Bioavailability Of Metals In Sediments Research Articles

Assessment of metal bioavailability in sediments and bioaccumulation in edible bivalves, and phyto-remediation potential of mangrove plants in the tropical (Kali) estuary, India

The bioavailability of metals (Fe, Mn, Zn, Cu, Co and Ni) in sediment cores (K-1, K-2, K-3 and K-4) and bioaccumulation in edible bivalves were studied to determine the toxicity of metals in the Kali Estuary, India. Enrichment Factor (EF) construed anthropogenic sources of Zn, Co and Ni, while Geo-accumulation Index (Igeo) revealed pollution of Zn and Ni based on total metal analysis. The Pollution Load Index (PLI >1) supported anthropogenic origin of metals in estuary. Metal speciation study indicated bioavailability of metals in sediments. The bioavailable Mn and Co equalled/exceeded the Apparent Effect Threshold (AET) limit (cores K-1, K-3 and K-4) and indicated toxicity to estuarine biota. The metals in Metetrix casta (Fe, Mn, Zn, Cu, and Ni), Saccostrea cucullata (Fe, Mn, Zn, Cu, Co and Ni) and Villorita cyprinoides (Fe, Mn, Zn, Cu, Co and Ni) exceeded the permissible bioaccumulation limit. Thus, revealed metal toxicity to bivalves and labelled them un-safe for human consumption. Translocation Factor (TF > 1) indicated the use of Kandelia candel in phyto-remediation of Fe, Zn, Cu, Co and Ni at station K-3, and Sonnaretia caseoloris in phyto-remediation of Fe, Zn and Ni at station K-4.

Effect of nanomaterials on the bioavailability of metals in sediments from a highly impacted tropical coastal environment

In this study, the impact of nanoparticles on the chemical behavior of metals in a tropical coastal environment was evaluated in a microcosm assay. The microcosms were assembled to reproduce the original environmental conditions, to evaluate the effects of two different nanoparticles. The aquariums were filled with water and sediment from Cunha River (Rio de Janeiro – Brazil) - which is highly contaminated by metals and organic compounds - and nanoparticles of hydroxyapatite (500 nm) and poly lactic-co-glycolic acid (PLGA) nanoparticles doped with Holmium-166 (200 nm), both radiolabeled with 99mTc. The quantification of trace metals (Cu, Zn, Mn, Fe, Cr and Pb) was performed in the water samples. The concentration data obtained for Fe, Cr and Pb were lower than ICP-OES Detection Limits (Fe: DL < 0.0343 mg.L−1, Cr: DL < 0.0036 mg.L−1 and Pb: DL < 0.0291 mg.L−1), while the results for Cu, Zn and Mn demonstrated that the presence of hydroxyapatite and PLGA nanoparticles had no influence on the behavior of dissolved metals, probably because of the high organic loads of the system, which may have overwhelmed or masked the interaction of nanomaterials with metals, once the natural organic matter could interact with the nanoparticles, favoring their aggregation and sedimentation and thus reducing their bioavailability and reactivity. Geochemical fractionation presented a relevant association of metals with the organic phase. In terms of environmental impact assessment of nanomaterials, it was concluded through 99mTc labelling that both nanomaterials (about 30% to 50%) remained in solution during the 49 h of the experiment.

Isotopically Modified Bioassay Bridges the Bioavailability and Toxicity Risk Assessment of Metals in Bedded Sediments.

The application of bioavailability-based risk assessment for the management of contaminated sediments requires new techniques to rapidly and accurately determine metal bioavailability. Here, we designed a multimetal isotopically modified bioassay to directly measure the bioavailability of different metals by tracing the change in their isotopic composition within organisms following sediment exposure. With a 24 h sediment exposure, the bioassay sensed significant bioavailability of nickel and lead within the sediment and determined that cadmium and copper exhibited low bioavailable concentrations and risk profiles. We further tested whether the metal bioavailability sensed by this new bioassay would predict the toxicity risk of metals by examining the relationship between metal bioavailability and metal toxicity to chironomid larvae emergence. A strong dose-toxicity relationship between nickel bioavailability (nickel assimilation rate) and toxicity (22 days emergence ratio) indicated exposure to bioavailable nickel in the sediment induced toxic effects to the chironomids. Overall, our study demonstrated that the isotopically modified bioassay successfully determined metal bioavailability in sediments within a relatively short period of exposure. Because of its speed of measurement, it may be used at the initial screening stage to rapidly diagnose the bioavailable contamination status of a site.

