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The restoration of mangroves in urban environments can increase the risk of contaminant exposure and subsequent health effects to resident biota, yet this risk is rarely considered in mangrove restoration programs. Here we assessed the influence of sediment chemistry on contaminant bioaccumulation in shore crabs from restored and natural mangroves in urban environments compared to a reference site. The concentrations of some trace elements were several-fold higher in the sediment and crab tissues of the urban restored site compared to the natural reference site (Cd = 6×, Co = 7×, Cr = 4×, Mn = 30×, and Ni = 18× greater in sediments, while Cd = 4×, Co = 2×, Cr = 2×, Mn = 6×, and Ni = 3× greater in crab tissues). NMR-based metabolomics on crabs revealed higher abundances of proline and glutamate at urban sites, which may be indicative of physiological stress from trace element contamination. Choice experiments were used to test habitat selectivity by crabs from each population, and showed that crabs avoided sediments from the contaminated urban sites. Our results suggest that restoring mangroves in contaminated environments could create ecological sinks, where animals take residence in the new habitat but are exposed to sediment-based contaminants, with potential implications for organism and population health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Seagrasses increase sediment complexity by trapping particulates and influencing biogeochemical cycles via root oxygen loss and organic matter exudation. However, their impact on trace metal sequestration is poorly studied. We found significantly higher trace metal concentrations in seagrass sediments compared to adjacent bare sediments, correlating with total organic carbon, iron, and fine sediments. Sequential extractions showed that most trace metals were dominated by recalcitrant fractions (oxidizable and residual fractions), representing phases such as organic matter, iron sulfides, and crystalline iron oxides. Depth-dependent trends in trace metal partitioning were evident. For example, arsenic in the oxidizable fraction only weakly correlated with Fe in surface sediments (r sp  = 0.55) but correlated strongly in deeper sediments (r sp  = 0.87), consistent with iron sulfides being a dominant host-phase. Overall, these results suggest that the unique geochemical conditions facilitated by seagrasses play an important role in sequestering trace metals in urban estuarine sediments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In the state of New South Wales (NSW), Australia, recent legislative action has focused on identifying key threats to the marine estate. We used a systematic literature review to evaluate the knowledge status of the effects of estuarine outflows on coastal marine ecosystems, within the environmental, hydrological, and physicochemical context of NSW waters. Results focussed on studies that measured outcomes for marine biota (n = 56). Trace elements and organochlorines were the most frequently studied contaminant types, with reported biological concentrations often below guideline values but detected at the highest concentrations adjacent to urban sources. Few studies measured the impacts of legacy and emerging contaminants to animal health, or the flow on effects to marine ecosystems in NSW. Our review highlights key biological and geographical data gaps in estuarine outflow research in NSW, particularly of the impact on ecosystems of exported carbon and nutrients to the oligotrophic waters of NSW., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Estuaries provide critical ecosystem services, and yet are increasingly under threat from urbanization. Non-invasive approaches to monitor biodiversity resident to or migrating through estuaries is critical to evaluate the holistic health of these ecosystems, often based entirely on water quality. In this study we compared tree of life metabarcoding (ToL-metabarcoding) biodiversity detections with measurements of physico-chemical variables (chlorophyll a, turbidity, total nitrogen, total phosphorous, dissolved oxygen) at eight sites of varying degrees of water quality in the Gold Coast Broadwater Estuary (Queensland, Australia). These sites were ranked according to an adapted Water Quality Index (WQI) score. Here, we detected 787 unique taxa, adding 137 new biodiversity records to the region, mostly micro-organisms such as bacteria, ciliates, diatoms, dinoflagellates, and cryptomonads. Sites with the lowest WQI were characterised by higher turbidity, lower dissolved oxygen, as well as higher total nitrogen and phosphorous, which correlated with an increased diversity of bacteria, ciliates, and green algae. Similarly, the composition of taxa was significantly different between sites with variable WQI values for most taxa but was less apparent for larger vertebrate groups. These findings suggest that rapid ToL-metabarcoding biodiversity detections, particularly for lower order taxonomic groups, can serve as valuable indicators of flora and fauna across the tree of life associated with dynamically shifting estuarine health along urbanized coastlines., Competing Interests: Declaration of competing interest Shaun P. Wilkinson is a director and shareholder of Wilderlab NZ Ltd., a commercial eDNA processing laboratory. All other co-authors declare no known competing financial interests or personal relationships that influenced the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Satellite retrieval of total suspended solids (TSS) and chlorophyll-a (chl-a) was performed for the Gold Coast Broadwater, a micro-tidal estuarine lagoon draining a highly developed urban catchment area with complex and competing land uses. Due to the different water quality properties of the rivers and creeks draining into the Broadwater, sampling sites were grouped in clusters, with cluster-specific empirical/semi-empirical prediction models developed and validated with a leave-one-out cross validation approach for robustness. For unsampled locations, a weighted-average approach, based on their proximity to sampled sites, was developed. Confidence intervals were also generated, with a bootstrapping approach and visualised through maps. Models yielded varying accuracies (R 2  = 0.40-0.75). Results show that, for the most significant poor water quality event in the dataset, caused by summer rainfall events, elevated TSS concentrations originated in the northern rivers, slowly spreading southward. Conversely, high chl-a concentrations were first recorded in the southernmost regions of the Broadwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Cell-based toxicity testing has emerged as a useful tool in (eco)toxicological research, allowing the ethical assessment of the effects of contaminants such as trace metals on marine megafauna. However, metal interactions with various dissolved ligands in the microplate environment may influence the effective exposure concentrations. Hence, the cells are not exposed to the nominal concentrations within the test system. This study aimed to establish and evaluate the effectiveness of cell-based bioassays for investigating the toxicity of selected metals in dugongs through the following objectives: (1) measure the cytotoxic potential of cadmium (Cd 2+ ), and chromium (Cr 6+ ) to dugong skin cell cultures, (2) investigate the interactions between media constituents and selected trace metals in cell-based bioassays, and (3) evaluate the risk to a free-ranging population of dugong based on effect values. Chromium was the most toxic of the metals tested (EC 50  = 1.14 µM), followed by Cd (EC 50  = 6.35 µM). Assessment of ultrafiltered (< 3 kDa) exposure media showed that 1% and 92.5% of Cr and Cd were associated with larger organic components of the media. Further, the binding of Cd to media constituents was calculated to underestimate Cd toxicity in cell-based assays by an order of magnitude. This understanding of metal partitioning in cell-based bioassays provides a more accurate method for assessing toxicity in cell-based bioassays. In addition, this study illustrated that dugong cells are more sensitive to Cr and Cd than other marine wildlife species. The chemical risk assessment found the dugong population in Moreton Bay to be at high risk from Cd exposure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

