Arsenic toxicity in a sediment-dwelling polychaete: detoxification and arsenic metabolism.

The accumulation, subcellular distribution and speciation of arsenic in the polychaete Arenicola marina were investigated under different laboratory exposure conditions representing a range of metal bioavailabilities, to gain an insight into the physiological mechanisms of how A. marina handles bioaccumulated arsenic and to improve our understanding of the potential ecotoxicological significance of bioaccumulated arsenic in this deposit-feeder. The exposure conditions included exposure to sublethal concentrations of dissolved arsenate, exposure to sublethal concentrations of sediment-bound metal mining mixtures, and exposure to lethal concentrations of sediment-bound metal mining mixtures and arsenic- and multiple metal-spiked sediments. The sub-lethal exposures indicate that arsenic bioaccumulated by the deposit-feeding polychaete A. marina is stored in the cytosol as heat stable proteins (~50%) including metallothioneins, possibly as As (III)-thiol complexes. The remaining arsenic is mainly accumulated in the fraction containing cellular debris (~20%), with decreasing proportions accumulated in the metal-rich granules, organelles and heat-sensitive proteins fractions. A biological detoxified metal compartment including heat stable proteins and the fraction containing metal-rich granules is capable of binding arsenic coming into the cells at a constant rate under sublethal arsenic bioavailabilities. The remaining arsenic entering the cell is bound loosely into the cellular debris fraction, which can be subsequently released and diverted to an expanding detoxified pool. Our results suggest that a metal sensitive compartment comprising the cellular debris, enzymes and organelles fractions may be more representative of the toxic effects observed.

Bioaccumulation of arsenic from water and sediment by a deposit-feeding polychaete (Arenicola marina): a biodynamic modelling approach.

Arsenic bioaccumulation in the deposit-feeding polychaete Arenicola marina has been investigated using biodynamic modelling. Radiotracer techniques were used to determine the rates of uptake of As as arsenate from water and sediment and its subsequent efflux in the laboratory. Lugworms accumulated As from solution linearly at concentrations of 2-20 microg l(-1), with a corresponding uptake rate constant of 0.1648+/-0.0135 l g(-1)d(-1). 7.8+/-0.8% (assimilation efficiency) of the As ingested bound to sediments was retained after egestion of unassimilated metal. Elimination of As followed a two-compartment model, with mean efflux rate constants (from the slow pool) very similar for As accumulated from solution and ingested sediments (0.0449+/-0.0034 and 0.0478+/-0.0225 d(-1), respectively) and a corresponding biological half-time of roughly 15 d. A biodynamic model was constructed and validated through the comparison of biodynamic model predictions against measured bioaccumulated concentrations in lugworms from five UK estuaries. The model accurately predicted bioaccumulated As concentrations in lugworms using mean values of relevant physiological parameters (uptake rate, efflux rate and growth rate constants), a site-specific ingestion rate (calculated according to mean worm size and sediment organic matter content and expressed as the rate of ingestion of the mass of fine sediment), a site-specific sediment concentration measured after HCl extraction, and a standard dissolved As concentration. This combination of parameters showed that sediment ingestion contributed 30-60% of the total As accumulated by lugworms at the studied sites, depending on the different geochemistry at each site. This study showed that it is difficult to predict accurately As bioaccumulation at sites with different chemistries, unless that chemistry is taken into account.

Pathways of trace metal uptake in the lugworm Arenicola marina.

