Evaluation of potential toxicity and bioavailability of chromium in sediments associated with chromite ore processing residue

Recent studies by researchers at the U.S. Environmental Protection Agency and U.S. Geological Survey have evaluated the toxicity of Cr in freshwater and marine sediments, primarily during laboratory studies in which clean sediments were spiked with Cr. Results of those studies showed that Cr is relatively insoluble and nontoxic when present in the trivalent form, Cr(III), rather than in the more soluble and more toxic hexavalent form, Cr(VI). The studies concluded that Cr toxicity should be low in sediments with measurable concentrations of acid-volatile sulfide (AVS), because AVS is formed only in anoxic sediments and Cr(VI) is thermodynamically unstable under such conditions. The present study evaluates the toxicity and bioavailability of Cr in sediments associated with chromite ore processing residue (COPR). Ten stations were sampled in the Hackensack River (NJ, USA) to represent a wide range of total Cr concentrations (199-3,970 mg/kg) with minimal interference from potentially toxic, co-occurring chemicals. Sediment toxicity was evaluated using two amphipod tests: The 10-d Ampelisca abdita test (survival as endpoint), and the 28-d Leptocheirus plumulosus test (survival and biomass as endpoints). Measurable concentrations of AVS were present at eight stations, and nearly all Cr was present as Cr(III). In addition, results of electron-microprobe analyses showed that most Cr was associated with phases in which Cr has limited bioavailability (i.e., chromite and iron oxide). Sediment toxicity showed no correlation with concentrations of total Cr, and the maximum no-effect concentration for total Cr was estimated as 1,310 mg/ kg. These results indicate that Cr can be present in sediments associated with COPR at highly elevated concentrations without causing sediment toxicity.     

Chromium Geochemistry and Bioaccumulation in Sediments from the Lower Hackensack River, New Jersey

Total and hexavalent chromium [Cr(VI)] were measured in sediment and sediment porewater in the lower Hackensack River (NJ) to assess the relationship between sediment geochemistry and chromium speciation, which in turn controls the mobility, bioavailability, and toxicity of chromium. Between 2003 and 2005, >100 surface (0 to 15 cm) sediment samples were tested for total chromium and Cr(VI), acid-volatile sulfides (AVS), ferrous iron (Fe(II)), divalent manganese (Mn(II)), ammonia, and organic carbon. Sediment porewater samples were collected by centrifugation or using in situ samplers colocated with the collection of sediments. In whole sediments, total chromium and Cr(VI) concentrations ranged from 5 to 9190 mg/kg dry weight (dw) and from <0.47 to 31 mg/kg dw, respectively. Sediment porewater concentrations ranged from <10 to 83 μg/l for total chromium; Cr(VI) was not detected in sediment porewater (n = 78). Concentrations of AVS (ranging between <10.6 to 4178 mg/kg) and other geochemistry measurements indicated anoxic, reducing conditions in the majority of sediment samples. In polychaetes (Nereis virens) and clams (Macoma nasuta) exposed in the laboratory for 28 days to sediments contained between 135 and 1780 mg/kg dw total chromium, concentrations in whole tissues after 24-hour depuration ranged between 1.2 and 14.8 mg/kg wet weight (ww; median 1.6 mg/kg ww) total chromium. In whole tissues of indigenous polychaetes collected from the sediment, tissue concentrations of total chromium ranged between 1.0 and 37.5 mg/kg ww (median = 2.1 mg/kg ww). Chromium concentrations in whole tissues of animals exposed in the field or in the laboratory showed no relationship with total chromium or Cr(VI) concentrations in the sediment. There were no statistical differences among animals exposed to sediments from site and reference locations. The results of this study are consistent with sediment studies conducted elsewhere indicating low chromium bioavailability in sediment under reducing conditions. This study also highlights the importance of sediment geochemistry and in situ porewater measurements to understand the ecological significance of chromium in sediment and the potential for human health and ecological exposures.     

Assessment of EDTA in Chromium (III–VI) Toxicity on Marine Intertidal Crab (Petrolisthes laevigatus)

Chromium poses a potential threat to coastal ecosystems. We used standard toxicity bioassays (semi-static, chronic) to evaluate EDTA as a chelating agent for reducing trivalent and hexavalent chromium toxicity on Petrolisthes laevigatus. Crab survival decreased linearly with increased chromium concentrations and dropped significantly beginning at 40 mg/L Cr (VI) and 80 mg/L Cr (III). No significant differences were observed with Cr (III) + EDTA as compared with untreated controls. Cr (VI) toxicity was greater than that of Cr (III), with low individual survival rates. The protective effect of EDTA in the medium increased crab survival by 41%-48%.     