This study establishes baseline water quality characteristics for the Gold Coast Broadwater, southern Moreton Bay (Australia) utilising routinely monitored parameters between 2016 and 2021, across 18 sites. Combined site mean concentrations of NO x -N, NH 3 -N and total nitrogen were 11.4 ± 33.4 μg/L, 12.7 ± 27.2 μg/L, and 169 ± 109 μg/L, respectively, whilst PO 4 -P and total phosphorous were 7.30 ± 5.10 μg/L and 21.7 ± 14.1 μg/L. Additionally, total suspended solids and turbidity combined site means were 6.6 ± 6.0 mg/L and 3.4 ± 2.9 NTU, respectively. During high rainfall periods nutrient concentrations increased by up to >200-, >150-, 15-, 12- and >12-fold for NO x -N, NH 3 -N, TN, PO 4 -P and TP, respectively, compared to quiescent conditions. Furthermore, TSS and NTU values increased by up to 15- and 40-fold during periods of measured rainfall compared to quiescent conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Stormwater runoff typically contains significant quantities of metal contaminants that enter urban waterways over short durations and represent a potential risk to water quality. The origin of metals within the catchment and processes that occur over the storm can control the partitioning of metals between a range of different forms. Understanding the fraction of metals present in a form that is potentially bioavailable to aquatic organisms is useful for environmental risk assessment. To help provide this information, the forms and dynamics of metal contaminants in an urban system were assessed across a storm. Temporal patterns in the concentration of metals in dissolved and particulate (total suspended solids; TSS) forms were assessed from water samples, and diffusive gradients in thin-films (DGTs) were deployed to measure the DGT-labile time-integrated metal concentration. Results indicate that the concentrations of dissolved and TSS-associated metals increased during the storm, with the metals Al, Cd, Co, Cu, Pb and Zn representing the greatest concern relative to water quality guideline values (GVs). The portion of labile metal as measured by DGT devices indicated that during the storm a substantial fraction (∼98%) of metals were complexed and pose a lower risk of acute toxicity to aquatic organisms. Comparison of DGT results to GVs indicate that current GVs are likely quite conservative when assessing stormwater pollution risks with regards to metal contaminants. This study provides valuable insight into the forms and dynamics of metals in an urban system receiving stormwater inputs and assists with the development of improved approaches for the assessment of short-term, intermittent discharge events., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Introduction: Poor gestational outcomes due to placental insufficiency can have lifelong consequences for mother and child., Objective: There is a need for better methods of diagnosis, and elemental metabolomics may provide a means to determine the risk of gestational disorders., Methods: This study used blood plasma samples collected at 36 weeks' gestation from women who later developed preeclampsia (n = 38), or small-for-gestational age babies (n = 91), along with matched controls (n = 193). Multi-element analysis was conducted by inductively coupled plasma mass spectrometer (ICP-MS), allowing simultaneous measurement of 28 elements., Results: Women who later developed PE, exhibited significantly increased concentrations of K, Rb and Ba. For SGA pregnancies, there was a significant increase in Cu and a decrease in As concentrations. Despite significant differences in single elements, the elemental profile of groups indicated no clustering of control, PE, or SGA samples. Positive predicative values correctly identified approximately 60% of SGA and 70% of PE samples., Conclusion: This is the first-time elemental metabolomics has been used to predict SGA and PE at 36 weeks. Though significant changes were identified, routine clinical use may be limited but may contribute to a multi marker test. Future analysis should include other biomarkers, metabolic data or clinical measurements made throughout gestation., (© 2021. Crown.)

