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.

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.

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.

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).

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" 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.

Characterizing microbial communities and processes in a modern stromatolite (Shark Bay) using lipid biomarkers and two-dimensional distributions of porewater solutes.

Modern microbial mats are highly complex and dynamic ecosystems. Diffusive equilibration in thin films (DET) and diffusive gradients in thin films (DGT) samplers were deployed in a modern smooth microbial mat from Shark Bay in order to observe, for the first time, two-dimensional distributions of porewater solutes during day and night time. Two-dimensional sulfide and alkalinity distributions revealed a strong spatial heterogeneity and a minor contribution of sulfide to alkalinity. Phosphate distributions were also very heterogeneous, while iron(II) distributions were quite similar during day and night with a few hotspots of mobilization. Lipid biomarkers from the three successive layers of the mat were also analysed in order to characterize the microbial communities regulating analyte distributions. The major hydrocarbon products detected in all layers included n-alkanes and isoprenoids, whilst other important biomarkers included hopanoids. Phospholipid fatty acid profiles revealed a decrease in cyanobacterial markers with depth, whereas sulfate-reducing bacteria markers increased in abundance in accordance with rising sulfide concentrations with depth. Despite the general depth trends in community structure and physiochemical conditions within the mat, two-dimensional solute distributions showed considerable small-scale lateral variability, indicating that the distributions and activities of the microbial communities regulating these solute distributions were equally heterogeneous and complex.

Simultaneous measurement of trace metal and oxyanion concentrations in water using diffusive gradients in thin films with a Chelex-Metsorb mixed binding layer.

A new diffusive gradients in thin films (DGT) technique with a mixed binding layer (Chelex-100 and the titanium dioxide based adsorbent Metsorb) is described for the simultaneous measurement of labile trace metal (Mn, Co, Ni, Cu, Cd, and Pb) and oxyanion (V, As, Mo, Sb, W, and P) concentrations in freshwater and seawater. The mixed binding layer (MBL) DGT technique was evaluated against the Chelex-DGT and Metsorb-DGT techniques, and all elution efficiencies and diffusion coefficients have been remeasured for the above analytes. Diffusion coefficients (D) measured using MBL-DGT generally agreed well with those measured by Chelex-DGT (DMBL/DChelex = 0.97-1.05), Metsorb-DGT (DMBL/DMetsorb = 0.97-1.01), and diffusion cell experiments. The measurement of trace metals and oxyanions by MBL-DGT was independent of pH (5.03-8.05) and ionic strength (I = 0.001-0.7 mol L(-1)). MBL-DGT accurately measured the concentration of trace metals and oxyanions in synthetic freshwater (CMBL/CSol = 0.82-1.18) over the 4 day deployment and also agreed well with Metsorb-DGT (CMBL/CMetsorb = 0.84-0.94) and Chelex-DGT (CMBL/CChelex = 0.88-1.11) measurements. In synthetic seawater, MBL-DGT accurately measured the concentration of metals and oxyanions (CMBL/CSol = 0.85-1.12) over 4 days, with the exception of Mo-none of the DGT techniques were capable of measuring Mo in seawater. MBL-DGT measured the Mn concentration accurately over the entire 4 day period, whereas Chelex-DGT only measured Mn accurately up to 2 days. The MBL-DGT method described in this study offers significant advantages over the ferrihydrite-Chelex-DGT method reported previously. These advantages include the commercial availability of both Metsorb and Chelex-100, the higher accuracy of Metsorb for measuring some oxyanions in freshwater and seawater, and the possibility of measuring Fe, which would not be possible using the Chelex-ferrihydrite binding layer.

DGT measurement of dissolved aluminum species in waters: comparing Chelex-100 and titanium dioxide-based adsorbents.

Aluminum is acutely toxic, and elevated concentrations of dissolved Al can have detrimental effects on both terrestrial and aquatic ecosystems. Robust analytical methods that can determine environmentally relevant Al fractions accurately and efficiently are required by the environmental monitoring community. A simple, robust passive sampling method, the diffusive gradients in thin films (DGT) technique, was evaluated for the measurement of dissolved Al species in freshwater and marine water using either Chelex-100 or Metsorb (a titanium dioxide-based binding agent) as the adsorbent. Mass vs time DGT deployments at pH 5.05 (Al(3+) and Al(OH)(2+) dominate) and 8.35 (Al(OH)(4)(-) dominates) demonstrated linear uptake of Al (R(2) = 0.989 and 0.988, respectively) for Metsorb. Similar deployments of Chelex-DGT showed linear uptake at pH 5.05 (R(2) = 0.994); however, at pH 8.35 the mass of Al accumulated was 40-70% lower than predicted, suggesting that Chelex-100 is not suitable for Al measurements at high pH. The Metsorb-DGT measurement was independent of pH (5.0-8.5) and ionic strength (0.001-0.7 mol L(-1) NaNO(3)), whereas the Chelex-DGT measurement was only independent of ionic strength at pH 5.0. At pH 8.4, increasing ionic strength led to considerable underestimation (up to 67%) of Al concentration. Deployments of Metsorb-DGT (up to 4 days) in synthetic freshwater (pH range 5.4-8.1) and synthetic seawater (pH 8.15) resulted in linear mass uptakes, and the concentration measured by DGT agreed well with solution concentrations. Conversely, deployment of Chelex-DGT in synthetic seawater and freshwater (pH ≥7.7 Al(OH)(4)(-) dominant species) resulted in a decrease in accumulated mass with increasing deployment time. In situ field evaluations in fresh, estuarine, and marine waters confirmed that Metsorb-DGT was more accurate than Chelex-DGT for the measurement of dissolved Al in typical environmental waters.