Radiotracer techniques were used to determine the rates of trace metal (Ag, Cd and Zn) uptake and elimination (33 psu, 10 degrees C) from water and sediment by the deposit-feeding polychaete Arenicola marina, proposed as a test species for estuarine-marine sediments in whole-sediment toxicity tests. Metal uptake rates from solution increase with increasing dissolved metal concentrations, with uptake rate constants (+/-SE) (lg(-1) d(-1)) of 1.21+/-0.11 (Ag), 0.026+/-0.002 (Zn) and 0.012+/-0.001 (Cd). Assimilation efficiencies from ingested sediments were measured using a pulse-chase radiotracer feeding technique in two different lugworm populations, one from a commercial supplier (Blyth, Northumberland, UK) and the other a field-collected population from the outer Thames estuary (UK). Assimilation efficiencies ranged from 2 to 20% for Zn, 1 to 6% for Cd and 1 to 9% for Ag for the Northumberland worms, and from 3 to 22% for Zn, 6 to 70% for Cd and 2 to 15% for Ag in the case of the Thames population. Elimination of accumulated metals followed a two-compartment model, with similar efflux rate constants for Zn and Ag and lower rates of elimination of Cd from the slow pool. Efflux rate constants (+/-SE) of Zn and Ag accumulated from the dissolved phase were 0.037+/-0.002 and 0.033+/-0.006 d(-1) whereas Cd was eliminated with an efflux rate constant one order of magnitude lower (0.003+/-0.002 d(-1)). When metals were accumulated from ingested sediments, the efflux rate constants for the slow-exchanging compartment were of the same order of magnitude for the three metals, and of the same order of magnitude as those derived after the dissolved exposure for Zn and Ag (0.042+/-0.004 and 0.056+/-0.012 d(-1) for Zn and 0.044+/-0.012 and 0.069+/-0.016 d(-1) for Ag for the Northumberland and Thames populations, respectively). Cd accumulated from ingested sediments was eliminated with a rate constant not different from the fast-exchanging compartment after the water-only exposure (0.025+/-0.012 and 0.020+/-0.004 d(-1) for the Northumberland and Thames populations, respectively). A biodynamic model was used to estimate the relative importance of the dissolved phase versus ingested sediment as source of metal for the worms, showing that more than 90% of the Zn and Cd and more than 70% of Ag in lugworms is accumulated from sediment ingestion at realistic environmental concentrations. The model also shows that metal accumulation is highly dependent on the ingestion rate and assimilation efficiency.

A multivariate assessment of sediment contamination in dredged materials from Spanish ports.

This paper summarises the performance of simple multivariate exploratory analyses to investigate on their potential application for dredged material characterization and management. The data from 25 sampling stations located at 7 different Spanish ports, produced a matrix consisting of 300 observations on 10 variables: the metals Cd, Cu, Cr, Hg, Ni, Pb and Zn, the metalloid As, the sum of PAHs and PCB congeners, and the proportion of fines and organic matter content. The cluster analysis was suitable to separate the sediments according to the extent of contamination while the PCA indicated that the data was defined by two principal factors: a first one that accounts for 56.4% of the total variance, describing the metallic contaminants except Ni and Cr, and a second one that accounts for 14.4% of the total variance describing the organic contaminants PAHs and PCBs. The use of these two simple and untutored multivariate techniques seems a cost-effective approach for future pre-dredging investigations in the studied areas providing useful information for dredged material characterization and management with little additional effort.

Is Arenicola marina a suitable test organism to evaluate the bioaccumulation potential of Hg, PAHs and PCBs from dredged sediments?

This paper presents the results of investigations on the suitability of lugworms (Arenicola marina) to study the bioaccumulation potential of Hg, PCB and PAH compounds from dredged sediments upon laboratory exposure. The results of tissue concentrations for several sediments from Spanish ports showed that it is possible to identify increased levels of contaminants in lugworms just after 10 days of exposure although different bioaccumulation trends were shown amongst compounds and sediments. Total and organic Hg compounds were accumulated following a non-linear trend, with a sharp increase of tissue concentrations in lugworms exposed to levels of contamination associated to a significant increase in mortality. Interestingly organic Hg compounds accounted for an average of 40% of the total Hg in lugworms exposed to sediments presenting sublethal concentrations while, when exposed to sediments presenting lethal concentrations, organic Hg compounds only accounted for 4% of the total Hg accumulated in lugworms. While lugworms seem to readily accumulate Hg and PCB compounds, with some variability explained by the organic matter content in sediments or other factor for which it accounts for, the results for PAHs suggest a more complex process of bioaccumulation as no relationship was observed between the measured concentrations in sediments and in lugworms, not even after correcting the results for this factor. Besides, the differences in the calculated BSAFs for each compound and for each sediment supported the use of bioassays for evaluating the bioaccumulation potential of sediment-bound contaminants as part of the assessment framework required in pre-dredging investigations, as they still offer unique information about the bioavailability of sediment-bound contaminants.

Direct comparison of amphipod sensitivities to dredged sediments from Spanish ports.

The sensitivity of the benthic amphipod species Ampelisca brevicornis and Corophium volutator to dredged sediments was compared through simultaneous testing on the standard 10 days sediment toxicity test. The results of mortality obtained for 22 harbor sediments sampled at several Spanish ports were studied together with the physico-chemical characteristics of the samples to obtain the incidence of toxicity in terms of dredged material categories and to identify possible differences in the amphipod mortality results when using one or another test species. The results showed a similar incidence of toxicity for medium-high and highly contaminated sediments for both amphipod species, similar to that obtained through the comparison of the chemical concentrations measured in sediments with the single limit values used in Spain for dredged material characterization and management. On the contrary, C. volutator presented a higher mortality and a higher incidence of toxicity when exposed to low and medium-low contaminated sediments, which may have been caused by the lower sensitivity of A. brevicornis when exposed to sediments from its natural environment. When compared to other amphipod species used for whole sediment toxicity assessment, both amphipod species used in this study reported slightly higher sensitivities although these differences could have been associated to the different set of chemical compounds considered when characterizing the sediment samples. In this sense, the amphipod mortality results were better predicted through the use of mean quotients than just by comparing the measured chemical concentrations with the single limit values used in Spain, which indicates that the toxic response of both species was caused by the cocktail of contaminants present in the sediments. Finally, the correlation analysis identified a higher association between A. brevicornis mortality and the metallic contaminants while C. volutator was more correlated with the organic micro-pollutants. Despite these differences, the results indicate that Ampelisca brevicornis can be used as test organism for dredged material characterization when enough individuals of other recommended species such as Corophium volutator are not available.

