Guidelines for copper in sediments with varying properties

A major weakness of sediment quality guidelines (SQGs) is their poor ability to predict how toxicity thresholds change for different sediment types. Using species sensitivity distributions (SSDs) of copper effects data, new guidelines were derived for copper in non-sulfidic marine sediments in which organic carbon (OC) and particle size strongly influence copper bioavailability. The derived SQGs varied in a predictable manner with changes in sediment particle size and organic carbon (OC), and were shown to offer a significant improvement on the existing ‘single value’ SQG. Adequate protection for all benthic organisms is expected to be achieved for a OC-normalised copper concentration of 3.5 mg Cu g⁻¹ OC in the <63 μm sediment fraction. For short-term exposures, the equivalent acute guideline is 11 mg < 63 μm Cu g⁻¹ OC. The new SQGs incorporate a high degree of conservatism owing to the use of copper-spiked sediments and laboratory-based bioassays that were expected to result in greater metal exposure of organisms to bioavailable copper than would be expected for field-contaminated sediments with similar total copper concentrations. SQGs that vary with sediment properties were prepared in an easily referenced tabular format.     

Evaluation of Cu potential bioavailability changes upon coastal sediment resuspension: an example on how to improve the assessment of sediment dredging environmental risks

Purpose  

Metal bioavailability-based sediment quality analysis, inferred from geochemical partitioning data, may contribute to improve sediment management policies. This is important because decision-making processes should not give similar priorities to sediments offering contrasting environmental risks associated to metal bioavailability. However, current uses of Sediment Quality Guidelines (SQGs) as interpretive tools to support decisions about dredging-related activities have not considered the changes in metal bioavailability upon sediment resuspension.     

Using Various Guidelines and Approaches for the Assessment of Marine Sediment Quality

The aim of the present study is to explore the implications of using different quality guidelines and approaches for marine sediment characterization. As a case study, the sediments of Souda Port, Crete, Greece, were examined in order to assess heavy metal contamination and to estimate anthropogenic contribution and potential adverse effects to aquatic environment, as well as to indicate feasible future management options. The concentration of six heavy metals (Co, Cr, Cu, Ni, Pb, and Zn) was determined and compared with different sediment quality guidelines (SQGs) and regional/national criteria established for dredged material characterization and management. In addition, the geo-accumulation index (I_geo) was calculated and the sediments toxicity and heavy metals bioavailability were determined. Based on the experimental data, it is deduced that Souda sediments are characterized as moderately polluted only in terms of Co, Ni, and Pb.     

The estimation of PAH bioavailability in contaminated sediments using hydroxypropyl-beta-cyclodextrin and Triton X-100 extraction techniques

A study was conducted to investigate whether cyclodextrins and surfactants can be used to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in contaminated sediments. Two sediment samples were extracted with aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD) and Triton X-100. PAH removal during extraction was compared with PAH removal during biodegradation and solid-phase extraction. The latter two methods were used as reference methods to establish which part of the PAHs could be biodegraded and to what extent biodegradation was governed by bioavailability limitations. It was demonstrated that HPCD extraction followed solid-phase extraction and removed primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly bioavailable PAHs. Moreover, HPCD did not affect the degradation of PAHs in biodegradation experiments, while Triton X-100 enhanced the degradation of low molecular weight PAHs. It was concluded that HPCD extraction may provide a good method for the prediction of PAH bioavailability. Triton X-100 extraction is unfit for the prediction of PAH bioavailability.     

Inconsistency and comprehensiveness of risk assessments for heavy metals in urban surface sediments

Numerous indices have been developed to assess environmental risk of heavy metals in surface sediments, including the total content based geoaccumulation index (I_geo), exchangeable fraction based risk assessment code (RAC), and biological toxicity test based sediment quality guidelines (SQGs). In this study, the three indices were applied to freshwater surface sediments from 10 sections along an urbanization gradient of the Grand Canal, China to assess the environmental risks of heavy metals (Cu, Pb, Zn, Cd, and Cr) and to understand discrepancies of risk assessment indices and urbanization effects regarding heavy metal contamination. Results showed that Cd, Zn, and Pb were the most enriched metals in urban sections assessed by I_geo and over 95% of the samples exceeded the Zn and Pb thresholds of the effect range low (ERL) of SQGs. According to RAC, Cu, Zn, Cd, and Cr had high risks of adversely affecting the water quality of the Grand Canal due to their remarkable portions of exchangeable fraction in surface sediment. However, Pb showed a relative low risk, and was largely bounded to Fe/Mn oxides in the urban surface sediments. Obviously, the three assessment indices were not consistent with each other in terms of predicting environmental risks attributed to heavy metals in the freshwater surface sediments of this study. It is recommended that risk assessment by SQGs should be revised according to availability and site specificity. However, the combination of the three indices gave us a comprehensive understanding of heavy metal risks in the urban surface sediments of the Grand Canal.     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