Investigating arsenic speciation and mobilization in sediments with DGT and DET: a mesocosm evaluation of oxic-anoxic transitions.

Mobilization of arsenic from freshwater and estuarine sediments during the transition from oxic to anoxic conditions was investigated using recently developed diffusive sampling techniques. Arsenic speciation and Fe(II) concentrations were measured at high resolution (1-3 mm) with in situ diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques. Water column anoxia induced Fe(II) and As(III) fluxes from the sediment. A correlation between water column Fe(II) and As(III) concentrations was observed in both freshwater (r(s) = 0.896, p < 0.001) and estuarine (r(s) = 0.557, p < 0.001) mesocosms. Porewater sampling by DGT and DET techniques confirmed that arsenic mobilization was associated with the reductive dissolution of Fe(III) (hydr)oxides in the suboxic zone of the sediment; a relationship that was visible because of the ability to measure the coincident profiles of these species using combined DGT and DET samplers. The selective measurement of As(III) and total inorganic arsenic by separate DGT samplers indicated that As(III) was the primary species mobilized from the solid phase to the porewater. This measurement approach effectively ruled out substantial As(V) mobilization from the freshwater and estuarine sediments in this experiment. This study demonstrates the capabilities of the DGT and DET techniques for investigating arsenic speciation and mobilization over a range of sediment conditions.

Speciation of dissolved inorganic arsenic by diffusive gradients in thin films: selective binding of AsIII by 3-mercaptopropyl-functionalized silica gel.

A diffusive gradients in thin films (DGT) technique for selectively measuring As(III) utilizes commercially available 3-mercaptopropyl-functionalized silica gel. Deployment of the new technique alongside the Metsorb-DGT for total inorganic arsenic allows the calculation of As(III) directly and As(V) by difference. Uptake of As(III) by mercapto-silica was quantitative and elution with a mixture of 1 mol L(-1) HNO(3) and 0.01 mol L(-1) KIO(3) gave a recovery of 85.6 ± 1.7%. DGT validation experiments showed linear accumulation of As(III) over time (R(2) > 0.998). Accumulation was unaffected by varying ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) and pH (3.5-8.5). Deployment of mercapto-silica DGT and Metsorb DGT in seawater spiked with As(III) and As(V) demonstrated the ability of the combined approach to accurately quantify both species in the presence of potential competing ions. Ferrihydrite DGT, which has been previously reported for the measurement of total inorganic arsenic, was evaluated in seawater and shown to underestimate both As(III) and As(V) at longer deployment times (72 h). Reproducibility of the new mercapto-silica DGT technique was good (relative standard deviations < 9%), and the average method detection limit was sufficiently low to allow quantification of ultratrace concentrations of As(III) (0.03 µg L(-1); 72 h deployment).

Contaminants in water, sediment and fish biomonitor species from natural and artificial estuarine habitats along the urbanized Gold Coast, Queensland.

Metal and pesticide contaminants were measured in water, sediment and fish species in various Gold Coast waterways, Queensland. With the exception of Cu, metal concentrations in water, measured using the diffuse gradients in a thin film (DGT) technique, complied with relevant Australian guidelines. Cu concentrations in these waterways have been related to recreational vessel activities previously. All sediment metal concentrations measured were below the national guidelines, although Cu, Zn and Pb were found to vary significantly between habitat types. Evidence of spikes in sediment pesticide concentrations (some banned over 50 years ago) was observed in some artificial residential waterways. Heavy metals and pesticides were measured in the tissue (muscle, gills and liver) of three economically important species of fish, with different feeding strategies (partly herbivore Arrhamphus sclerolepis, carnivore Acanthopagrus australis, detritivore Mugil cephalus). We tested the hypothesis that fish accumulate different amounts of contaminants from wetland habitats affected by different intensities of anthropogenic activities (i.e., marinas, artificial residential canals, artificial residential lakes, estuaries and natural, vegetated waterways). Significantly higher concentrations of Cu were found in the gills of each fish species from marinas compared to fish caught in other waterways. Furthermore, fish caught in canals had the second highest Cu and natural waterways the lowest. These results support the stated hypothesis for Cu and furthermore indicate that these fish species are suitable as biomonitors in estuarine waterways. Metal and pesticide concentrations in the edible muscle tissue of all fish complied with the Australian Food Standard Code recommended limits for human consumption, apart from As which is likely to be due to bioconcentration of lower toxicity organo-As species. These results indicate a low health risk for humans consuming fish, in terms of contaminant levels. The accumulated body of evidence on contaminants within Gold Coast waterways generally suggests that there are no major threats of metal or pesticide contamination, except for marina facilities which are a major source of Cu which also accumulates in fish. Water quality threats are also highlighted in residential canals, presumably as a consequence of their hydrological design.

