Vertical distribution of acid-volatile sulfide and simultaneously extracted metals in mangrove sediments from the Jiulong River Estuary,Fujian, China

Background Acid-volatile sulfide (AVS) is operationally defined as sulfides in sediment, which are soluble in cold acid, and is reported as the most active part of the total sulfur in aquatic sediments. It is a key partitioning phase controlling the activities of divalent cationic heavy metals in sediment. Methods In order to examine this in mangrove environments, six sites were selected along the Jiulong River Estuary in Fujian, China, which had previously been reported to be polluted by heavy metals. Sediments were sampled from 0–60 cm depth at each site, and the spatial distribution of AVS and SEM (simultaneously extracted metals: copper, cadmium, zinc, and lead) were determined. Results and Discussion The results indicate that the AVS concentrations had a spatial variation, ranging from 0.24 to 16.10 μmol g⁻¹ sediment dry weight. The AVS concentration in the surface layer is lower than that of the deeper sediment, with peak values in the 15–30 cm horizon. There was no correlation between the AVS value and organic matter content or total dissolved salts, but a significant positive correlation of AVS with surface sediment (0–5 cm) moisture content was found. This indicates that water logged sediments tend to have a high AVS value. The amount of SEM was within the range of 0.33–2.80 μmol g⁻¹ sediment dry weight and decreased with sediment depth. Conclusions There was a marked variation in AVS and SEM among different sites studied. AVS concentrations were generally lower in the surface sediments, while SEM concentrations slightly decreased with the depth. Higher concentrations of SEM found in the upper layers of the sediments confirm the earlier suggestions that this study area may suffer from increasing heavy metal pollution. Recommendations and Perspectives When monitoring environmental impacts by using AVS, the micro and large-scale spatial variation as well as vertical distribution need to be estimated to avoid misleading results. Both AVS and SEM concentrations in different sediment layers should be taken into account in assessing the potential impact of heavy metals on the biotic environment.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

Nickel partitioning in formulated and natural freshwater sediments

A natural, field-collected sediment high in organic carbon (OC) and low in acid-volatile sulfide (AVS) was used to evaluate nickel (Ni) complexation to organic matter (OM) over a range of pH under anoxic conditions. It was found that OM strongly influenced Ni partitioning and that Ni complexation to OM was significantly influenced by pH, with complexation increasing with increasing pH (from pH 6 to 8). Using an equilibrium partitioning approach incorporating both [SEM(Ni)]-[AVS] and OC content, lethal and non-lethal toxicity test endpoints were calculated (predicted) and compared to observed toxicity test results using the amphipod, Hyalella azteca, exposed to four Ni-spiked natural sediments varying in OC and AVS content. Generally, lethal and non-lethal toxicity test endpoints were reasonably predictable in low AVS sediments. Due to the apparent lack of equilibrium between dissolved pore-water Ni and the pure Ni sulfide (likely the result of additional dissolved metal binding ligands), and the possible competition of liberated Fe2+ with Ni2+ for binding sites on organic matter, toxicity predictions (based on sediment OC and AVS content) overestimated the combined protective effects of AVS and OC in the sediments containing mid to high (27.87-44.05 micromol/g d.w.) AVS concentrations. Overall, it was found that equilibrium partitioning-based sediment quality guidelines can be improved through the incorporation of nickel complexation to sedimentary OM (in addition to AVS), although further research is required to fully describe nickel-OM interaction.     

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.     

Influence of Spartina alterniflora on the mobility of heavy metals in salt marsh sediments of the Yangtze River Estuary, China

Using bio-disturbed sulphide to trace the mobility and transformation of Cu, Pb, Ni and Zn in the sediments of the Spartina alterniflora-dominated salt marsh in the Yangtze River Estuary, measurements were made of the seasonal variations of acid-volatile sulphide (AVS) and of the simultaneously extracted metals (SEM) in the rhizosphere sediments. Microcosm incubation experiments recreating flooding conditions were conducted to evaluate the effect of AVS and other metal binding phases upon the dynamics of Cu, Pb, Ni and Zn in the salt marsh sediments. The results demonstrate that the ratio values of SEM/AVS have a significant seasonal variation in the rhizosphere sediments and that the anoxic conditions in the sediments were likely enhanced by S. alterniflora during the summer and autumn compared with the anoxic conditions resulting from the native species Phragmites australis and Scirpus mariqueter. The incubation experiments suggest that Fe(III) and Mn(IV/III) (hydr)oxides provide important binding sites for heavy metals under oxic conditions, and sulphide provides important binding sites for the Cu and Pb under anoxic conditions. Our observations indicate that the mobility of heavy metals in the salt marsh sediments is strongly influenced by biogeochemical redox processes and that the invasive S. alterniflora may increase the seasonal fluctuation in heavy metal bioavailability in the salt marsh ecosystem.     

