An integrated approach to the toxicity assessment of Irish marine sediments: application of porewater Toxicity Identification Evaluation (TIE) to Irish marine sediments

An integrated approach to the ecotoxicological assessment of Irish marine sediments was carried out between 2004 and 2007. Phase I Toxicity Identification Evaluation (TIE) of sediment porewaters from two sites on the east coast of Ireland were conducted. Initial Tier I screening of three Irish sites identified the need for TIE after significant toxicity was observed with Tisbe battagliai and the Microtox assay at two of the assayed sites (Alexandra Basin and Dunmore East). Porewaters classified as toxic were characterised using four manipulations, ethylenediaminetetraacetic acid (EDTA) chelation, sodium thiosulphate addition, C(18) Solid Phase Extraction (SPE) and Cation Exchange (CE) SPE. Prior to initial testing, and TIE manipulations, all porewater samples were frozen at -20 degrees C for several months until required. After initial Tier I testing Alexandra Basin porewater was classified as highly toxic by both assays while Dunmore East porewater only warranted a TIE with T. battagliai. Results of TIE manipulations for Alexandra Basin porewater and the Microtox Basic test were inconclusive. The toxicity of the porewater in this assay was significantly reduced after freezing. Three experimental episodes were conducted with one month between each for the Alexandra Basin porewater. After each month of freezing the baseline toxicity was further reduced in the Microtox assay, therefore it was not possible to draw accurate conclusions on the nature of the active contaminants in the sample. However, toxicity to T. battalgiai did not change after storage of the porewater. The C(18) and CE SPE decreased the toxicity of Alexandra Basin porewater to the copepod indicating that both organic and cationic compounds (e.g. metals) were active in the sample. Dunmore East porewater was assayed with T. battalgiai and again a combination of organic and inorganic compounds were found to be partly responsible for the observed toxicity (C(18), CE SPE and EDTA reduced toxicity). Results from these TIEs provide insight into the complexity of interpreting marine TIE data from porewater studies where mixtures of unknown substances are present.     

Physico-chemical and toxicological characterization of the historic estuarine sediments: a multidisciplinary approach

The accumulation rates, the geochronology of metals and PAH contamination, and the Microtox toxicity are studied in five sediment cores (50 cm length) covering different areas of the Santander Bay, Northern Spain. Chronology given by (210)Pb and (137)Cs reveals significant differences in accumulation rates between sites (0.2-1.1 cm/year), as well as a variable degree of anthropogenic enrichment factors for Fe, Mn, Cu, Pb, Zn, Ni (from 1 to 15) and concentrations of summation Sigma 16PAHs (from 0.01 to 23.84 mg/kg dw) in sediments over the last 90 years. The results indicate the increasing contamination pressure from industrial and urban activities along the Bay. No toxic results from the Microtox test are obtained either with pore water or with normalised sediment aqueous extracts (European Norm EN 12457), suggesting low water solubility and low availability of contaminants in the studied sediments. However, the EC50 values from the Microtox Basic Solid Phase Test (BSPT) ranged from 0.03% to 2.35%, showing vertical toxicity profiles in accordance with metal and PAHs behaviour. The correlation degrees of Microtox BSPT toxicity to chemical concentration in sediment profiles are widely variable showing a high site-dependent toxicity. The oligochaete Limnodrilus hoffmeisteri has been used as a chronic bioassay over surface sediments of two of the studied sites, showing results coherent with the Microtox BSPT acute test results. Global results of the present work provide regional geochemical baselines for metals and PAHs and toxicological data now make it possible to obtain a preliminary quality assessment of the Santander Bay sediment profiles.     

Novel approach for assessing heavy metal pollution and ecotoxicological status of rivers by means of passive sampling methods

In order to study the pollution of fluvial ecosystems, it is necessary to analyze not only the levels of chemical contaminants in water, but also those accumulated in the sediment matrix, as well as to assess its ecotoxicological status. Eleven Catalan (Spain) river sections (one sampling point per river) located near urban and industrial areas were sampled during winter of 2009. Water pollutants were collected by using passive samplers as Diffusive Gradient in Thin-Films (DGTs) and Semi-Permeable Membrane Devices (SPMDs). Point water samples were also collected. The concentrations of potentially toxic elements (PTE) in water, filtered water, DGTs and sediment samples were analyzed. Aqueous and organic solvent extracts of sediments samples and organic extracts of SPMDs were performed to assess acute toxicity to Vibrio fischeri by Microtox(?), and chronic toxicity to the green alga Pseudokirschneriella subcapitata. Microtox(?) test was also performed with DGT extracts. The results show that metals content of Catalan river waters are below the freshwater screening US EPA benchmarks, excepting some industrial areas (for Hg, Pb, and Zn). In contrast, sediments levels of some rivers were far above freshwater sediment screening US EPA benchmarks (for Zn, As, Cr, Pb, Ni, Hg, and Mn), particularly in the most industrialized areas. A good correlation was found between toxicity values of extracts (from sediments and DGTs) and PTE levels in sediments. The current results support the suitability of using combined point and passive sampling methods for assessing the chemical and ecotoxicological status of aqueous environments.     