Evaluation of the Bioavailability of Metals in Sediment from the Southern Coastal Wetland of the Qiantang Estuary by Using Diffusive Gradients in Thin Films Technique

Evaluation of the Bioavailability of Metals in Sediment from the Southern Coastal Wetland of the Qiantang Estuary by Using Diffusive Gradients in Thin Films Technique

Refining our understanding of metal bioavailability in sediments using information from porewater: Application of a multimetal biotic ligand model as an extension of the equilibrium partitioning sediment benchmarks.

The equilibrium partitioning sediment benchmarks (ESBs) derived by the US Environmental Protection Agency (USEPA) in 2005 provide a mechanistic framework for understanding metal bioavailability in sediments by considering equilibrium partitioning (EqP) theory, which predicts that metal bioavailability in sediments is determined largely by partitioning to sediment particles. Factors that favor the partitioning of metals to sediment particles, such as the presence of acid volatile sulfide (AVS) and sediment organic matter, reduce metal bioavailability to benthic organisms. Because ESBs link metal bioavailability to partitioning to particles, they also predict that measuring metals in porewater can lead to a more accurate assessment of bioavailability and toxicity to benthic organisms. At the time of their development, sediment ESBs based on the analysis of porewater metal concentrations were limited to comparison with hardness-dependent metals criteria for the calculation of interstitial water benchmark units (IWBUs). However, the multimetal biotic ligand model (mBLM) provides a more comprehensive assessment of porewater metal concentrations, because it considers factors in addition to hardness, such as pH and dissolved organic carbon, and allows for interactions between metals. To evaluate the utility of the various sediment and porewater ESBs, four Hyalella azteca bioassay studies were identified that included sediment and porewater measurements of metals and porewater bioavailability parameters. Evaluations of excess simultaneously extracted metals, IWBUs, and mBLM toxic units (TUs) were compared among the bioassay studies. For porewater, IWBUs and mBLM TUs were calculated using porewater metal concentrations from samples collected using centrifugation and peepers. The percentage of correct predictions of toxicity was calculated for each benchmark comparison. The mBLM-based assessment using peeper data provided the most accurate predictions for the greatest number of samples among the evaluation methods considered. This evaluation demonstrates the value of porewater-based evaluations in conjunction with sediment chemistry in understanding toxicity observed in bioassay studies. Integr Environ Assess Manag 2022;18:1335-1347. © 2021 SETAC.

Application of a Multi-Metal Stable-Isotope-Enriched Bioassay to Assess Changes to Metal Bioavailability in Suspended Sediments.

The direct measurement of particulate contaminant bioavailability is a challenging aspect for the environmental risk assessment of contaminated sites. Here, we demonstrated a multi-metal stable-isotope-enriched bioassay to simultaneously measure the bioavailability of Cd, Cu, and Zn in naturally contaminated sediments following differing periods of resuspension treatment. Freshwater filter-feeding clams were pre-labeled with the isotopes 114Cd, 65Cu, and 68Zn to elevate isotope abundances in their tissues and then exposed to metal-contaminated suspended sediments. The assimilation of sediment-associated metals by clams would decrease the isotope ratios (Cd114/111, Cu65/63, and Zn68/64) in tissues, providing a direct measurement of metal bioavailability. For the sediments tested here, the method revealed bioavailable cadmium and non-bioavailable copper in sediments but was inconclusive for zinc. With a longer resuspension time, the bioavailability of particulate cadmium increased, but that of copper was unaffected. Metal bioavailability predicted using traditional wet-chemical extraction methods was inconsistent with these findings. The study indicated that multi-metal stable-isotope-enriched bioassay provides a new tool for directly assessing metal bioavailability in sediments, and this method is amenable for use in in situ assessments.