Synchrotron-based X-ray fluorescence microscopy (XFM) coupled with X-ray absorption near-edge structure (XANES) imaging was used to study selenium (Se) biodistribution and speciation in Limnodynastes peronii tadpoles. Tadpoles were exposed to dissolved Se (30 μg/L) as selenite (Se IV ) or selenate (Se VI ) for 7 days followed by 3 days of depuration. High-resolution elemental maps revealed that Se partitioned primarily in the eyes (specifically the eye lens, iris, and retinal pigmented epithelium), digestive and excretory organs of Se IV -exposed tadpoles. Speciation analysis confirmed that the majority of accumulated Se was converted to organo-Se. Multielement analyses provided new information on Se colocalization and its impact on trace element homeostasis. New insights into the fate of Se on a whole organism scale contribute to our understanding of the mechanisms and risks associated with Se pollution.

A normal pregnancy is essential to establishing a healthy start to life. Complications during have been associated with adverse perinatal outcomes and lifelong health problems. The ability to identify risk factors associated with pregnancy complications early in gestation is vitally important for preventing negative foetal outcomes. Maternal nutrition has been long considered vital to a healthy pregnancy, with micronutrients and trace elements heavily implicated in maternofoetal metabolism. This study proposed the use of elemental metabolomics to study multiple elements at 18 weeks gestation from blood plasma and urine to construct models that could predict outcomes such as small for gestational age (SGA) (n = 10), low placental weight (n = 18), and preterm birth (n = 13) from control samples (n = 87). Samples collected from the Lyell McEwin Hospital in Adelaide, South Australia, were measured for 27 plasma elements and 37 urine elements by inductively coupled plasma mass spectrometry. Exploratory analysis indicated an average selenium concentration 20 μg/L lower than established reference ranges across all groups, low zinc in preterm (0.64 μg/L, reference range 0.66-1.10 μg/L), and higher iodine in preterm and SGA gestations (preterm 102 μg/L, SGA 111 μg/L, reference range 40-92 μg/L). Using random forest algorithms with receiver operating characteristic curves, low placental weight was predicted with 86.7% accuracy using plasma, 78.6% prediction for SGA with urine, and 73.5% determination of preterm pregnancies. This study indicates that elemental metabolomic modelling could provide a means of early detection of at-risk pregnancies allowing for more targeted monitoring of mothers, with potential for early intervention strategies to be developed.

There is increasing interest in understanding potential impacts of complex pollutant profiles to long-lived species such as the green sea turtle (Chelonia mydas), a threatened megaherbivore resident in north Australia. Dietary ingestion may be a key exposure route for metals in these animals and marine plants can accumulate metals at higher concentrations than the surrounding environment. We investigated concentrations of 19 metals and metalloids in C. mydas forage samples collected from a group of offshore coral cays and two coastal bays over a period of 2-3 years. Although no samples exceeded sediment quality guidelines, coastal forage Co, Fe, and V concentrations were up to 2-fold higher, and offshore forage Sr concentrations were ~3-fold higher, than global seagrass means. Principal Component Analysis differentiated coastal bay from coral cay forage according to patterns consistent with underlying terrigenous-type or marine carbonate-type sediment geochemistry, such that coastal bay forage was higher in Fe, Co, Mn, Cu, and Mo (and others) but forage from coral cays was higher in Sr and U. Forage from the two coastal bays was differentiated according to temporal variation in metal profiles, which may be associated with a more episodic sediment disturbance regime in one of the bays. For all study locations, some forage metal concentrations were higher than previously reported in the global literature. Our results suggest that forage metal profiles may be influenced by the presence of some metals in insoluble forms or bound to ultra-fine sediment particles adhered to forage surfaces. Metal concentrations in Great Barrier Reef forage may be present at levels higher than expected from the global seagrass literature and appear strongly influenced by underlying sediment geochemistry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.)

Background: Trace elements are an essential requirement for human health and development and changes in trace element status have been associated with pregnancy complications such as gestational diabetes mellitus (GDM), pre-eclampsia (PE), fetal growth restriction (FGR), and preterm birth. Elemental metabolomics, which involves the simultaneous quantification and characterisation of multiple elements, could provide important insights into these gestational disorders., Methods: This study used an Agilent 7900 inductively coupled plasma mass spectrometer (ICP-MS) to simultaneously measure 68 elements, in 166 placental cord blood samples collected from women with various pregnancy complications (control, hypertensive, PE, GDM, FGR, pre-term, and post-term birth)., Results: There were single element differences across gestational outcomes for elements Mg, P, Cr, Ni, Sr, Mo, I, Au, Pb, and U. Hypertensive and post-term pregnancies were significantly higher in Ni concentrations when compared to controls (control = 2.74 μg/L, hypertensive = 6.72 μg/L, post-term = 7.93 μg/L, p < 0.05), iodine concentration was significantly higher in post-term pregnancies (p < 0.05), and Pb concentrations were the lowest in pre-term pregnancies (pre-term = 2.79 μg/L, control = 4.68 μg/L, PE = 5.32 μg/L, GDM = 8.27 μg/L, p < 0.01). Further analysis was conducted using receiver operating characteristic (ROC) curves for differentiating pregnancy groups. The ratio of Sn/Pb showed the best diagnostic power in discriminating between control and pre-term birth with area under the curve (AUC) 0.86. When comparing control and post-term birth, Mg/Cr (AUC = 0.84), and Cr (AUC = 0.83) had the best diagnostic powers. In pre-term and post-term comparisons Ba was the best single element (81.5%), and P/Cu provided the best ratio (91.7%)., Conclusions: This study has shown that analysis of multiple elements can enable differentiation between fetal cord blood samples from control, hypertensive, PE, GDM, FGR, pre and post-term pregnancies. This data highlights the power of elemental metabolomics and provides a basis for future gestational studies., Competing Interests: Declaration of Competing Interest There are no conflicts of interest to declare., (Crown Copyright © 2019. Published by Elsevier GmbH. All rights reserved.)