Chromium occurrence and speciation in Baltimore harbor sediments and porewater, Baltimore, Maryland, USA

Industrial activities in the Baltimore Harbor, Baltimore, Maryland, USA, have resulted in widespread chromium contamination of sediments. A comprehensive analysis of Cr speciation in sediment and porewater collected from 22 locations in the Baltimore Harbor was completed to understand Cr bioavailability and probability of toxicity due to Cr in sediments. The analysis employed a reverse-phase ion-pair high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) method. Sub-microgram-per-liter determination of Cr(III) and Cr(VI) in environmental samples was found, with method validation revealing broad method applicability of HPLC-ICP-MS to a wide range of sample types. The major limitation of the method was poor Cr species separation in high ionic strength solutions (greater than 0.1 M NaCl). Total Cr concentrations in Baltimore Harbor sediments ranged from 2.5 to 1,050 mg/kg with 11 of the 22 sites containing total Cr in excess of the 370 mg/ kg effects range-median (ER-M) sediment quality guideline. The Cr(VI) concentrations in sediments, however, were markedly lower, ranging from 0.10 to 0.38 mg/kg with Cr(VI) not detected in 14 of the 22 stations. Porewater concentrations, both for total Cr and Cr(VI), were quite low, with total Cr ranging from 0.20 to 2.16 microg/L and Cr(VI) ranging from 0.73 to 1.17 microg/L. The Cr(VI)-reducing capacity of the sediments, based on a sediment-spiking experiment, was found to be strongly correlated with the acid volatile sulfides content of the sediment. Overall, our results provide field validation of the hypothesis that Cr(VI) will not persist in sediments with excess acid volatile sulfides. Given the low concentrations of Cr(VI) in sediment and porewater, it appears unlikely that Cr in Baltimore Harbor sediments contributes appreciably to previously observed sediment toxicity.     

Assessment of supercritical fluid extraction use in whole sediment toxicity identification evaluations

Supercritical fluid extraction (SFE) with pure CO(2) was assessed as a confirmatory tool in phase III of whole sediment toxicity identification evaluations (TIEs). The SFE procedure was assessed on two reference sediments and three contaminated sediments by using a combination of toxicological and chemical measurements to quantify effectiveness. Sediment toxicity pre- and post-SFE treatment was quantified with a marine amphipod (Ampelisca abdita) and mysid (Americamysis bahia), and nonionic organic contaminants (NOCs) polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were measured in sediments, overlying waters, and interstitial waters. In general, use of SFE with the reference sediments was successful, with survival averaging 91% in post-SFE treatments. Substantial toxicity reductions and contaminant removal from sediments and water samples generated from extracted sediments of up to 99% in two of the contaminated sediments demonstrated SFE effectiveness. Furthermore, toxicological responses for these SFE-treated sediments showed comparable results to those from the same sediments treated with the powdered coconut charcoal addition manipulation. These data demonstrated the utility of SFE in phase III of a whole sediment TIE. Conversely, in one of the contaminated sediments, the SFE treatments had no effect on sediment toxicity, whereas sediment concentrations of PCBs and PAHs were reduced. We propose that, for some sediments, the SFE treatment may result in the release of otherwise nonbioavailable cationic metals that subsequently cause toxicity to test organisms. Overall, SFE treatment was found to be effective for reducing the toxicity and concentrations of NOCs in some contaminated sediments. However, these studies suggest that SFE treatment may enhance toxicity with some sediments, indicating that care must be taken when applying SFE and interpreting the results.     

