DGT-induced copper flux predicts bioaccumulation and toxicity to bivalves in sediments with varying properties

Many regulatory frameworks for sediment quality assessment include consideration of contaminant bioavailability. However, the “snap-shots” of metal bioavailability provided by analyses of porewaters or acid-volatile sulfidesimultaneously extractable metal (AVS-SEM) relationships do not always contribute sufficient information. The use of inappropriate or inadequate information for assessing metal bioavailability in sediments may result in incorrect assessment decisions. The technique of diffusive gradients in thin films (DGT) enables the in situ measurement of metal concentrations in waters and fluxes from sediment porewaters. We utilized the DGT technique to interpret the bioavailability of copper to the benthic bivalve Tellina deltoidalis in sediments of varying properties contaminated with copper-based antifouling paint particles. For a concentration series of copper-paint contaminated sandy, silty-sand, and silty sediment types, DGTprobes were used to measure copper fluxes to the overlying water, at the sedimentwater interface, and in deeper sediments. The overlying water copper concentrations and DGT-Cu fluxes were shown to provide excellent exposure concentration−response relationships in relation to lethal effects occurring to the copper-sensitive benthic bivalve, T. deltoidalis. The study demonstrates the strength of the DGT technique, which we expect will become frequently used for assessing metal bioavailability in sediments

The impact of sediment bioturbation by secondary organisms on metal bioavailability, bioaccumulation and toxicity to target organisms in benthic bioassays: implications for sediment quality assessment

Bioturbation alters the properties of sediments and modifies contaminant bioavailability to benthic organisms. These naturally occurring disturbances are seldom considered during the assessment of sediment quality. We investigated how the presence (High bioturbation) and absence (Low bioturbation) of a strongly bioturbating amphipod within three different sediments influenced metal bioavailability, survival and bioaccumulation of metals to the bivalve Tellina deltoidalis. The concentrations of dissolved copper decreased and manganese increased with increased bioturbation. For copper a strong correlation was observed between increased bivalve survival (53-100%) and dissolved concentrations in the overlying water. Increased bioturbation intensity resulted in greater tissue concentrations for chromium and zinc in some test sediments. Overall, the results highlight the strong influence that the natural bioturbation activities from one organism may have on the risk contaminants pose to other organisms within the local environment. The characterisation of field-based exposure conditions concerning the biotic or abiotic resuspension of sediments and the rate of attenuation of released contaminants through dilution or readsorption may enable laboratory-based bioassay designs to be adapted to better match those of the assessed environment

Diffusive Gradients in Thin Films Technique Provide Robust Prediction of Metal Bioavailability and Toxicity in Estuarine Sediments

Many sediment quality assessment frameworks incorporate contaminant bioavailability as a critical factor regulating toxicity in aquatic ecosystems. However, current approaches do not always adequately predict metal bioavailability to organisms living in the oxidized sediment surface layers. The deployment of the diffusive gradients in thin films (DGT) probes in sediments allows labile metals present in pore waters and weakly bound to the particulate phase to be assessed in a time-integrated manner in situ. In this study, relationships between DGT-labile metal fluxes within 5 mm of the sediment–water interface and lethal and sublethal effects to the amphipod Melita plumulosa were assessed in a range of contaminated estuarine sediments during 10-day laboratory-based bioassays. To account for differing toxicities of metals, DGT fluxes were normalized to water (WQG) or sediment quality guidelines or toxicity thresholds specific for the amphipod. The better dose–response relationship appeared to be the one based on WQG-normalized DGT fluxes, which successfully predicted toxicity despite the wide range of metals and large variations in sediment properties. The study indicated that the labile fraction of metals measured by DGT is useful for predicting metal toxicity to benthic invertebrates, supporting the applicability of this technique as a rapid monitoring tool for sediments quality assessments

The mismatch between bioaccumulation in field and laboratory environments: interpreting the differences for metals in benthic bivalves

Laboratory-based bioaccumulation and toxicity bioassays are frequently used to predict the ecological risk of contaminated sediments in the field. This study investigates the bioassay conditions most relevant to achieving environmentally relevant field exposures. An identical series of metal-contaminated marine sediments were deployed in the field and laboratory over 31 days. Changes in metal concentrations and partitioning in both sediments and waters were used to interpret differences in metal exposure and bioaccumulation to the benthic bivalve Tellina deltoidalis. Loss of resuspended sediments and deposition of suspended particulate matter from the overlying water resulted in the concentrations of Cu, Pb and Zn (major contaminants) becoming lower in the 1-cm surface layer of field-deployed sediments. Lower exchange rates of overlying waters in the laboratory resulted in higher dissolved metal exposures. The prediction of metal bioaccumulation by the bivalves in field and laboratory was improved by considering the metal partitioning within the surface sediments