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 (C DGT ), soil solution (C sol ), and SEP (C SEP-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 C SEP-labile , C DGT , and C sol (R 2  = 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., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The Macleay River in eastern Australia is severely impacted by historic stibnite- and arsenopyrite-rich mine-tailings. We explore the partitioning, speciation, redox-cycling, mineral associations and mobility of antimony and arsenic along >70 km reach of the upper Macleay River. Elevated Sb/As occur throughout the active channel-zone and in floodplain pockets up to the regolith margin, indicating broad dispersal during floods. Sb concentrations in bulk-sediments decay exponentially downstream more efficiently than As, likely reflecting sediment dilution, hydraulic sorting and comparatively greater leaching of (more mobile) Sb(V) species. However, Sb in bulk-sediments becomes proportionally more bio-available downstream. Sb(V) and As(V) species dominate stream fine-grained (<180 μm) bulk-sediments, reflecting oxidative weathering downstream. Increasing poorly-crystalline Fe(III) [Fe(III) HCl ] in bulk-sediments also indicates progressive oxidative weathering of Fe(II)-bearing minerals downstream and significant (P < .05) correlations exist between PO 4 - 3 -exchangeable As and Sb fractions and Fe(III) HCl . Accumulations of poorly-crystalline Fe(III) precipitates (mainly ferrihydrite/feroxyhyte) occur intermittently in hyporheic-zone seeps and are enriched in As relative to Sb and contain some As(III) and Sb(III) (~30-40%). There is dynamic in-stream redox-cycling of both Sb and As, with localised S-coordinated As and Sb species re-forming in organic-rich, hyporheic sediments subject to contemporary sulfidogenesis. Sb [mainly Sb(V)] is comparatively more mobile in hyporheic and surface waters under oxic conditions, whereas As [mainly As(III)] is more mobile in hyporheic porewaters subject to reducing/sulfidogenic conditions. Repeat water-leaching of bulk-sediments confirms that Sb is proportionally more mobile than As. Mean concentrations of Sb in river water 168 km downstream from the mine are significantly (P < .05) higher than As, while K d data indicate Sb is more strongly partitioned to the aqueous phase than As. Although the (mainly) oxic flow path of this river favours aqueous Sb mobility compared to As, localised redox-driven shifts in speciation of both elements strongly influence their respective mobility and partitioning., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

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.

Seagrasses thrive in anoxic sediments where sulphide can accumulate to phytotoxic levels. So how do seagrasses persist in this environment? Here, we propose that radial oxygen loss (ROL) from actively growing root tips protects seagrasses from sulphide intrusion not only by abiotically oxidising sulphides in the rhizosphere of young roots, but also by influencing the abundance and spatial distribution of sulphate-reducing and sulphide-oxidising bacteria. We used a novel multifaceted approach combining imaging techniques (confocal fluorescence in situ hybridisation, oxygen planar optodes, and sulphide diffusive gradients in thin films) with microbial community profiling to build a complete picture of the microenvironment of growing roots of the seagrasses Halophila ovalis and Zostera muelleri. ROL was restricted to young root tips, indicating that seagrasses will have limited ability to influence sulphide oxidation in bulk sediments. On the microscale, however, ROL corresponded with decreased abundance of potential sulphate-reducing bacteria and decreased sulphide concentrations in the rhizosphere surrounding young roots. Furthermore, roots leaking oxygen had a higher abundance of sulphide-oxidising cable bacteria; which is the first direct observation of these bacteria on seagrass roots. Thus, ROL may enhance both abiotic and bacterial sulphide oxidation and restrict bacterial sulphide production around vulnerable roots, thereby helping seagrasses to colonise sulphide-rich anoxic sediments.