Biological response to variation of acid-volatile sulfides and metals in field-exposed spiked sediments

Vertical and temporal variations of acid-volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediment can control biological impacts of metals. To assess the significance of these variations in field sediments, sediments spiked with cadmium, copper, lead, nickel, and zinc were deployed in Narragansett Bay for four months and recolonization by benthic organisms investigated. In surface sediments, concentrations of AVS decreased with time whenever AVS exceeded SEM but remained unchanged when AVS was less than SEM; in subsurface sediments, concentrations increased slightly. Concentrations of total SEM decreased with time only in surface sediments in which SEM exceeded AVS. Metals were not detected in interstitial waters of sediments where AVS exceeded SEM but were significant when SEM exceeded AVS and followed the order of solubilities of their sulfides. Concentrations in interstitial waters decreased with time, but exceeded U.S. Environmental Protection Agency chronic water quality criteria for 56 to 119 d. After 119 d, faunal assemblages in all treatments were similar to controls. Lack of biological response was related to vertical distributions of AVS and SEM. Biological exposure took place in near-surface sediments, where AVS exceeded SEM in even the highest treatments. Therefore, concentrations of metals in interstitial waters were low and consequently biological impacts were undetectable.     

Toxicity of chromium(III) and chromium(VI) to the earthworm Eisenia fetida

The effects of Cr(III) and Cr(VI) on the survival, behavior, and morphology of the earthworm, Eisenia fetida, in water at pH 6, 7, and 8 and their toxicity in 10 different soils and an organic substrate have been assessed. A decrease in the pH of water resulted in increased toxicity of Cr to the earthworm. In water, both Cr species produced behavioral changes and morphological symptoms. The 48-h LC(50) values of Cr(III) at pH 6, 7, and 8 were 1.93, 2.55, and 2.78 mg/L, and those of Cr(VI) were 0.47, 0.61, and 0.63 mg/L, respectively. The 14-day median lethal concentrations (LC(50)) of Cr(III) and Cr(VI) for earthworm range from 1656 to 1902 mg/kg for Cr(III) and from 222 to 257 mg/kg for Cr(VI) in soil. In the organic substrate, the LC(50) values of Cr(III) and Cr(VI) were 1635 and 219 mg/kg, respectively. Stepwise multiple regression analysis predicted that clay content of soils accounted for 92% and 88% of the variation in the LC(50) values of Cr(III) and Cr(VI), respectively.     

Toxicity assessment of sediments from the Grand Calumet River and Indiana Harbor Canal in Northwestern Indiana,USA

The objective of this study was to evaluate the toxicity of sediments from the Grand Calumet River and Indiana Harbor Canal located in northwestern Indiana, USA. Toxicity tests used in this assessment included 10-day sediment exposures with the amphipod Hyalella azteca, 31-day sediment exposures with the oligochaete Lumbriculus variegatus, and the Microtox Solid-Phase Sediment Toxicity Test. A total of 30 sampling stations were selected in locations that had limited historic matching toxicity and chemistry data. Toxic effects on amphipod survival were observed in 60% of the samples from the assessment area. Results of a toxicity test with oligochaetes indicated that sediments from the assessment area were too toxic to be used in proposed bioaccumulation testing. Measurement of amphipod length after the 10-day exposures did not provide useful information beyond that provided by the survival endpoint. Seven of the 15 samples that were identified as toxic in the amphipod tests were not identified as toxic in the Microtox test, indicating that the 10-day H. azteca test was more sensitive than the Microtox test. Samples that were toxic tended to have the highest concentrations of metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs). The toxic samples often had an excess of simultaneously extracted metals (SEM) relative to acid volatile sulfide (AVS) and had multiple exceedances of probable effect concentrations (PECs). Metals may have contributed to the toxicity of samples that had both an excess molar concentration of SEM relative to AVS and elevated concentrations of metals in pore water. However, of the samples that had an excess of SEM relative to AVS, only 38% of these samples had elevated concentration of metals in pore water. The lack of correspondence between SEM-AVS and pore water metals indicates that there are variables in addition to AVS controlling the concentrations of metals in pore water. A mean PEC quotient of 3.4 (based on concentrations of metals, PAHs, and PCBs) was exceeded in 33% of the sediment samples and a mean quotient of 0.63 was exceeded in 70% of the thirty sediment samples from the assessment area. A 50% incidence of toxicity has been previously reported in a database for sediment tests with H. azteca at a mean quotient of 3.4 in 10-day exposures and at a mean quotient of 0.63 in 28-day exposures. Among the Indiana Harbor samples, most of the samples with a mean PEC quotient above 0.63 ( i.e., 15 of 21; 71%) and above 3.4 ( i.e., 10 of 10; 100%) were toxic to amphipods. Results of this study and previous studies demonstrate that sediments from this assessment area are among the most contaminated and toxic that have ever been reported.     