Zhong guo ji sheng chong xue yu ji sheng chong bing za zhi

The use of diffusive gradients in thin films (DGT) for predicting metal bioavailability was investigated by exposing the bivalve Tellina deltoidalis to an identical series of metal-contaminated sediments deployed simultaneously in the field and laboratory. To understand the differences in metal exposure occurring between laboratory- and field-based bioassays, we investigated changes in metal fluxes to DGT probes in sediments and in metal concentrations and partitioning to porewaters and overlying waters. DGT-metal fluxes (Cu, Pb, and Zn) were lower in the overlying waters of most field bioassays compared to the laboratory, causing differences in Pb and Zn bioaccumulation between bivalves exposed to laboratory and field conditions. Overall, DGT-metal fluxes provided predictions of metal bioaccumulation similar to those obtained using dilute-acid extractable metal measurements. This study demonstrates that, irrespective of the physicochemical properties of the sediment and type of exposure (laboratory or field), sediments pose a significant risk of bioaccumulation by T. deltoidalis when the Cu, Pb, and Zn DGT flux exceeds 3.5, 1.3, and 156 μg/h/m², respectively. The results presented here support the use of the DGT technique for sediment quality assessment and the hypothesis that DGT-metal fluxes may potentially be useful surrogates for the lability of metals for all exposure routes

Unusual Electronic Structure of the Donor–Acceptor Cocrystal Formed by Dithieno[3,2‑<i>a</i>:2′,3′‑<i>c</i>]phenazine and 7,7,8,8-Tetracyanoquinodimethane

Mixed cocrystals derived from electron-rich donor (D) and electron-deficient acceptor (A) molecules showcase electronic, optical, and magnetic properties of interest for a wide range of applications. We explore the structural and electronic properties of a cocrystal synthesized from dithieno­[3,2-<i>a</i>:2′,3′-<i>c</i>]­phenazine (DTPhz) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), which has a mixed-stack packing arrangement of the (π-electronic) face-to-face stacks in a 2:1 D:A stoichiometry. Density functional theory investigations reveal that the primary electronic characteristics of the cocrystal are not determined by electronic interactions along the face-to-face stacks, but rather they are characterized by stronger electronic interactions orthogonal to these stacks that follow the edge-to-edge donor–donor or acceptor–acceptor contacts. These distinctive electronic characteristics portend semiconducting properties that are unusual for semiconducting mixed cocrystals and suggest further potential to design organic semiconductors with orthogonal transport characteristics for different charge carriers

DGT-Induced Copper Flux Predicts Bioaccumulation and Toxicity to Bivalves in Sediments with Varying Properties

Many regulatory frameworks for sediment quality assessment include consideration of contaminant bioavailability. However, the “snap-shots” of metal bioavailability provided by analyses of porewaters or acid-volatile sulfide-simultaneously extractable metal (AVS-SEM) relationships do not always contribute sufficient information. The use of inappropriate or inadequate information for assessing metal bioavailability in sediments may result in incorrect assessment decisions. The technique of diffusive gradients in thin films (DGT) enables the in situ measurement of metal concentrations in waters and fluxes from sediment porewaters. We utilized the DGT technique to interpret the bioavailability of copper to the benthic bivalve <i>Tellina deltoidalis</i> in sediments of varying properties contaminated with copper-based antifouling paint particles. For a concentration series of copper-paint contaminated sandy, silty-sand, and silty sediment types, DGT-probes were used to measure copper fluxes to the overlying water, at the sediment-water interface, and in deeper sediments. The overlying water copper concentrations and DGT-Cu fluxes were shown to provide excellent exposure concentration–response relationships in relation to lethal effects occurring to the copper-sensitive benthic bivalve, <i>T. deltoidalis</i>. The study demonstrates the strength of the DGT technique, which we expect will become frequently used for assessing metal bioavailability in sediments

Journal of northeast Asian studies

The burrowing and feeding activities of benthic organisms can alter metal speciation in sediments and affect an organisms’ exposure to metals. Recently, the performance of the in situ technique of diffusive gradients in thin films (DGT) for predicting metal bioavailability has been investigated in response to the increasing demand of considering contaminant bioavailability in sediment quality assessments. In this study, we test the ability of the DGT technique for predicting the metal bioavailability in clean and contaminated sediments that are being subjected to varying degrees of sediments disturbance: low bioturbation (bivalve Tellina deltoidalis alone) and high bioturbation (bivalve and actively burrowing amphipod, Victoriopisa australiensis). Significant release of DGT-labile Cd, Ni, Pb, and Zn, but lower Cu and Fe, occurred in the pore and overlying waters of sediments exposed to high bioturbation conditions, resulting in higher bioaccumulation of zinc in bivalves. Strong relationships were found between bioaccumulation of Pb and Zn and time-integrated DGT-metal fluxes, whereas poor relationships were obtained using total or dilute-acid extractable metal concentrations. This results demonstrate that DGT is a useful tool for assessing metal bioavailability in sediments and can provide useful predictions of metal bioavailable to benthic organisms in dynamic sediment environments