Metals and metalloids are priority contaminants due to their non-degradable and bioaccumulative nature, and their ability to regulate and perturb diverse physiological processes in various species. Metal(loid)s are known to cause oxidative stress through production of reactive oxygen species (ROS), thus related endpoints like lipid peroxidation (LPO) have received considerable attention as biomarkers of exposure. However, the implications of metal(loid) toxicity including LPO on actual lipid profiles of species inhabiting contaminated systems are poorly understood. Here we applied Nuclear Magnetic Resonance (NMR) spectroscopy for untargeted lipidomics of mosquitofish (Gambusia holbrooki) collected from reference and metal(loid)-contaminated wetlands. We measured a range of trace elements in water and fish using inductively coupled plasma - mass spectrometry (ICP-MS), and interpreted site differences in the lipid profiles of mosquitofish in the context of known physiological responses to sub-lethal metal(loid) exposure. Results indicate deregulation of cellular membrane lipids (i.e., glycerophospholipids, cholesterol and sphingolipids) and increased energy storage molecules (i.e., triacylglycerols and fatty acids) in fish from the contaminated wetland. These responses are consistent with the recognised induction of oxidative stress pathways in organisms exposed to metal(loid)s and could also be symptomatic of mitochondrial dysfunction and endocrine disruption. It is difficult to attribute metal(loid)s as the sole factor causing differences between wetlands, and a more controlled experimental approach is therefore warranted to further explore mechanistic pathways. Nevertheless, our study highlights the benefits of untargeted 1 H NMR-based lipidomics as a relatively fast and simple approach for field-scale assessment and monitoring of organisms inhabiting metal(loid) contaminated environments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

There is considerable interest in applying omics techniques, which have proven extremely valuable for laboratory-based toxicology studies, towards field-scale ecotoxicology and environmental monitoring. Concerns that confounding factors in natural ecosystems may exacerbate variability in omics datasets must be addressed to validate the transition from laboratory to field. This study explores how temporal variability related to seasonal and climatic trends influence qualitative and quantitative metabolomics outcomes, in fish from reference and metal(loid)-polluted wetlands in Australia. Female mosquitofish (Gambusia holbrooki) were sampled on two separate occasions, from a rehabilitated tailings wetland at the site of historic antimony (Sb) processing and a reference wetland with comparable water quality. The first sampling coincided with greater monthly rainfall and colder water temperature, whereas the second sampling was drier and water was warmer. Despite temporal changes and associated differences in metal(loid) concentrations, site differences in metabolite profiles were qualitatively very similar between sampling events. However, quantitative differences were observed, with a greater number of significantly altered metabolites identified during the second sampling event, which coincided with greater metal(loid) concentrations in both water and fish. The majority of identified metabolites were elevated in fish from the contaminated wetland, but with notable decreases in several metabolites that are known to play a role in various aspects of metal(loid) binding, detoxification and excretion. Specifically, decreased aspartate, histidine, myo-inositol, taurine and choline were observed in fish from the contaminated wetland, and may therefore represent a metabolite suite that is broadly indicative of metal toxicity. Quantitative differences between sampling events are suggestive of a dose-response relationship observable at the cellular level which, if harnessed, may be useful for assigning levels of concern based on the degree of change in a multi-parameter set of metabolite biomarkers., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In undisturbed, metal-contaminated marine sediments, porewater metal concentrations are generally low due to their associations with strong binding phases such as organic matter, Fe/Mn (oxy)hydroxides and sulfides. Bioturbating fauna can alter redox conditions and, therefore, metal binding, potentially leading to increased metal bioavailability and subsequent toxicity to inhabiting organisms. Here we assessed the impacts of bioturbation (by bivalves and large amphipod species) on sediment biogeochemistry, metal bioaccumulation and toxicity to a smaller amphipod species in a metal contaminated sediment with low and high acid volatile sulfide (AVS) concentrations. Active bioturbation lowered metal toxicity to reproduction in the sediment with low-AVS (from 90% toxic (non-bioturbated) to 50% toxic (bioturbated)). This corresponded with lower dissolved metal concentrations in the overlying water column and lower metal bioaccumulation. Conversely, toxicity increased due to bioturbation in the sediment with high-AVS (40% toxic (non-bioturbated) to 80% toxic (bioturbated)), coinciding with sulfide oxidation, metal release and greater metal bioaccumulation. The results indicate that the AVS-SEM paradigm (commonly used to estimate the risks of adverse effects to benthic organisms in metal-contaminated sediments) may result in incorrect assessment outcomes in cases where bioturbating organisms rework and oxidize the sediment, or for those sediments where AVS has accumulated due to the inability of larger bioturbating benthic organisms to establish populations.

Hypersaline sediments derived from poor land management or the decommissioning of large-scale salt production contribute to the long-term degradation of aquatic environments. Obstacles impeding remediation of these environments include salt crusts restricting benthic recolonisation, hypersalinity-induced toxicity to organisms, and disruption of biogeochemical cycles. Remediation often focuses on engineered solutions, despite sediment-biota interactions often playing a crucial role in improving long-term remediation and restoration of contaminated areas. The presence of extensive bioturbating communities can assist with flushing of excess salt ions, and the reduction of excess nutrients. Here we investigated the tolerance limits that may impede benthic organism recolonisation of hypersaline sediments. Bioassays on dilutions of a hypersaline sediment (∼400 psu (practical salinity units)) and extracted porewaters were used to assess the acute and chronic tolerances of a range of benthic species. Amphipod, copepod and shrimp species were the least tolerant to hypersalinity; bivalve and gastropod species displayed intermediate tolerance; and crab and polychaete species were the most tolerant, i.e. able to endure prolonged exposure in waters at ≥60 psu. Avoidance tests found many species avoid salinities >50 psu. Short-term endurance tests (time to death) indicated thresholds in the 52-70 psu range through tidal cycle exposures of 6 h (semi-diurnal), 12 h (diurnal), 24 h and 48 h (prolonged). Amphipod reproduction and shrimp larvae development bioassays had EC30's of 46 psu and EC50's in the 54-65 psu range, indicating potential to maintain populations at salinities up to 65 psu. These results will assist in designing successful monitored natural recovery strategies for salt ponds that may supplement the initial engineered approaches.