Phytotoxicity and phytoaccumulation of trivalent and hexavalent chromium in brake fern

A recently recognized hyperaccumulator plant, Chinese brake fern (Pteris vittata), has been found to extract very high concentration of arsenic from arsenic-contaminated soil. Chromium usually is a coexisting contaminant with arsenic in most contaminated soils. The potential application of ferns for phytoremediation of chromium(III)- and chromium(VI)-contaminated soils and their phytotoxicity to ferns has not been studied before. In this study, chromium distribution and phytotoxicity at the plant and cellular levels of brake ferns were studied using chemical analyses and scanning electron microscopy. The results show a higher phytotoxicity of Cr from Cr(VI)-contaminated soil to Chinese brake fern than from Cr(III)-contaminated soil. Phytotoxicity symptoms included significant decreases both in fresh biomass weight and relative water content (RWC), and also in leaf chlorosis during the late stage of growing. At higher concentrations (500 mg/kg Cr[VI] and 1,000 mg/kg Cr[III] addition), plants showed reduction in the number of palisade and spongy parenchyma cells in leaves. Compared with other plant species reported for phytoremediation of Cr(VI)-contaminated soil, brake fern took up and accumulated significant amounts of Cr (up to 1,145 mg/kg in shoots and 5,717 mg/kg in roots) and did not die immediately from phytotoxicity. Our study suggests that Chinese brake fern is a potential candidate for phytoremediation of Cr(VI)-contaminated soils, even though plants showed severe phytotoxic symptoms at higher soil Cr concentrations.     

Laboratory Toxicity and Benthic Invertebrate Field Colonization of Upper Columbia River Sediments: Finding Adverse Effects Using Multiple Lines of Evidence

From 1930 to 1995, the Upper Columbia River (UCR) of northeast Washington State received approximately 12 million metric tons of smelter slag and associated effluents from a large smelter facility located in Trail, British Columbia, approximately 10 km north of the United States-Canadian border. Studies conducted during the past two decades have demonstrated the presence of toxic concentrations of heavy metals in slag-based sandy sediments, including cadmium, copper, zinc, and lead in the UCR area as well as the downstream reservoir portion of Lake Roosevelt. We conducted standardized whole-sediment toxicity tests with the amphipod Hyalella azteca (28-day) and the midge Chironomus dilutus (10-day) on 11 samples, including both UCR and study-specific reference sediments. Metal concentrations in sediments were modeled for potential toxicity using three approaches: (1) probable effects quotients (PEQs) based on total recoverable metals (TRMs) and simultaneously extracted metals (SEMs); (2) SEMs corrected for acid-volatile sulfides (AVS; i.e., ∑SEM - AVS); and (3) ∑SEM - AVS normalized to the fractional organic carbon (f(oc)) (i.e., ∑SEM - AVS/f(oc)). The most highly metal-contaminated sample (∑PEQ(TRM) = 132; ∑PEQ(SEM) = 54; ∑SEM - AVS = 323; and ∑SEM - AVS/(foc) = 64,600 umol/g) from the UCR was dominated by weathered slag sediment particles and resulted in 80% mortality and 94% decrease in biomass of amphipods; in addition, this sample significantly decreased growth of midge by 10%. The traditional ∑AVS - SEM, uncorrected for organic carbon, was the most accurate approach for estimating the effects of metals in the UCR. Treatment of the toxic slag sediment with 20% Resinex SIR-300 metal-chelating resin significantly decreased the toxicity of the sample. Samples ∑SEM - AVS > 244 was not toxic to amphipods or midge in laboratory testing, indicating that this value may be an approximate threshold for effects in the UCR. In situ benthic invertebrate colonization studies in an experimental pond (8-week duration) indicated that two of the most metal-contaminated UCR sediments (dominated by high levels of sand-sized slag particles) exhibited decreased invertebrate colonization compared with sand-based reference sediments. Field-exposed SIR-300 resin samples also exhibited decreased invertebrate colonization numbers compared with reference materials, which may indicate behavioral avoidance of this material under field conditions. Multiple lines of evidence (analytical chemistry, laboratory toxicity, and field colonization results), along with findings from previous studies, indicate that high metal concentrations associated with slag-enriched sediments in the UCR are likely to adversely impact the growth and survival of native benthic invertebrate communities. Additional laboratory toxicity testing, refinement of the applications of sediment benchmarks for metal toxicity, and in situ benthic invertebrate studies will assist in better defining the spatial extent, temporal variations, and ecological impacts of metal-contaminated sediments in the UCR system.     