Screening ecological risk assessment of persistent organic pollutants in Mediterranean sea sediments

A screening ecological risk assessment (ERA) was conducted for the first time in the Mediterranean basin in order to assess the toxicity posed to the benthic community by PCBs, DDTs and HCB in marine sediments. The characterization of the exposure was conducted by means of an extensive literature survey, generating a database with more than 2000 samples. The effects were assessed by the adoption of guidelines previously developed in the literature, because ecotoxicological information about persistent organic pollutants (POPs) in the Mediterranean sediments was lacking. Existing sediment quality guidelines (SQGs) for the target pollutants were compiled and consensus values were calculated for three different categories of toxicity, namely threshold effect concentration (TEC), probable effect concentration (PEC) and extreme effect concentration (EEC). The combination of exposure and effects characterization enabled the identification of some areas of concern in the vicinity of industrial and urban locations and in the mouths of the main Mediterranean rivers. Beyond the Mediterranean continental shelf, the level of toxicity for the benthic community was generally low. The evaluation of the toxicity induced by the mixture of the target pollutants spotted the importance of DDT contamination in the Mediterranean sediments, despite the fact that main inputs to the sea have been significantly reduced during the last decades.     

Derivation of predicted no effect concentrations (PNEC) for marine environmental risk assessment: application of different approaches to the model contaminant Linear Alkylbenzene Sulphonates (LAS) in a site-specific environment

Four sediment-dwelling marine organisms were exposed to sediments spiked with increasing concentrations of Linear Alkylbenzene Sulphonate (LAS). The selected endpoint mortality was reported daily and acute LC(50) (96 h), as well as final LC(10) values were calculated for the derivation of environmentally safe predicted no effect concentrations (PNEC) for the sediment compartment. PNECs were estimated by both application of assessment factors (AF) and the equilibrium partitioning method (EPM) as proposed by the EU TGD. Finally, environmental risk assessment in a site-specific environment, the Sancti Petri Channel, South Iberian Peninsula, was carried out at three different sampling stations with known environmental LAS concentrations. PNECs obtained by the assessment factor approach with acute toxicity data were one to two orders of magnitude lower than those from the equilibrium partitioning method. On the other hand, when applying lower AFs to the estimated LC(10) values, the PNECs obtained by both approaches were more similar. Environmental risk assessment carried out with the estimated PNECs in a site specific environment with known sediment LAS concentrations revealed that PNECs obtained with acute toxicity data were over conservative whereas those obtained with AF=10 on LC(10) data and EPM produced more realistic results in accordance with field observations carried out in the study area.     

A phytochelatin-based bioassay in marine diatoms useful for the assessment of bioavailability of heavy metals released by polluted sediments

The aim of the present work was to develop a new bioassay involving the presence of phytochelatins (PCs), detoxifying intracellular metal-binding peptides, in microalgae as response to metal bioavailability in re-suspensions of metal-polluted marine sediments. For this purpose, the synthesis of PCs has been studied in laboratory cultures of three marine diatoms, namely Phaeodactylum tricornutum, Thalassiosira weissflogii and Skeletonema costatum, exposed to elutriates of sediments collected in a polluted coastal area in the province of Pisa (Tuscany, Italy). Short- and long-term incubations in the elutriates of two marine sediments (named A and B) exhibited an increase of PCs synthesis in all the phytoplanktonic species examined, when the elutriate concentration increased from 0% to 100%. Elutriate B, which was mainly contaminated by Cd, was shown to be more effective to induce PCs than elutriate A, which was richer in Cu and TOC. The results show that the PCs response, in the microalgae examined, was species-specific. Our data also show that the PCs synthesis occurred before the growth rate was affected, thereby indicating that PCs can be considered as an early warning response of metal exposure. The PCs response in exponentially growing cultures of T. weissflogii, which was found to be the most sensitive alga, increased when the initial cellular density decreased. Finally, the positive relationship obtained between the cellular PCs concentration in T. weissflogii and the degree of metal contamination of the elutriates from twelve sediments collected in a metal-polluted coastal area, confirmed that the PCs-induction test can be applied in field studies. In conclusion, the response of these marine microalgae suggests that these cellular peptides could represent an excellent biomarker of metal exposure, which is useful for the assessment of sediment toxicity, by carrying out PCs-induction tests on sediment elutriates.     