Metal equilibration in laboratory-contaminated (spiked) sediments used for the development of whole-sediment toxicity tests

The equilibration and bioavailability of metals in laboratory-contaminated sediments have been investigated in order to provide better guidance on acceptable procedures for spiking sediments with metals for use in the development of whole-sediment toxicity tests. The equilibration rates of Cd, Cu, Ni and Zn spiked into three estuarine surface sediments with varying properties were investigated. Changes to sediment pH, redox potential, porewater and acid-soluble metals, acid-volatile sulfide and bacterial activity during equilibration, effects of temperature and disturbances following equilibration are reported. The addition of metals to sediments caused major decreases in pH and increases in redox potential as metals displaced iron(II) into the porewaters and added metals and iron (following oxidation) were hydrolyzed. The rates of equilibration of metals in porewaters varied considerably and were dependent on sediment and metal properties. For the oxic/sub-oxic sediments studied, metal-spikes of Cd, Cu, Ni and Zn appeared near equilibrium after 25-45, 10-15, 30-70 and 20-40 days, respectively. Acid-soluble metal concentrations decreased during the equilibration period indicating that the metals become more strongly associated with the sediments with time (less bioavailable). Bacterial activity was greatest in the sediment equilibrated at pH 7 and decreased following the addition of metals. During the equilibration period, bacterial activity increased in sediments equilibrated at pH 6, remained low in sediments at pH 8 and varied erratically in sediments at pH 7. Spiked sediments were shown to equilibrate more slowly at lower temperatures resulting in high porewater metal concentrations. Disturbances to equilibrated sediments because of sample manipulation caused significant iron(II) oxidation and losses of metals from porewaters. The importance of documenting spiking and equilibration procedures and carefully measuring and reporting sediment parameters is highlighted so that contaminant bioavailability and exposure pathways can be interpreted and organism sensitivity accurately determined. Recommendations are given for the preparation of metal-spiked sediments for toxicity testing purposes.     

Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments

Experiments were undertaken to examine the key variables affecting metal release and sequestration processes in marine sediments with metal concentrations in sediments reaching up to 86, 240, 700, and 3000 mg kg(-1) (dry weight) for Cd, Cu, Pb and Zn, respectively. The metal release and sequestration rates were affected to a much greater extent by changes in overlying water pH (5.5-8.0) and sediment disturbance (by physical mixing) than by changes in dissolved oxygen concentration (3-8 mg l(-1)) or salinity (15-45 practical salinity units). The physical disturbance of sediments was also found to release metals more rapidly than biological disturbance (bioturbation). The rate of oxidative precipitation of released iron and manganese increased as pH decreased and appeared to greatly influence the sequestration rate of released lead and zinc. Released metals were sequestered less rapidly in waters with lower dissolved oxygen concentrations. Sediments bioturbated by the benthic bivalve Tellina deltoidalis caused metal release from the pore waters and higher concentrations of iron and manganese in overlying waters than non-bioturbated sediments. During 21-day sediment exposures, T. deltoidalis accumulated significantly higher tissue concentrations of cadmium, lead and zinc from the metal contaminated sediments compared to controls. This study suggests that despite the fact that lead and zinc were most likely bound as sulfide phases in deeper sediments, the metals maintain their bioavailability because of the continued cycling between pore waters and surface sediments due to physical mixing and bioturbation.     

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically <10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment.     

Seasonal bioavailability of sediment-associated heavy metals along the Mississippi river floodplain.

A value of simultaneously extracted metal to acid-volatile sulfide (SEM-AVS) can provide important information regarding metal availability in anaerobic sediment. SEM and AVS concentrations were obtained by the cold-acid purge-and-trap technique during spring and summer at six locations along the Mississippi River floodplain. SEM-AVS values and AVS concentrations did not vary significantly between locations during both seasons. AVS concentrations were significantly greater during summer than spring, resulting in significantly lower SEM-AVS values in summer. Total SEM concentrations did not significantly vary between seasons or specific locations. SEM-AVS values were greater than one at each location during both seasons. Sediment metal toxicity was predicted to be absent for benthic organisms along the river floodplain.     

The effect of emergent macrophytes on the dynamics of sulfur species and trace metals in wetland sediments

This study focuses on the effect of plants on the biogeochemistry of sulfur species and the mobility of heavy metals in wetland sediments. Results showed that, in the presence of plants, sediments had elevated sulfate concentrations in the rhizosphere during the growing season, ranging from 0.2 to 6.20 mmol L(-1), whereas only a small difference in the sulfate profiles between vegetated and non-vegetated sediments was observed during senescence. Based on the sulfate concentration increase, the oxygen release rate from the roots to achieve the corresponding oxidation of sulfide was estimated as 0.85 g m(-2) day(-1). Evapotranspiration-induced advection is a major contributor to the transport of sulfate from the water column into the sediments, and also allows dissolved trace metals (i.e. Cd, Pb, and Zn) to be transported into the sediments and react with the acid volatile sulfide pool, resulting in the immobilization of trace metals in these sediments.     