Effects of acid-volatile sulfide on metal bioavailability and toxicity to midge (Chironomus tentans) larvae in black shale sediments

Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been studied intensely in recent years. Few studies, however, have determined the spatial variability of AVS and its interaction with simultaneously extracted metals (SEM) in sediments containing elevated concentrations of metals resulting from natural geochemical processes, such as weathering of black shales. We collected four sediment samples from each of four headwater bedrock streams in northcentral Arkansa (USA; three black shale-draining streams and one limestone-draining stream). We conducted 10-d acute whole-sediment toxicity tests using the midge Chironomus tentans and performed analyses for AVS, total metals, SEMs, and organic carbon. Most of the sediments from shale-draining streams had similar total metal and SEM concentrations but considerable differences in organic carbon and AVS. Zinc was the leading contributor to the SEM molar sum, averaging between 68 and 74%, whereas lead and cadmium contributed less than 3%. The AVS concentration was very low in all but two samples from one of the shale streams, and the sum of the SEM concentrations was in molar excess of AVS for all shale stream sediments. No significant differences in mean AVS concentrations between sediments collected from shale-draining or limestone-draining sites were noted (p > 0.05). Midge survival and growth in black shale-derived sediments were significantly less (p < 0.001) than that of limestone-derived sediments. On the whole, either SEM alone or SEM-AVS explained the total variation in midge survival and growth about equally well. However, survival and growth were significantly greater (p < 0.05) in the two sediment samples that contained measurable AVS compared with the two sediments from the same stream that contained negligible AVS.     

Linking ecological impact to metal concentrations and speciation: a microcosm experiment using a salt marsh meiofaunal community

Microcosm experiments addressed the impact of a mixture of Cu, Cr, Cd, Pb, and Hg at three concentrations after 36 h, 12 d, and 30 d on a meiofauna-dominated salt marsh community. In addition to analyzing effects on meiofaunal abundances, the study quantified the sediment metal concentrations of all five metals and pore-water concentrations, speciation, and ligand complexation of Cu. Abundances of deposit feeders such as the polychaete Streblospio benedicti, gastropods, and bivalves were impacted at lower metal concentrations than the mainly algal-feeding copepods, ostracods, and nematodes. We suggest that this might be due to bulk ingestion of metal-contaminated sediments resulting in relatively higher metal exposure in the deposit feeders than in the other, nondeposit feeding taxa. Copepod and ostracod abundances decreased only in the highest metal treatment, where levels of inorganic Cu ([Cu']) in pore waters were similar to levels associated with both acute and subacute toxicity in published in vivo toxicity studies of marine copepods. The higher metal treatments yielded disproportionately higher pore-water [Cu] compared with sediment [Cu], suggesting saturation of sediment-associated ligands with increased additions of Cu. Similarly, the higher metal treatments appeared to reach saturation of the organic Cu ligands, with the excess pore-water [Cu] present in the more toxic, inorganic species of Cu. Acid-volatile sulfide (AVS) concentrations at sediment horizons inhabited by meiofauna were low and AVS was not considered a significant metal ligand at these depths. Since meiofauna are predominantly associated with oxic surface sediments, it is doubtful that AVS is a major factor controlling availability of free metal for exposure to these taxa.     

Effects of organic amendments on the toxicity and bioavailability of cadmium and copper in spiked formulated sediments

We evaluated the partitioning and toxicity of cadmium (Cd) and copper (Cu) spiked into formulated sediments containing two types of organic matter (OM), i.e., cellulose and humus. Amendments of cellulose up to 12.5% total organic carbon (TOC) did not affect partitioning of Cd or Cu between sediment and pore water and did not significantly affect the toxicity of spiked sediments in acute toxicity tests with the amphipod Hyalella azteca. In contrast, amendments of natural humus shifted the partitioning of hoth Cd and Cu toward greater concentrations in sediment and lesser concentrations in pore water and significantly reduced toxic effects of both metals. Thresholds for toxicity, based on measured metal concentrations in whole sediment, were greater for both Cd and Cu in sediments amended with a low level of humus (2.9% TOC) than in sediments without added OM. Amendments with a high level of humus (8.9% TOC) eliminated toxicity at the highest spike concentrations of both metals (sediment concentrations of 12.4 microg Cd/g and 493 microg Cu/g). Concentrations of Cd in pore water associated with acute toxicity were similar between sediments with and without humus amendments, suggesting that toxicity of Cd was reduced primarily by sorption to sediment OM. However, toxic effects of Cu in humus treatments were associated with greater pore-water concentrations than in controls, suggesting that toxicity of Cu was reduced both by sorption and by complexation with soluble ligands. Both sorption and complexation by OM tend to make proposed sediment quality guidelines (SQGs) based on total metal concentrations more protective for high-OM sediments. Our results suggest that the predictive ability of SQGs could be improved by models of metal interactions with natural OM in sediment and pore water.     