Correlation of field-measured toxicity with chemical concentration and pollutant availability.

Direct field toxicity tests were performed in two Louisiana waterways, Bayous Trepagnier and St. John, on sediments containing organic/heavy metal mixtures. Our approach involved bioluminescent bacterial toxicity assays (using DeltaTox, which qualitatively identifies polluted areas, and Microtox, which quantifies toxicity). Samples were more completely analyzed in our laboratory using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and gas chromatography/mass spectrometry (GC/MS). Results indicate that lead is the primary toxic metal at the sites examined, though concentrations of metals fluctuate due to spatial variation and the dynamic nature of the waterways. Polycyclic aromatic hydrocarbons (PAHs) are the most abundant group of organics measured and appear to contribute to the overall toxic response. DeltaTox located toxic hotspots where there was an average light loss of 53-100%. Toxicity results from both assays agree but are well correlated with concentration measurements only for certain sediment fractions. Overall, the DeltaTox/Microtox approach appears to be rapid and cost effective for on-site hotspot identification, and may increase understanding of hazards associated with heavy metal and organic contaminants in these waterways.     

Impact of dredging in a shallow coastal lagoon: Microtox Basic Solid-Phase Test, trace metals and Corophium bioassay

The aim of this work was to measure survival of the amphipod Corophium insidiosum and luminescence inhibition in the marine bacterium Vibrio fisheri on surface sediment samples collected from a shallow coastal lagoon (Pialassa Baiona, northern Adriatic Italian coast) before execution of dredging operations to deepen the main inner channel of the lagoon and restore the water circulation. Trace metal (Cd, Cu, Cr, Hg, Ni, Pb) concentrations, grain size and organic carbon matter content as loss of ignition were also measured. Toxicity testing with V. fisheri was carried out according to the Microtox Basic Solid-Phase Test (BSPT) protocol. The preliminary outcomes of this work show that: (a) the investigated area can be categorised as moderately degraded; (b) there is no evident spatial pattern in sediment toxicity and trace metal concentrations; (c) Microtox responses are not biased by sediment characteristics such as silt, clay and organic matter content.     

Determining sediment quality for regulatory proposes using fish chronic bioassays

Sediment quality assessments for regulatory purposes (i.e. dredged material disposal) are characterized by linking chemical and acute ecotoxicological data. The design of chronic bioassays that incorporate more sensible endpoints than acute tests is discussed to address sediment quality for environmental quality assessment and regulatory proposes. The chronic tests use juveniles of commercial species of fish Sparus aurata and Solea senegalensis, to assess sediment toxicity in samples collected along different littoral areas in the North and the South of Spain. The organisms were exposed during 60 days and sublethal endpoints were selected including biomarkers of exposure to metals (metallothioneins - MTs) and to organic contaminants (ethoxyresorufin-O-deethylase activity - EROD activity) and biomarkers of effect (histopathology in different tissues, gill and liver). A Multivariate Analysis Approach was conducted in order to associate these biological responses with sediment metal concentration from the ports and with chemical residues in biological tissues exposed to sediments under laboratory conditions.     

Effects of a spill of bunker oil on the marine biological communities in Hong Kong

The effects of a recent bunker oil spill on the marine environment were assessed through investigation of the rocky shore fauna, phytoplankton population and macrobenthic communities over a study period of 150 days. In addition, toxicity experiments were carried out in the laboratory to ascertain the toxic effects of the oil-plus-dispersant on selected test organisms. The impacts of the spill on the marine fauna were minimal with no visible reduction in species and individual numbers. Possible reasons were the small amount of oil spilled, the rapid containment and dispersion in the clean-up operations, and the less toxic effects of the heavy bunker oil. On Hong Kong shores, the limpets can be identified as indicator species to oil pollution. A quick survey of the limpet fauna on the rocky shores immediately after a spill provides an initial assessment of the impacts on the shoreline. However, faunal recovery over a long-term period may be difficult to assess in view of the lack of baseline data on most of the marine biological communities in Hong Kong waters.     

Causes and ecological effects of resuspended contaminated sediments (RCS) in marine environments