Distribution, risk and bioavailability of metals in sediments of Lake Yamdrok Basin on the Tibetan Plateau, China

Total contents of metals in soil and sediments on the Tibetan Plateau of China have been widely analyzed, but existing information is insufficient to effectively evaluate metal ecological risk because of a lack of metal bioavailability data. In this study, distribution, potential risk, mobility and bioavailability of metals in sediments of Lake Yamdrok Basin in Tibet of China were explored by combined use of total digestion, sequential extraction and the diffusive gradient in thin-films (DGT). Average concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb in surface sediments were 31.25, 30.31, 22.00, 45.04, 31.32, 0.13 and 13.39 mg/kg, respectively. Higher levels of metals were found near the inflowing rivers. Residual form was dominant in Cr, Ni, Zn, Cd and Pb, and reducible form was dominant in As and Cd. Metals in surface sediments showed a low enrichment degree overall, but Cd and As had higher ecological risk levels than the other metals. Furthermore, there was a larger average proportion of exchangeable form of As (20.4%) and Cd (9.0%) than the other metals (1.7%-3.3%), implying their higher mobility and release risk. Average DGT-labile concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb were 0.5, 4.5, 0.7, 25.1, 60.0, 0.22 and 1.0 µg/L, respectively. The DGT-labile As was significantly correlated with extractable As forms (p< 0.01), suggesting that extractable As in sediments acts as a “mobile pool” for bioavailable As. These results suggest potential risks of As and Cd, especially As, deserve further attention in Lake Yamdrok Basin.

Speciation and Bioavailability of Metals in Sediments from a Stream Impacted by Abandoned Mines in Maoshi Town, Southwest of China.

The speciation of metals in surface sediments, as well as metal concentrations in muscle and liver of sharpbelly Hemiculter leucisculus from a stream near the Mo-Ni polymetallic mines in Maoshi town were investigated. The results indicated that metal concentrations were generally highest in the most upstream sampling location that is closest to the former mine operation. The total concentrations of Mn in sediments were higher than other metals. The Cr was mainly associated with residual fraction, while the order of bioavailability of metals (sum of the concentrations of exchangeable, reducible, and oxidizable fractions) was as follows: Cd (89.95%) > Mn (82.32%) > Ni (45.58%) > Mo (29.39%) > Hg (29.23%) > As (22.60%) > Pb (17.38%) > Cr (6.21%). The Cd concentration in muscle of H. leucisculus exceeded the permissible limit which indicated that the fish from this area are not safe for human consumption. The potential ecological risks of Cd cannot be ignored in this study area.

Effects of dissolved oxygen, salinity, nitrogen and phosphorus on the release of heavy metals from coastal sediments

Great amounts of nutrients discharged into the urbanized coastal areas, which are continuously subject to violently anthropogenic metal contamination, will result in eutrophication and hypoxic episode. In order to study the effects of dissolved oxygen (DO), salinity, nitrogen and phosphorus on the release of six metals including Zn, Pb, Cd, Cu, As and Cr from coastal sediments, a series of 60-days microcosm experiments consisting of sediments and seawater were conducted. Severe hypoxia could result in the enhanced peak values of Pb, Cd, Cu and Cr concentrations in the overlying water. A higher level of water salinity could elevate the peak value of As concentration in water column, and a higher level of nitrogen could increase the peak value of Zn concentration in water. The exchange fluxes demonstrated that the diffusion from the sediments was a dominant process during the first 10 days, However, a relative equilibrium of adsorption and precipitation in the sediment-water interface reached during the later periods. In addition, the bioavailability of the studied metals in sediments was elevated under severe hypoxia, or a high level of water salinity, or high levels of nitrogen and phosphorus. The results of linear regression analysis suggested that higher metal bioavailability in sediments could facilitate the metal release, but the process could be restrained by the higher aqueous phosphorus due to the precipitation of metal phosphates.