Field validation of sediment zinc toxicity

A field study was conducted to validate concentrations of zinc in freshwater sediments that are tolerated by benthic macroinvertebrate communities and to determine whether a relationship exists with the acid volatile sulfide (AVS)-simultaneously extracted metal (SEM) model. In both the lake and riverine systems, one sediment type was high in AVS and one low in AVS, which resulted in zinc-spiked sediments that ranged from low to high SEM to AVS ratios. The colonization trays were sampled seasonally, ranging from 6 to 37 weeks of exposure, and were evaluated using several appropriate benthic indices. Results of the field evaluations at the four test sites confirmed the validity of the AVS-SEM model, predicting benthic macroinvertebrate effects correctly 92% of the time. In sediments where the SEM to AVS ratio or the AVS and organic (OC)-normalized fractions exceeded 8 and 583 micromol/g of OC, toxicity was observed from the zinc-spiked sediments. Conversely, when the SEM to AVS ratio or OC-normalized AVS fractions were less than 2 or 100 micromol/g of OC, no toxicity was observed. In the range of 148 to 154 micromol/g of OC, toxicity varied in two treatments. Total zinc concentrations in sediments showed no relationship to benthic effects. The most impaired benthic community occurred in the high-gradient stream sediments, which had low OC and AVS concentrations and SEM to AVS ratios of 33 and 44 in the spiked sediments. Five to six benthic metrics were depressed at SEM to AVS ratios of 8.32 and 9.73. The no-observed-effect level appeared to be near a SEM to AVS ratio of 2, with slight to no effects between ratios of 2.34 and 2.94. No sites with ratios of less than 2 showed any adverse effects.     

Determination of chromium picolinate and trace hexavalent chromium in multivitamins and supplements by HPLC-ICP-QQQ-MS

Chromium picolinate (CrPic) and trace hexavalent chromium (Cr(VI)) content were characterized in VITA-1 and VITB-1, two new multivitamin and mineral supplement candidate reference materials from National Research Council Canada, by two methods of high performance liquid chromatography inductively-coupled plasma triple quadrupole mass spectrometry. The conditions for the separation of Cr(VI) from EDTA-complexed Cr(III) were optimized such that species interconversions were not observed during analysis. Following extraction with dilute NH₄OH in water at pH 10 (for Cr(VI)) or 3:2 acetonitrile:water (for CrPic) and quantification by standard addition, it was concluded that CrPic accounted for 95–96 % of the Cr in VITA-1 and VITB-1, while Cr(VI) was not present above the detection limit of 0.13 μg Cr g⁻¹. Using the two developed methodologies, commercially-available nutritional supplements, in the form of vitamin tablets and dried food supplements, were assessed, and it was determined that CrPic accounted for the majority (92 %–98 %) of the chromium present in the tablets, and that Cr(VI) concentrations were below the detection limit for all samples except for the powdered beets where it accounted for nearly half of the total Cr present.     

The influence of sediment particle size and organic carbon on toxicity of copper to benthic invertebrates in oxic/suboxic surface sediments

