrations during field deployments were very similar to the average values obtained from 0.45 µm filtered grab samples, which confirmed that the new DGT technique produced highly representative results.