Predicting trace metal bioavailability to chironomids in sediments by diffusive gradients in thin films

The technique of diffusive gradients in thin films (DGT) has been developed as a promising tool to assess metal bioavailability in sediment. However, it has yet to be determined whether the DGT-labile metal in sediment is representative of bioavailable fraction for benthic organisms. In this study, the performance of DGT for predicting metal bioavailability was evaluated by exposing DGT and chironomids Chironomus tentans to a series of metal-contaminated natural sediments in the laboratory. Conventional methods, including acid-volatile sulfides and simultaneously extracted metals method, and total recoverable and dilute-acid extractable metal concentrations were also used to assess the availability of Zn, Cu and Pb to chironomids. The bioassay results showed that >70% of the larvae (73 ± 1.7%–98 ± 0.5%) survived in all sediment samples, however, an enhanced uptake of Zn, Cu and Pb by C. tentans in contaminated sediments was observed compared to control sediments. The correlation analyses indicated that the total recoverable metal concentrations and DGT-metal fluxes in the surficial sediment (−1 cm) were all significantly associated with metal bioaccumulation in C. tentans (p < 0.01). Given the advantages of DGT devices for in situ and time-averaged measurement of the potentially bioavailable fraction, DGT-metal fluxes were proved to be a better surrogate to predict C. tentans response to metal contamination. The results further supported the applicability of the DGT technique as an alternative method to assess the bioavailability of metals in sediment to benthic invertebrates.

Evaluating the diffusive gradients in thin films technique for the prediction of metal bioaccumulation in plants grown in river sediments

The diffusive gradients in thin films (DGT) technique is a useful tool for assessing metal bioavailability in sediments. However, the DGT technique has not been used to predict metal bioaccumulation in plants grown in sediments in river systems. In this study, the DGT technique was evaluated for predicting metal bioaccumulation in Phragmites australis growing in contaminated sediments. In sediments with high levels of contamination, release of DGT-labile Cr, Zn, Cu, and Cd occurred, which resulted in high bioaccumulation of these metals in P. australis. Bioaccumulation of Cr, Cu, Zn, and Cd was strongly correlated with the metal concentrations in the sediments measured by the DGT technique. By contrast, the correlation between sediment content and bioaccumulation for As was weak. There were significant negative correlations between the content of Ni in the plant tissues and the contents of the other metals. Overall, the DGT technique provided predictions of metal bioaccumulation similar to those obtained using total metal measurements in multiple polluted sediment samples. Therefore, DGT analysis could be used for assessing heavy metal bioavailability, and metal bioaccumulation in P. australis was not all significantly correlated with the bioavailability concentrations of metals in river sediments.

Sediment Zn-release during post-drought re-flooding: Assessing environmental risk to Hyalella azteca and Daphnia magna

Hydrologic variability exacerbated by climate change affects biogeochemical cycling in sediments through changes in pH, redox, and microbial activity. These alterations affect the lability and speciation of metals, such that toxicity may be observed in otherwise non-toxic sediments. In this study, we investigate the effects of drought and reflooding on metal bioavailability in sediments with low to moderate concentrations of Zn (18–270 mg kg−1). Sediments were collected from coastal wetlands in Michigan, dried (36-days) and re-inundated in lab microcosms. We investigated the relationships between key parameters, for surface/porewater (dissolved and particulate metals, dissolved oxygen, redox (Eh), reduced iron, and temperature) and sediment (simultaneously extracted metals (SEM), acid volatile sulfide (AVS), Fe/Mn-oxyhydroxide, organic carbon, water content analyses, and diffusive gradient in thin films (DGTs) metal concentrations). Porewater Zn increased with inundation of dried sediments for all sediment types, exceeding United States Environmental Protection Agency (U.S. EPA) chronic criteria for freshwater organisms, and decreased as sediments became reduced. Effects on Hyalella azteca (7-day exposure) and Daphnia magna (10-day exposure) were quantified. Results show decreased growth of H. azteca for sites with elevated Zn and increased Zn-body concentration (BCZn) in the most contaminated sediment type. Further, BCZn was negatively correlated with H. azteca growth. D. magna survival, growth, and reproduction were not affected. DGT metal concentrations were more reflective of porewater than organism bioaccumulation. Outcomes of predictive toxicology methods are compared to toxicity test results and suggestions are provided for model improvements. This study demonstrates that post-drought re-flooding of sediments affects Zn biogeochemical cycling with potentially adverse effects on benthic organisms, even in sediments with only moderately elevated concentrations (>150 mg kg−1).