The use of sediment quality guidelines to predict the toxicity of metals in sediments is limited by an inadequate understanding of exposure pathways and by poor causal links between exposure and effects. For a 10-d exposure to Cu-spiked sediments, toxicity to the amphipod Melita plumulosa was demonstrated to occur through a combination of dissolved and dietary Cu exposure pathways, but for the bivalves Spisula trigonella and Tellina deltoidalis, toxicity occurred primarily by exposure to dissolved Cu. For relatively oxidized sediments that had moderate amounts of organic carbon (2.6-8.3% OC), silt (20-100% <63-μm particles) but low acid-volatile sulfide (AVS), acute toxicity thresholds for the three species were derived based on the OC-normalized Cu concentration of the less than 63-μm sediment fraction. For all three species, no effects were observed at concentrations below 10 μg/L dissolved Cu (in pore water and overlying water) or below 12 mg Cu/g OC (for <63?μm sediment). For sediments with silt/OC properties of 20/0.5, 50/1, or 70/4%, the particulate Cu-based threshold equated to 60, 120, or 480 mg Cu/kg, respectively. For oxic/suboxic sediments in which AVS is not limiting metal availability, sediment quality guidelines of this form will provide adequate protection against toxicity and improve the prediction of effects for sediments with varying properties.     

Acid volatile sulfide and simultaneously extracted metals in the sediment cores of the Pearl River Estuary, South China

The acid-volatile sulfide (AVS), simultaneously extracted metals (SEM), total metals, and chemical partitioning in the sediment cores of the Pearl River Estuary (PRE) were studied. The concentrations of total metals, AVS, and SEM in the sediment cores were generally low in the river outlet area, increased along the seaward direction, and decreased again at the seaward boundary of the estuary. The amounts of AVS were generally greater in deeper sediments than in surface sediments. SEM/AVS was >1 in the surface sediments and in the river outlet cores. The ratio was <1 in the sediments down the profiles, suggesting that AVS might play a major role in binding heavy metals in the deep sediments of the PRE. The SEM may contain different chemical forms of trace metals in the sediments, depending on the metal reaction with 1M cold HCl in the AVS procedure compared with the results of the sequential chemical extraction. The SEM/AVS ratio prediction may overestimate trace metal availability even in the sediments with high AVS concentrations.     

Mobility and bioavailability of trace metals in sulfidic coastal sediments

High concentrations of Hg, Cd, Pb, Cu, and Zn were found in the euxinic sediment of the inner archipelago of Stockholm. In the sulfide-rich sediment, they are precipitated as metal sulfides with low dissolving capacity and bioavailability. In two experiments, the significance of acid-volatile sulfide (AVS) and dissolved sulfides for mobility, bioavailability, and toxicity of metals were studied by oxygenation of intact sediment cores. Influence of bioturbating deposit-feeding amphipods, that is, Monoporeia affinis, was examined on studied sediment processes. Results showed a low mobility of most metals except Cd and Zn. Bioturbation did not enhance mobility. Cd and Zn, released from the sediment, were not bioaccumulated in amphipods. In contrast, the less mobile metals Hg and Pb were bioaccumulated. A low toxicity of contaminated sediments, in terms of mortality and embryonic malformations of amphipods, was recorded. Results indicate that Cd, Zn, and Cu are comparatively unavailable after oxygenation of the metal sulfides. Similar results were recorded in contaminated sediments differing in redox potential, AVS, dissolved sulfides, and organic contents, suggesting that other metal ligands, in addition to AVS, are important for metal bioavailability and toxicity in anoxic and suboxic environments.     

Evaluating the ecological significance of laboratory response data to predict population-level effects for the estruarine amphipod Ampelisca abdita

Ten-day acute mortality of the benthic amphipod Ampelisca abdita is used in a number of regulatory, research, and monitoring programs to evaluate chemical contamination of marine sediments. Although this endpoint has proven to be valuable for characterizing the relative toxicities of sediments, the significance of acute mortality with respect to population viability has not yet been established. In this study, population modeling along with empirical extrapolation were used to describe a relationship between acute mortality and population-level response of A. abdita. The research involved the performance of a standard 10-d sediment toxicity bioassay and a 70-d full life-cycle chronic population (including reproduction) bioassay exposing A. abdita to sediments spiked with concentrations of the divalent metal cadmium (normalized to acid volatile sulfide) expected to produce a range of biological effects. These data provided age-specific schedules of survival and fecundity that were used to parameterize an age-classified projection matrix model for A. abdita. Measured exposure data and population growth rate estimates, obtained using the demographic information collected during the 70-d assay, were used to develop exposure-response models. These data were also used to develop an empirical relationship between population growth rate (lambda) and acute mortality. This relationship describes how acute data may be used to predict concentrations that produce population-level effects. Model manipulations permit extrapolation of early life-stage mortality (the acute endpoint) to changes in population growth rate. These relationships were used to evaluate a range of ecologically acceptable acute mortality for A. abdita.