Measuring acid volatile sulphide in floodplain lake sediments: effect of reaction time, sample size and aeration

For the routine measurement of acid volatile sulphide (AVS) in floodplain lake sediments, an earlier published diffusion method was adapted and optimised. We evaluated the effect of reaction time, sample weight and passive sample aeration on AVS recovery, and determined the method's reproducibility. The optimal reaction time was 4 h. Losses of AVS due to sample aeration did not occur within 15 min of sample-air contact. Relative standard deviation was <2.5% for known sulphide solutions, was between 10% and 15% for AVS concentrations in sediments and <12% for SEM concentrations in sediments, generally. Sediment samples with known SEM and AVS content were used to compare results of the developed method with the purge-and-trap method. There is a good agreement with the purge-and-trap method for SEM concentrations. AVS concentrations measured with the diffusion method are higher than with the purge-and-trap method. We conclude that the adapted diffusion method is well suited for the routine measurement of AVS concentrations in floodplain sediments.     

Sampling method, storage and pretreatment of sediment affect AVS concentrations with consequences for bioassay responses

Sediment treatment and sediment storage may alter sediment toxicity, and consequently biotic response. Purpose of our study was to combine these three aspects (treatment-toxicity-biotic response) in one integrated approach. We used Acid Volatile Sulfide (AVS) concentrations as a proxy of the disturbance of the sediment. AVS and Simultaneously Extracted Metal (SEM) concentrations were compared to bioassay responses with the freshwater benthic macroinvertebrate Asellus aquaticus. Storage conditions and sediment treatment affected AVS but not SEM levels. AVS can be used as a proxy for sediment disturbance. The best way to pretreat the sediment for use in a bioassay in order to maintain initial AVS conditions was to sample the sediment with an Ekman grab, immediately store it in a jar without headspace, and freeze it as soon as possible. In a survey using seven different sediments, bioassay responses of A. aquaticus were correlated with SEM and AVS characteristics.     

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.     

Assessing the cause of impacts on benthic organisms near Rouyn-Noranda, Quebec

Sediments from lakes near Rouyn-Noranda, Quebec, contain elevated concentrations of several metals, including Cd, Cu, Pb and Zn. Amphipods, fingernail clams, mayflies and tanytarsid midges were absent, and sediment toxicity was observed in chronic tests with Hyalella in sediments from Lac Dufault, the lake closest to Rouyn-Noranda. Bioaccumulation by Hyalella demonstrated elevated bioavailability of Cd, Co, Cr, Pb and Tl, but only Cd was accumulated to levels close to the toxic threshold. Copper, which is regulated by Hyalella, was not elevated in these amphipods, but it was elevated in overlying water in the toxicity tests. Toxic effects in Lac Dufault sediments are probably caused primarily by Cd, at least in amphipods, with a possible minor contribution from Cu. An integrated assessment, including sediment chemistry, benthic community composition, sediment toxicity, metal bioaccumulation in benthos, and comparison of bioaccumulation and/or overlying water concentrations with threshold effect concentrations, provides the best indication of effects and their cause.     

The effect of manipulating sediment pH on the porewater chemistry of copper- and zinc-spiked sediments

Spiking of sediment with metal cations that readily hydrolyse causes the sediment pH to decrease. Displaced iron and manganese also oxidise and hydrolyse, further lowering sediment pH. The lower pH of metal-spiked sediments requires a subsequent sediment neutralisation. This research compared the pH adjustment of Cu- and Zn-spiked sediments using single and multiple additions of 1M NaOH. Sediment pH, redox potential, and porewater metal concentrations were monitored over 40 days. Depth profiles were also measured to investigate stratification. A single pH adjustment to pH 7 and 8 initially counteracted the pH change caused by metal additions, however, pH continued to decrease slowly thereafter. Multiple pH adjustments diminished porewater Cu, Zn and Fe concentrations to a greater extent than a single pH adjustment, but the ongoing oxidative precipitation of porewater metals continued to consume OH(-) ions and impede pH maintenance. Displacement of high iron(II) concentrations and the opposing rates of iron(II) oxidative precipitation and bacterially-mediated iron(II) production, affected the partitioning of the added metals between the sediment and pore water. Despite similar pH over the spiked-metal concentration gradient following pH adjustment, sediments spiked with higher metal concentrations produced lower porewater Fe concentrations, possibly due to toxicity to iron(III) oxyhydroxide reducing bacteria. Distinct stratification of redox potential and dissolved Fe and Cu developed over a depth of 6cm during the 40-day equilibration period. Recommendations are provided on methods for preparing metal-spiked sediments in which the partitioning of metals between dissolved and particulate phases better resembles that of in situ (field) metal-contaminated sediments.     