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).

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. C 8 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 -5 ngcm 2 s -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 C 8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A modified diffusive gradients in thin films (DGT) technique uses both a mixed binding layer (PrCH and A520E resins for NH 4 -N and NO 3 -N, respectively) and multiple binding layers (Metsorb binding layer for PO 4 -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 PO 4 -P. Diffusion coefficients (D) obtained from DGT time-series experiments (conductivity 180 μS cm -1 ) for NH 4 -N, NO 3 -N and PO 4 -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 NO 3 -N and PO 4 -P were constant over a range of ionic strengths (between 100 and 800 μS cm -1 ) while the diffusion coefficient for NH 4 -N decreased with increasing ionic strength, as reported previously. The measurement of NH 4 -N, NO 3 -N and PO 4 -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 NH 4 -N, up to 0.014 mol L -1 NaCl for NO 3 -N and over 0.1 mol L -1 NaCl for PO 4 -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 NH 4 -N measurements being most sensitive. Representative performance was determined for NO 3 -N (90-330 μS cm -1 ) and PO 4 -P (all tested conductivities) over a 72 h deployment period and for NH 4 -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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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 (C restricted /C open ) 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.

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 NH 4 -N and NO 3 -N changed dramatically in most of the studied freshwater systems over short time scales, while there were only relatively small fluctuations in PO 4 -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 NH 4 -N, NO 3 -N, and PO 4 -P in a diverse range of dynamic freshwater systems.

Commercially-available AMI-7001 anion exchange and CMI-7000 cation exchange membranes were utilised as binding layers for DGT measurements of NO 3 -N and NH 4 -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 NO 3 -N and NH 4 -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 NO 3 -N and NH 4 -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 NO 3 -N and NH 4 -N, respectively, as (i) membrane-based DGT have a consistent composition, (ii) avoid the use of toxic chemicals, (iii) provided highly representative results (C DGT  : C SOLN between 0.81 and 1.3), and (iv) agreed with resin-based DGTs to within 85-120%.

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The enrichment of soil arsenic (As) and antimony (Sb) is putting increasing pressure on the environment and human health. The biogeochemical behaviour of Sb and its uptake mechanisms by plants are poorly understood and generally assumed to be similar to that of As. In this study, the lability of As and Sb under agricultural conditions in historically contaminated soils was assessed. Soils were prepared by mixing historically As and Sb-contaminated soil with an uncontaminated soil at different ratios. The lability of As and Sb in the soils was assessed using various approaches: the diffusive gradients in thin films technique (DGT) (as CDGT), soil solution analysis, and sequential extraction procedure (SEP). Lability was compared to the bioaccumulation of As and Sb by various compartments of radish (Raphanus sativus) grown in these soils in a pot experiment. Irrespective of the method, all of the labile fractions showed that both As and Sb were firmly bound to the solid phases, and that Sb was less mobile than As, although total soil Sb concentrations were higher than total soil As. The bioassay demonstrated low bioaccumulation of As and Sb into R. sativus due to their low lability of As and Sb in soils and that there are likely to be differences in their mechanisms of uptake. As accumulated in R. sativus roots was much higher (2.5-21 times) than that of Sb, while the Sb translocated from roots to shoots was approximately 2.5 times higher than that of As. As and Sb in R. sativus tissues were strongly correlated with their labile concentrations measured by DGT, soil solution, and SEP. These techniques are useful measures for predicting bioavailable As and Sb in the historically contaminated soil to R. sativus. This is the first study to demonstrate the suitability of DGT to measure labile Sb in soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Antimony is a priority environmental contaminant typically present as either the trivalent (Sb(III)) or the pentavalent (Sb(V)) oxidation state in aquatic systems. Both the toxicity and mobility of antimony are affected by its speciation, and thus the accurate measurement of antimony speciation is essential for investigating the behaviour of this contaminant in aquatic systems. Here we present a diffusive gradients in thin films (DGT) technique, which utilises a binding layer containing a thiol-based adsorbent (3-mercaptopropyl functionalised silica gel), for the selective measurement of Sb(III) in surface waters and sediment porewaters. We also evaluated the Metsorb DGT technique, which has been previously reported to accurately measure Sb(V), for its ability to accumulate Sb(III) and thus allow the measurement of total inorganic antimony. Both the mercapto-silica and Metsorb DGT techniques showed a high affinity for Sb(III), with uptake efficiencies >97%. Elution efficiencies of 86.9 ± 2.6% and 88.1 ± 1.2% were obtained for mercapto-silica and Metsorb, respectively, with 1 mol L(-1) H2O2 in 1 mol L(-1) NaOH. The accumulation of Sb(III) by these DGT techniques was linear with time (R(2) > 0.99) and unaffected by pH (4.07-8.05), ionic strength (0.001-1.0 mol L(-1) NaCl), bicarbonate (1-15 mmol L(-1)), and an artificial seawater matrix (pH 8.34; salinity 34.8). Finally, the mercapto-silica DGT technique was applied to measure porewater concentrations of Sb(III) and As(III) in a contaminated freshwater sediment at high resolution.