Bioaccumulation kinetics of sediment-associated DE-83 in benthic invertebrates (Nereis succinea, polychaete)

Polychaetes (Nereis succinea) were exposed to DE-83 contaminated sediments to investigate the bioaccumulation and bioavailability of nona- and deca-BDEs in sediment. All the major congeners in DE-83 were bioavailable to the lugworms. The uptake coefficients (K_s) of nona- and deca-BDE congeners in lugworms were in the range of 0.18-0.65 (d⁻¹), with the values of BDE-207 and -208 slightly higher than those of BDE-206 and -209. Elimination of nona- and deca-BDE congeners from lugworms was very fast. The estimated half-lives of nona- and deca-BDE congeners in the lugworms were at 0.7 d. The bioavailability of nona- and deca-BDE congeners was very low, with BSAF of 0.017 for BDE-206 and -209 and 0.054 for BDE-207 and -208. These may be due to the large molecular size and high affinity of PBDEs to sediment particles. The contribution of BDE-206 in the profile of nona-BDEs in lugworm tissue decreased with exposure time while those of BDE-207 and -208 increased, which could be the result of the biotransformation of BDE-209 to BDE-207 and -208.     

Selective supercritical fluid extraction to identify aged sediment-bound PCBs available for uptake by eel

A naturally contaminated sediment was partially extracted with selective supercritical fluid extraction (SFE) to remove a fraction of supposedly bioavailable PCBs from the matrix. Eels (Anguilla anguilla) were cultured in systems with untreated and pre-extracted sediment, respectively, and it was shown that the SFE treatment selectively removed bioavailable PCBs from the sediment, since relative biota-to-sediment accumulation factors (BSAFs) for the eight studied PCB congeners were much lower in the pre-extracted than in the untreated system at the end of the study. Relative BSAF values decreased with about the same relative amount for all eight congeners, independent of the degree of chlorination and the initial concentration in the sediment. The results demonstrate the ability of SFE to selectively remove sediment-bound PCBs that are available for uptake by the eels, thus demonstrating the feasibility of using selective SFE to estimate bioavailability of PCBs in sediments.     

Total,dissolved, and bioavailable metals at Lake Texoma marinas

Dissolved metals in water and total metals in sediments were measured at marina areas in Lake Texoma during June 1999 to October 2001, and October 2001, respectively. The metals most often found in the highest concentrations in marina water were Na and Ca, followed by Mg and K. Elevated Cu levels detected in lake water appeared to be associated with Cu based anti-fouling paint used on boats. Metal concentrations in sediment were much higher than in water. The relative order of the concentration in sediment was Ca > Al > Fe > K > Mg > Na. Elevated Cu level at specific locations appeared to be associated with local anthropogenic sources of boat repair activities. There were positive relationships between several metal elements in water and sediment. Metals in 16 sediments from lake marinas were extracted with a weak electrolyte solution [0.1 M Ca(NO3)2] to predict the bioavailability of metals. Among the five heavy metals studied (As, Cd, Cr, Cu and Zn), Cu was the most bioavailable in Lake Texoma marinas.     

Accumulation and histopathological damage in the clam Ruditapes philippinarum and the crab Carcinus maenas to assess sediment toxicity in Spanish ports

The degree of contamination and toxicity in sediment from four Spanish ports (Cádiz, Huelva, Pasajes and Bilbao) was assessed in the present study. Two marine invertebrate species, the shore crab Carcinus maenas and the clam Ruditapes philippinarum, were exposed to the different sediments under laboratory conditions for 28 days. Relationships were developed among metal contamination (As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in sediments, metal accumulation in gill tissues and histopathological lesions in different biological tissues to assess sediment toxicity. A multivariate analysis approach was used to calculate sediment quality guidelines (SQGs) by linking metal concentration in sediments with histopathological lesions measured in the exposed organisms. The results showed significant contaminant accumulation and histopathological lesions due to As, Pb and Zn in sediments at the port of Huelva; As, Cr, Cu, Hg and Ni at the ports of Pasajes and Cádiz; and Cr and Hg at the port of Bilbao. The link between chemical concentration in sediments and histopathological lesions allowed the determination of SQGs for the chemicals As, Cd, Cu, Cr, Hg, Ni and Zn.     