Spatiotemporal trend analysis of metal concentrations in sediments of a residential California stream with toxicity and regulatory implications

ABSTRACTThe objective of this study was to determine if concentrations of arsenic, cadmium, chromium, copper, lead, nickel and zinc measured in the sediments of a residential stream in California (Pleasant Grove Creek) have changed temporally or spatially from 2006 to 2016. Threshold Effect Levels (TELs), conservative ecological effects benchmarks, and exceedances for the seven metals were also evaluated over the 11-year time period to provide insight into potential metal toxicity to resident benthic communities. In addition, the bioavailability of metals in sediments was also determined by calculating Simultaneous Extracted Metal/Acid Volatle Sulfide (SEM/AVS) ratios to allow an additional assessment of toxicity. Regulatory implications of this data set and the role of metal toxicity are also discussed. Stream-wide temporal trend analysis showed no statistically significant trends for any of the metals. However, spatial analysis for several sites located near storm drains did show a significant increase for most metals over the 11-year period. TEL exceedances during the 7 years of sampling, spanning 2006–2016, were reported for all metals with the number of exceedances ranging from 47 for copper and zinc to 1 for lead. A spatial analysis showed that the highest number of TEL exceedances and the highest number of SEM/AVS ratios greater than one with at least one metal exceeding a TEL occurred at upstream sites. The potentially toxic metal concentrations reported in Pleasant Grove Creek should be used in the 303 (d) listing process for impaired water bodies in California.

Comparison of partial extraction reagents for assessing potential bioavailability of heavy metals in sediments

Assessment of heavy metal bioavailability in sediments is complex because of the number of partial extraction methods available for the assessment and the general lack of certified reference materials. This study evaluates five different extraction methodologies to ascertain the relative strengths and weaknesses of each method. The results are then compared to previously published work to ascertain the most effective partial extraction technique, which was established to dilute (0.75–1M) nitric acid solutions. These results imply that single reagent; weak acid extractions provide a better assessment of potentially bioavailable metals than the chelating agents used in sequential extraction methods.

Trace metal bioavailability in sediments from a reference site, Ribeira Bay, Brazil

Surface sediments were collected near potential contamination sources impacting Ribeira Bay (Brazil), a system considered as a ‘reference site’ for trace metals. Physicochemical properties (pH and Eh), grain size and concentrations of total organic carbon (TOC), total phosphorus (TP), acid-volatile sulfides (AVS) and simultaneously-extracted metals (Fe, Mn, Cd, Cu, Ni, Pb and Zn) were analyzed. Although relatively low metal concentrations were found, correlations of Zn and Ni with high TP levels suggested an association with sewage inputs, while other metals presented associations with specific geochemical carriers (TOC, Fe and Mn compounds). AVS levels exceeding those of the sums of Cd, Cu, Ni, Pb and Zn (ΣSEM) by at least one order of magnitude and TOC-normalized differences between ΣSEM and AVS ((ΣSEM–AVS)/fOC) near to or below than −200μmolgOC−1 indicated that there were sufficient AVS and TOC levels to control trace metal bioavailability in sediment pore water.

Assessing the Effects of Bioturbation on Metal Bioavailability in Contaminated Sediments by Diffusive Gradients in Thin Films (DGT).

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.