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A new diffusive gradients in a thin film (DGT) technique, using Microlite PrCH cation exchange resin, was developed and evaluated for measuring NH4-N in freshwaters. Microlite PrCH had high uptake (>92.5%) and elution efficiencies (87.2% using 2 mol L(-1) NaCl). Mass vs. time validation experiments over 24 h demonstrated excellent linearity (R(2) ≥ 0.996). PrCH-DGT binding layers had an extremely high intrinsic binding capacity for NH4-N (∼3000 μg). NH4-N uptake was quantitative over pH ranges 3.5-8.5 and ionic strength (up to 0.012 mol L(-1) as NaCl) typical of freshwater systems. Several cations (Na(+), K(+), Ca(2+) and Mg(2+)) were found to compete with NH4-N for uptake by PrCH-DGT, but NH4-N uptake was quantitative over concentration ranges typical of freshwater (up to 0.012 mol L(-1) Na(+), 0.006 mol L(-1) K(+), 0.003 mol L(-1) Ca(2+) and 0.004 mol L(-1) Mg(2+)). Effective diffusion coefficients determined from mass vs. time experiments changed non-linearly with electrical conductivity. Field deployments of DGT samplers with varying diffusive layer thicknesses validated the use of the technique in situ, allowed deployment times to be manipulated with respect to NH4-N concentration, and enable the calculation of the diffusive boundary layer thickness. Daily grab sample NH4-N concentrations were observed to vary considerably independent of major rainfall events, but good agreements were obtained between PrCH-DGT values and mean grab sample measurements of NH4-N (CDGT:CSOLN 0.83-1.3). Reproducibility of DGT measurements in the field was good (relative standard deviation < 11%). Limit of detection was 0.63 μg L(-1) (equivalent to 0.045 μmol L(-1)) based on 24 h deployments., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Four different DGT binding layers were used to make selective measurements of trace metals in coastal waters within The Broadwater (Gold Coast, Queensland). Chelex and PAMPAA (polyacrylamide-polyacrylic acid) binding layers were used to measure cations (Cd, Co, Cu, Mn, Ni, Pb, Zn), and Metsorb was used to measure anions (Al, As, Mo, Sb, V, W). A mixed binding layer (MBL) containing both Chelex and Metsorb was used to measure each of the trace metals and determine diffusive boundary layer (DBL) thicknesses. DGT measurements that were not corrected for the DBL thickness (0.049-0.087) were underestimated by 70% on average. Good agreement was observed between DGT-MBL and DGT-Chelex for measurement of Cd, Co, Cu, Ni, Pb and Zn, and between DGT-MBL and DGT-Metsorb for As, Sb and V. DGT-MBL measured significantly higher concentrations for Mn (compared with DGT-Chelex) and Al (compared with DGT-Metsorb). DGT-Chelex measured only 6-8% of Al species measured by either DGT-MBL or DGT-Metsorb. DGT-PAMPAA measurements of Cu, Pb and Al were lower than those of either DGT-MBL or DGT-Chelex varying from 74-81% for Cu to 54-70% for Pb and 51-55% for anionic Al(OH)4(-), suggesting that this binding layer may make more selective measurements. All measured trace metal concentrations were well below ANZECC water quality guidelines, except for Cu which was 2 to 10 times higher than trigger values. Each of the DGT techniques was deployed using both open and restricted diffusive layers (ODL and RDL). Most trace metal measurements were not significantly different with ODL and RDL for all binding layers. However, concentrations of Cu (CRDL/CODL = 0.68-0.75) and Al (CRDL/CODL = 0.73-0.79) were significantly different with DGT-MBL, DGT-Chelex and DGT-Metsorb.