Ecological risk assessment of arsenic and metals in sediments of coastal areas of northern Bohai and Yellow Seas, China

Distributions of arsenic and metals in surface sediments collected from the coastal and estuarine areas of the northern Bohai and Yellow Seas, China, were investigated. An ecological risk assessment of arsenic and metals in the sediments was evaluated by three approaches: the Sediment Quality Guidelines (SQGs) of the United States Environmental Protection Agency (USEPA), the degree of contamination, and two sets of SQGs indices. Sediments from the estuaries of the Wuli and Yalu Rivers contained some of the greatest concentrations of arsenic, cadmium, copper, mercury, lead, and zinc. Median concentrations of cadmium and mean concentrations of lead and zinc were greater than background concentrations determined for the areas. All sediments were considered to be heavily polluted by arsenic, but moderately polluted by chromium, lead, and cadmium. Current concentrations of arsenic and metals are unlikely to be acutely toxic, but chronic exposures would be expected to cause adverse effects on benthic invertebrates at 31.4% of the sites.     

Fractionation and extractability of sulfur, iron and trace elements in sulfidic sediments

This study describes iron and sulfur fractionation, and the related extractability of selected trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in estuarine sediments. The sediments were sulfidic, with moderately high concentrations of pore-water sulfide (200-600 micromol l(-1)) and acid-volatile sulfide (AVS; 9.9-129 micromol g(-1)). Pyrite-S concentrations increased with depth, with 63-251 micromol g(-1) at site W1 and 312-669 micromol g(-1) at site W2. The degree of sulfidisation was generally high (>80%), indicating that Fe may be limiting pyrite accumulation. The ratios of AVS to pyrite-S increased with sediment depth, as expected for the pyritisation of solid-phase AVS. Cadmium, Pb and Zn extractability in 1M HCl indicated that these elements are not significantly sequestered during pyritisation, whereas sequestration may be important for As, Cu and possibly Ni. Extractability trends for Cr suggest that diagenesis in sulfidic sediments may enhance Cr reactivity. Overall, replacement of AVS by pyrite during diagenesis may enhance the reactivity of Cd, Cr, Pb and Zn, whereas As, Cu and possibly Ni may be rendered less reactive.     

The Role of a Salt Marsh Plant on Trace Metal Bioavailability in Sediments. Estimation By Different Chemical Approaches * (7 pp)

Goal, Scope and Background The presence or absence of vegetation can condition sediment characteristics. The main aim of this work was to investigate the influence of the sea rush Juncus maritimus on metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) availability to organisms living on or in estuarine sediments, from Douro River (NW Portugal), by comparing the characteristics and chemical behaviour of rhizosediments (collected within the plant assemblage) and those of sediment (collected around the plant). In order to evaluate whether and how sediment characteristics condition the role of plants on metal availability, sandy and muddy sediments colonised by J. maritimus were studied in parallel. Methods Metal availability was estimated by enzymatic digestion with pepsin (ED), which may provide an estimate of metal availability to organisms living at estuarine sediments. Nevertheless, since no consensus exists yet on the most suitable methodologies to estimate metal bioavailability in sediments, two more conventional approaches, BCR sequential extraction (SE) and AVS/SEM model, were also used, in parallel, and the information these approaches provided was compared with that provided by ED. Total-recoverable metal contents were determined by atomic absorption spectrophotometry after sediment digestion using a high-pressure microwave system. Results and Discussion Plants could concentrate metals around its roots and rhizomes. In addition, they were capable of oxidizing (release of oxygen by the roots) the anaerobic medium surrounding their roots in muddy sediment (reducing AVS). As sulphide oxidation renders metals (Cd, Cu, Ni, Pb and Zn) into more soluble forms, according to the AVS/SEM model, metals from muddy sites would be more available in rhizosediment than in sediment. The SE approach led to a similar conclusion. Nevertheless, the results provided by ED pointed at opposite conclusion, particularly for Cd and Zn, indicating less availability at rhizosediments than in the surrounding sediment. ED results were interpreted as a consequence of an enrichment of the rhizosediment in organic ligands exuded by the roots or liberated by dead plants. The effect of complexation of metals by organic compounds, which ED could not decompose/dissolve, seemed to overcome that caused by sediment oxidation. In general, a comparison of the information about metal availability by ED, SE, AVS/SEM, showed that it did not always match and in few cases it was even contradictory. Conclusion and Outlook Therefore, a thorough evaluation of the metal availability in sediments requires a combination of different chemical approaches, so as to take into consideration differences in ways of organism exposure (interstitial water and/or ingestion of sediment particles). - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.