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.

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.

New diffusive gradients in a thin film technique for measuring inorganic arsenic and selenium(IV) using a titanium dioxide based adsorbent.

A new diffusive gradients in a thin film (DGT) technique, using a titanium dioxide based adsorbent (Metsorb), has been developed and evaluated for the determination of dissolved inorganic arsenic and selenium. As(III), As(V), and Se(IV) were found to be quantitatively accumulated by the adsorbent (uptake efficiencies of 96.5-100%) and eluted in 1 M NaOH (elution efficiencies of 81.2%, 75.2%, and 88.7%). Se(VI) was not quantitatively accumulated by the adsorbent (<20%). Laboratory DGT validation experiments gave linear mass uptake over time (R(2) >or= 0.998) for As(III), As(V), and Se(IV). Consistent uptake occurred over pH (3.5-8.5) and ionic strength (0.0001-0.75 mol L(-1) NaNO(3)) ranges typical of natural waters, including seawater. Field deployments of DGT probes with various diffusive layer thicknesses confirmed the use of the technique in situ, allowing calculation of the diffusive boundary layers and an accurate measurement of inorganic arsenic. Reproducibility of the technique in field deployments was good (relative standard deviation <8%). Limits of detection (4 day deployments) were 0.01 microg L(-1) for inorganic arsenic and 0.05 microg L(-1) for Se(IV). The results of this study confirmed that DGT with Metsorb was a reliable and robust method for the measurement of inorganic arsenic and the selective measurement of Se(IV) within useful limits of accuracy.

Titanium dioxide-based DGT technique for in situ measurement of dissolved reactive phosphorus in fresh and marine waters.

A new diffusive gradients in a thin film (DGT) technique for measuring dissolved reactive phosphorus (DRP) in fresh and marine waters is reported. The new method, which uses a commercially available titanium dioxide based adsorbent (Metsorb), was evaluated and compared to the well-established ferrihydrite-DGT method (ferrihydrite cast within the polyacrylamide gel). DGT time-series experiments showed that the mass of DRP accumulated by Metsorb and ferrihydrite was linear with time when deployed in simple solutions. Both DGT methods showed predictable uptake across the pH (4.0-8.3) and ionic strength (0.0001-1 mol L(-1) NaNO(3)) ranges investigated, and the total capacity of the Metsorb binding phase (∼40,000 ng P) was 2.5-5 times higher than the reported total capacity of the ferrihydrite binding phase. The measurement of DRP in synthetic freshwater and synthetic seawater by Metsorb-DGT over a 4 day deployment period showed excellent agreement with the concentration of DRP measured directly in solution, whereas the ferrihydrite-DGT method significantly underestimated (23-30%) the DRP concentration in synthetic seawater for deployment times of two days or more. Field deployments of Metsorb-DGT samplers with various diffusive layer thicknesses allowed accurate measurement of both the diffusive boundary layer thickness and DRP concentration in situ. The Metsorb-DGT method performs similarly to ferrihydrite-DGT for freshwater measurements but is shown to be more accurate than the ferrihydrite method for determining DRP in seawater.

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).

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.

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.

Decline in recycled water quality during short-term storage in open ponds.

Changes were assessed in urban wastewater treatment plant (WWTP) effluent quality during short-term storage in open surface ponds. Water quality was monitored over five years at the inlets and outlets of open storage ponds located at three biological nutrient removal plants. Pond influent temperature, rainfall and sewage inflow were not found to be major factors. However, there was a trend for water temperature to be correlated negatively with nitrogenous nutrient and positively with faecal coliform values. The observed increases in faecal coliforms, nutrients and chemical oxygen demand were most likely caused through avian faecal contamination. These increases challenge the notion that pond storage has a positive or negligible effect on effluent quality. The observed one to two orders of magnitude increase in faecal coliforms may affect reuse scheme viability by limiting the range of uses under Australian water recycling guidelines. Potential improvements to short-term recycled water storage management at WWTPs could include the integration of monitoring requirements in WWTP discharge licences and recycling guidelines and the monitoring of all water quality parameters, including microbiological ones, at the point of entry into the recycled water distribution system, after WWTP storage, rather than directly post-disinfection.