A systematic comparison of the diffusion coefficients of cations (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and oxyanions (Al, As, Mo, Sb, V, W) in open (ODL) and restricted (RDL) diffusive layers used by the DGT technique was undertaken. Diffusion coefficients were measured using both the diffusion cell (Dcell) method at pH 4.00 and the DGT time-series (D(DGT)) method at pH 4.01 and 7.04 (pH 8.30 was used instead of 7.04 for Al) using the Chelex-Metsorb mixed binding layer. The performance of Chelex-Metsorb as a new DGT binding layer for Al uptake was also evaluated for the first time. Reasonable agreement was observed between D(cell) and D(DGT) measurements for both ODL and RDL, except for V and W. The ratios of D(cell)/D(DGT) for V of 0.44 and 0.39, and for W of 0.66 and 0.63 with ODL and RDL respectively, were much lower due to the formation of a high proportion of polyoxometalate species at the higher concentrations required with the D(cell) measurements. This is the first time that D values have been reported for several oxyanions using RDL. Except for Al at pH 8.30 with ODL, all D(DGT) measurements were retarded relative to diffusion coefficients in water (DW) for both diffusive hydrogels. Diffusion in RDL was further retarded compared with ODL, for all elements (0.66-0.78) with both methods. However, the degree of retardation observed changed for cations and anions at each pH. At pH 7.04 cations had a slightly higher D(DGT) and oxyanions had a slightly lower D(DGT) than at pH 4.01 for both ODL and RDL. It is proposed that this is due to partial formation of acrylic acid functional groups (pKa ≈4.5), which would be fully deprotonated at pH 7.04 (negative) and mostly protonated at pH 4.01 (neutral). As Al changes from being cationic at pH 4.01 to anionic at pH 8.30 the results were more complex., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Measurements of porewater alkalinity are fundamental to the study of organic matter mineralization in sediments, which plays an essential role in the global cycles of carbon and nutrients. A new colorimetric diffusive equilibration in thin film (DET) technique is described for measuring two-dimensional total alkalinity distributions in sediment porewaters at high resolution (1-2 mm(2)). Thin polyacrylamide hydrogel layers (0.8 mm) equilibrate with the porewater and, after removal, are immediately laid onto another hydrogel containing formic acid, which reacts with alkalinity-generating species, and the pH-indicator bromophenol blue. The resultant color change is quantified using computer-imaging densitometry. The lower limit of detection is 0.2 meq L(-1) and the upper measurement limit is 8 meq L(-1). Deployment in seagrass colonized sediment revealed high levels of spatial heterogeneity in the porewater alkalinity distribution, with concentrations ranging from 2.28 meq L(-1) in the overlying water to 5.13 meq L(-1) in some parts of the sediment. This is the first time that two-dimensional, high-resolution distributions of porewater alkalinity have been measured., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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., (© 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.)

"Dissolved" concentrations of contaminants in sediment porewater (Cfree ) provide a more relevant exposure metric for risk assessment than do total concentrations. Passive sampling methods (PSMs) for estimating Cfree offer the potential for cost-efficient and accurate in situ characterization of Cfree for inorganic sediment contaminants. In contrast to the PSMs validated and applied for organic contaminants, the various passive sampling devices developed for metals, metalloids, and some nonmetals (collectively termed "metals") have been exploited to a limited extent, despite recognized advantages that include low detection limits, detection of time-averaged trends, high spatial resolution, information about dissolved metal speciation, and the ability to capture episodic events and cyclic changes that may be missed by occasional grab sampling. We summarize the PSM approaches for assessing metal toxicity to, and bioaccumulation by, sediment-dwelling biota, including the recognized advantages and limitations of each approach, the need for standardization, and further work needed to facilitate broader acceptance and application of PSM-derived information by decision makers., (© 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC.)

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.

A titanium dioxide-based DGT method (Metsorb-DGT) was evaluated for the measurement of As(V), V(V), Sb(V), Mo(VI), W(VI) and dissolved reactive phosphorus (DRP) in synthetic waters. Mass vs. time DGT deployments at pH 6.06 (0.01 mol L(-1) NaNO3) demonstrated linear uptake of all analytes (R(2) ≥ 0.994). Diffusion coefficients measured using a diffusion cell were in reasonable agreement with diffusion coefficients measured using DGT samplers (DCell/DDGT=0.82-1.10), although a systematic difference was apparent. The Metsorb-DGT method was independent of ionic strength (0.001-0.7 mol L(-1) NaNO3 at pH 7.1) for the measurement of all analytes (CDGT/CSol=0.88-1.11) and, with the exception of V(V), the method was independent of pH (3.98-8.24, 0.01 mol L(-1) NaNO3), indicated by CDGT/CSol values in the range 0.88-1.13 for short-term deployments (up to 10h). For V(V) at pH 3.98, Metsorb-DGT underestimated the solution concentration by 17%, presumably due to weak binding of the VO2(+) species. The Metsorb-DGT and ferrihydrite-DGT (in situ precipitated ferrihydrite) methods were compared by deploying samplers in synthetic freshwater (pH 7.20, conductivity 223 μS cm(-1)) and synthetic seawater (pH 8.3. salinity 34.6) for up to four days. For synthetic freshwater, CDGT/CSol values between 0.87-1.17 were obtained for all analytes measured by the Metsorb-DGT method over the deployment period. For ferrihydrite-DGT, CDGT/CSol values between 0.97-1.23 were obtained for As(V), V(V), W(VI) and DRP. However, Mo and Sb(V) showed reduced uptake and CDGT/CSol values were in the range 0.18-1.14 and 0.39-0.98, respectively. In synthetic seawater deployments, Metsorb-DGT was capable of measuring As(V), V(V), Sb(V), W(VI) and DRP for up to 4 days (CDGT/CSol=0.89-1.26), however, this method was not capable of measuring Mo for deployment times >4h (CDGT=0.27-0.72). For ferrihydrite-DGT, CDGT/CSol values in the range 0.92-1.16 were obtained for As(V), V(V) and DRP, however, Mo(VI), Sb(V) and W(VI) could not be measured to within 15% of the solution concentration (CDGT/CSol 0.02-0.83)., (Copyright © 2012 Elsevier B.V. All rights reserved.)