Bioavailability of Pb and Cu in Sediments of Vegetated Seagrass, Enhalus acoroides, from Spermonde Islands, Makassar, South Sulawesi, Indonesia

Seagrass might impact metal bioavailability in sediments with physiological processes that occur at the root and rhizome. Seagrass growth may increase bioavailability due to oxygen transport from leaves to the root systems. This study aims to analyze the concentrations of bioavailable Pb and Cu in sediments with and without seagrass. This study was done at two sites in Spermonde Islands, South Sulawesi, Indonesia. All metals analysis and sediment parameters were conducted on dry, <63 μm grain size sediment samples. Metal speciation in sediment was determined using the Community Bureau of Reference (BCR) three steps sequential that extract exchangeable and acid soluble fraction, reducible and oxidisable fraction. The average concentrations of bioavailable fraction of Pb and Cu (fraction 1) was higher in vegetated sediments associated with Enhalus acoroides than in unvegetated sediments. Higher concentration of Cu in fraction 1 was also associated with higher concentration in Enhalus roots. This indicates that the presence of seagrass may increase the bioavailability of metals in sediments. Increased metal bioavailability in vegetated sediment will imply increase toxicity.

Heavy metals in red crabs, Chaceon quinquedens, from the Gulf of Mexico

The red crab, Chaceon quinquedens, is distributed in deep waters of the Gulf of Mexico (GOM) and is most abundant in an area associated with sediment deposition from the Mississippi River. Sediment geochemistry and biological and ecological traits of red crabs favor accumulation of contaminants. Red crabs, sediment, and bottom water samples were taken from three distinct geographic locations representing areas with differing exposure to contaminant laden effluents from the Mississippi River. Inductively coupled plasma spectrophotometry and atomic absorption spectrophotometry were employed to determine levels of heavy metals in red crab muscle tissue. Ion site partitioning was used to determine metal speciation in sediments. Red crabs showed evidence of heavy metal bioaccumulation in all sample areas with high variability in contaminant levels in individual crabs for some metals. Bioavailability of metals in sediment did not always result in accumulation in muscle tissue.

Sediment metal bioavailability in Lake Taihu, China: evaluation of sequential extraction, DGT, and PBET techniques.

The European "Community Bureau of Reference" (BCR) sequential extraction procedure, diffusive gradient in thin-films technique (DGT), and physiologically based extraction test were applied to assess metal bioavailability in sediments of Lake Taihu (n = 13). Findings from the three methods showed that Cd was a significant problem in the western lake whereas Cu, Zn, and Ni pollution was most severe in the northern lake. Results from the sequential extraction revealed that more than 50% of the Cu and Zn were highly mobile and defined within the extractable fraction (AS1 + FM2 + OS3) in the majority of the sediments, in contrast extractable fractions of Ni and Cd were lower than 50% in most of the sampling sites. Average Cu, Zn, Ni, and Cd bioaccessibilities were <50% in the gastric phase. Zn and Cd bioaccessibility in the intestinal phase was ∼50% lower than the gastric phase while bioaccessibilities of Cu and Ni were 47-57% greater than the gastric phase. Linear regression analysis between DGT and BCR measurements indicated that the extractable fractions (AS1 + FM2 + OS3) in the reducing environment were the main source of DGT uptake, suggesting that DGT is a good in situ evaluation tool for metal bioavailability in sediments.

Experimental Study of Mobility and Kinetic Characterization of Trace Elements in Contaminated Sediments from a River Basin in Northern Peru

ABSTRACTIn the Jequetepeque basin (Peru), gold extraction activity has been performed in the last decades, leading to a release of metals and metalloids into the environment. Sediment samples were taken in the vicinity of two mines and analyzed. Extraction of metals and metalloids from sediments was carried out using single extraction procedures, acidic (HNO3), and complexation (EDTA) leaching, in order to determine the mobility of trace elements. Results indicated that acidic extraction at low pH values increased the leachability of trace elements. EDTA showed a higher bioavailability of metals in sediments than acidic extraction under similar pH conditions because of its greater leaching capacity. This is an important issue in view of risk assessment analysis. The highest extractability was observed for Cd in all sediments with up to 90% of extraction after 1 h. The mobility index analysis indicated that faster kinetic leachability of some trace elements leads to a higher mobility in sediments, especially those near the active gold extraction mine. The ecological risk assessment suggested that the four river sediments were at high and very high risk levels, indicating that sediment contamination is an issue of environmental concern in the Jequetepeque basin of northern Peru.