Liquid versus solid phase bioassays for dredged material toxicity assessment.

Since 1994 the results of the analyses of key chemical compounds (trace metals, polychlorinated biphenyls and polycyclic aromatic hydrocarbons) and the comparison with the corresponding sediment quality guidelines (SQGs) are used in decision-making for dredged material management in Spain. Nonetheless in the last decades a tiered testing approach is promoted for assessing the physical and chemical characteristics of dredged sediments and their potential biological effects in the environment. Bioassays have been used for sediment toxicity assessment in Spain but few or no experiences are reported on harbour sediments. We studied the incidence of toxicity in the 7 d bioassay using rotifers (Brachionus plicatilis) and the 48 h bioassay using sea urchin (Paracentrotus lividus) embryos over a series of experiments employing 22 different elutriates. The relative performance of this exposure phase was not comparable to data on the 10-d acute toxicity test using the burrowing amphipod Corophium volutator and the polychaete Arenicola marina, carried out on the whole sediments. These results evidence the importance of the exposure route and the test selected in decision-making, as the toxicity registered for the undiluted elutriates was largely due to the different solubility of sediment-bound contaminants. This work and other studies indicate that for many sediments, a complete battery of test is recommended together with physico-chemical analyses to decide whether dredged sediments are suitable for open water disposal or not.

Using sediment quality guidelines for dredged material management in commercial ports from Spain.

Dredged material contamination was assessed in different commercial ports from Spain: Port of Cádiz and Huelva, South West; Bilbao and Pasajes, North; Cartagena and Barcelona, East; Coruña, North West. Sediment from different locations of these ports was sampled and was characterized following the Spanish recommendations for dredged material management. This characterization included grain size distribution, organic matter content and concentration of the chemical compounds included in the list of pollutants and hazardous substances (As, Cd, Cu, Cr, Hg, Ni, Pb and Zn; PCB congeners IUPAC number 28, 52, 101, 118, 138, 153 and 180; PAHs were also analyzed). The results were compared to the limit values of Spanish Action Levels that define the different categories for assessment and management. A set of empirically derived sediment quality guidelines (SQG) was used to assess the possible toxicity of the dredged materials and to improve the use of the chemical approach to characterize dredged material for its management.

Linking sediment chemical and biological guidelines for characterization of dredged material.

Dredged material management in Spain and possible options for the different categories is discussed according to chemical sediment quality guidelines. Also an approach using an integrated assessment that includes biological end points as part of a tiered testing schema is discussed for future implementation in Spanish recommendations. To establish the feasibility of using both kinds of guidelines, an example of the utility and validity of the approach that links both chemical and biological guidelines proposed for the management of dredged material characterization processes data from a particular case study associated with a port in the north of Spain are discussed. The use of both kinds of methodologies, together with the necessity of assessing the bioavailability of some contaminants, has been shown as a powerful tool for the best selection of different disposal options of dredged material in the case study described.

Bioavailability of heavy metals bound to sediments affected by a mining spill using Solea senegalensis and Scrobicularia plana.

After the Aznalcóllar mining spill (April, 1998) different ecosystems along the Guadiamar river and the Guadalquivir estuary were impacted by high concentrations of metals. The concentration of metals Zn, Cd, Pb, Cu and As has been detected as a good tracer of the pathway of the toxic spill. Different individuals of the fish Solea senegalensis and the clam Scrobicularia plana were exposed to contaminated sediments after the accidental spill in the south-west Spain. The induction of metallothioneins in fish and the bioaccumulation of metals in clams were determined in different tissues to determine the biological adverse effect associated with the heavy metals from the spill. A relationship between the enrichment of metals in the tissues and the induction of metallothioneins was determined for those assays performed using contaminated sediments. The bioaccumulation of metals indicates that the risk associated with the spill should be continuously evaluated to establish the sublethal effects related to the accident.