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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.

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.

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.

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%.

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.

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.