The effect of resuspending sediment contaminated with antifouling paint particles containing Irgarol 1051 on the marine macrophyte Ulva intestinalis

The effect of resuspending sediment contaminated with Irgarol 1051 based antifouling paint particles on the green macroalga Ulva intestinalis was examined. U. intestinalis was also exposed to sediment spiked with Irgarol 1051. The macroalga were exposed over 21 days to the resuspension of sediments containing 61.2 mg kg(-1) of antifouling paint particles containing Irgarol 1051 that provided aqueous Irgarol 1051 concentrations of approximately 0.3 microg l(-1), Irgarol 1051 and appropriate controls. The growth response was compared with that for 'clean' sediment. Resuspension of sediment was associated with reduced growth when compared to seawater alone. Resuspension of sediment spiked with Irgarol 1051 was associated with a greater reduction in growth, with growth being significantly reduced when sediment containing antifouling paint particles was resuspended. The data suggest that the prolonged disturbance of sediments containing antifouling paint particles in marinas represents a potential and as yet unquantified hazard to photosynthetic organisms.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa

Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Spatial distribution of acid-volatile sulphide concentration and metal bioavailability in mangrove sediments from the Brisbane River, Australia

Acid-volatile sulphide (AVS) was measured at regular positions along eight transects through a mangrove forest in the Brisbane River, Queensland, Australia. Concentrations ranged from 0.33 to 22.61 micromol S g(-1) sediment dry weight. There was no correlation between AVS concentration and the proportion of clay-sand in the sediment, but sediments with high AVS concentrations tended to contain more water (rs=0.43; p=0.01). AVS concentrations were used to assess the potential bioavailability of the sediment heavy metal burden. The spatial variability of potential bioavailability was high and depended to a great extent on which metals were considered as part of the AVS complexing system. It is suggested seasonal variations would further increase the observed variability in bioavailability. This variation should be taken into account when monitoring and assessing long-term trends in sediment toxicity.     

Toxicity of sediment cores from Yangtze River estuary to zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) embryos

Toxicity evaluation is an important segment in sediment quality monitoring in order to protect aquatic organisms and human health. The purpose of this study is to assess the toxicity of sediments from three sediment cores in Yangtze River Estuary, China, using the zebrafish (Danio rerio) embryo tests. Fertilized zebrafish eggs were exposed to both whole sediments and sediment organic extracts prepared from collected sediments, in order to provide a comprehensive and realistic insight into the bioavailable toxicity potential of the sediments. As end points, development parameters (mortality, hatching rate, and abnormality) in the developing embryos were recorded during the 96-h exposure. The results showed that some samples increased mortality, inhibited the hatching of embryos, and induced morphological abnormalities. The embryonic toxicities presented serrated changes and irregular distribution with depth, which may be related to hydrodynamic effect and unstable environmental input. However, lethal and sub-lethal effects were more significant at the sub-surface sediments (10～40 cm), which indicated that the pollution is more serious in recent decades.     

Ex situ remediation of contaminated sediments using mineral additives: assessment of pollutant bioavailability with the Microtox solid phase test

The aim of this work is to assess the potential ecotoxicological effects of contaminated sediments treated with mineral additives. The Microtox solid phase test was used to evaluate the effect of mineral additives on the toxicity of sediment suspensions. Four Mediterranean port sediments were studied after dredging and bioremediation: Sample A from navy harbor, sample B from commercial port and samples C and D from pleasure ports. Sediment samples were stabilized with three mineral additives: hematite, zero-valent iron and zeolite. Results show that all studied mineral additives can act as stabilizer agent in highly contaminated sediments (A and C) by decreasing dissolved metal concentrations and sediment toxicity level. On the contrary, for the less contaminated samples (B and D) hematite and zeolite can provoke toxic effect towards Vibrio fischeri since additive particles can favor bacteria retention and decrease bioluminescence emission.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

Influence of Chironomus riparius (Diptera, Chironomidae) and Tubifex tubifex (Annelida, Oligochaeta) on oxygen uptake by sediments. Consequences of uranium contamination

The diffusive oxygen uptake (DOU) of sediments inhabited by Chironomus riparius and Tubifex tubifex was investigated using a planar oxygen optode device, and complemented by measurements of bioturbation activity. Additional experiments were performed within contaminated sediments to assess the impact of uranium on these processes. After 72 h, the two invertebrate species significantly increased the DOU of sediments (13-14%), and no temporal variation occurred afterwards. Within contaminated sediments, it was already 24% higher before the introduction of the organisms, suggesting that uranium modified the sediment biogeochemistry. Although the two species firstly reacted by avoidance of contaminated sediment, they finally colonized it. Their bioturbation activity was reduced but, for T. tubifex, it remained sufficient to induce a release of uranium to the water column and an increase of the DOU (53%). These results highlight the necessity of further investigations to take into account the interactions between bioturbation, microbial metabolism and pollutants.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.