Sediments act as a net sink for anthropogenic contaminants in marine ecosystems and contaminated sediments may have a range of toxicological effects on benthic fauna and associated species. When resuspended, however, particulate-bound contaminants may be remobilised into the water column and become bioavailable to an additional assemblage of species. Such resuspension occurs through a range of natural and anthropogenic processes each of which may be thought of as pulsed disturbances resulting in pulsed exposures to contaminants. Thus, it is important to understand not only the toxicological responses of organisms to resuspended contaminated sediments (RCS), but also the frequency, magnitude and duration of sediment disturbance events. Such information is rarely collected together with toxicological data. Rather, the majority of published studies (> 50% of the articles captured in this review) have taken the form of fixed-duration laboratory-based exposures with individual species. While this research has clearly demonstrated that resuspension of contaminated sediments can liberate sediment-bound contaminants leading to toxicity and bioaccumulation under controlled conditions, the potential for ecological effects in the field is often unclear. Monitoring studies suggest that recurrent natural disturbances such as tides and waves may cause the majority of contaminant release in many environments. However, various processes also act to limit the spatial and temporal scales across which contaminants are remobilised to the most toxic dissolved state. Various natural and anthropogenic disturbances of contaminated sediments have been linked to both community-level and sub-lethal responses in exposed populations of invertebrates and fish in the field. Together these findings suggest that resuspension of contaminated sediments is a frequently recurring ecological threat in contaminated marine habitats. Further consideration of how marine communities respond to temporally variable exposures to RCS is required, as well as research into the relative importance of various disturbances under field conditions.     

A multidisciplinary weight of evidence approach for classifying polluted sediments: Integrating sediment chemistry, bioavailability, biomarkers responses and bioassays

Evaluation of chemical bioavailability and onset of biological alterations is fundamental to assess the hazard of environmental pollutants, particularly when associated to sediments which need to be removed. In the present work, five sediment samples were collected from the Venice Lagoon and data from sediment chemistry were integrated with those of bioaccumulation of chemicals in European eel (Anguilla anguilla) exposed under laboratory conditions, responses of a wide battery of biomarkers, and standardized ecotoxicological bioassays. The overall results were elaborated within a recently developed, software-assisted weight of evidence (WOE) model which provides synthetic indices for each of considered line of evidence (LOE), before a general evaluation of sediment hazard. Levels of chemicals in sediments were not particularly elevated when compared to sediment quality guidelines of Venice Protocol. On the other hand, bioavailability was evident in some samples for Cd, Cu, Zn and, especially, polycyclic aromatic hydrocarbons. The ecotoxicological approach provided further evidence on the biological and potentially harmful effects due to released contaminants, and oxidative-mediated responses appeared of primary importance in modulating sublethal responses and the onset of cellular alterations. Biomarkers variations were sensitive, and more evident variations included significant changes of cytochrome P450 biotransformation pathway, antioxidant responses, onset of oxidative damages, lysosomal membrane stability and genotoxic effects. The results obtained from the battery of bioassays indicated that responses measured at organism level were in general accordance but less marked compared to the onset of sublethal changes measured through biomarkers. Overall this study revealed differences when comparing evaluations obtained from different LOEs, confirming the importance of considering synergistic effects between chemicals in complex mixtures. Compared to a qualitative pass-fail approach toward normative values, the proposed WOE model allowed a quantitative characterization of sediment hazard and a better discrimination of on the basis of various types of chemical and biological data.     

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.     

Pollution of the Begej Canal sediment--metals, radioactivity and toxicity assessment

The Begej Canal is one among a large number of canals in Vojvodina (Northern Province of Serbia and Montenegro). The paper describes a study of metal and radioactivity contamination of the Begej Canal sediment. It is also concerned with the evaluation of sediment acute toxicity based on standard test species Daphnia magna and simultaneously extracted metals and acid volatile sulfides. The quality of sediment was assessed according to Dutch standards, but the results were also compared with some Canadian and USEPA (United States Environmental Protection Agency) guidelines for sediment quality. The results showed severe pollution with chromium, copper, cadmium and zinc, whereby the anthropogenic origin of these contaminants was indicated. The tests of toxicity of sediment pore water to D. magna, gave no indication of the presence of substances in acutely toxic concentrations to this species. It can be speculated that, despite of high metal contents, the observed toxicity was low because of the high contents of clay and iron, as well as sulphide. Also, based on a comparison with the Danube sediment and Vojvodina soil in general, the data of the Begej sediment contamination with 238U and 137Cs. The 137Cs data were used for approximate dating of the sediment. No traces of contamination by nuclear power plants in the region were found, while the presence of technologically enhanced naturally occurring radioactive materials (TENORM) was proved. Conclusions based on different criteria for sediment quality assessment were in some cases contradictory. Study also showed that radioactivity aspects can be useful in sediment quality surveys. The obtained results will be invaluable for the future activities regarding integrated water management based on EC Water Framework Directive (2000/60/EC) in the Danube basin, and particularly in the region of crossborder water body of the Begej Canal.     

Development and application of an innovative expert decision support system to manage sediments and to assess environmental risk in freshwater ecosystems

With the aim of supporting decision makers to manage contamination in freshwater environments, an innovative expert decision support system (EDSS) was developed. The EDSS was applied in a sediment quality assessment along the Bormida river (NW, Italy) which has been heavily contaminated by an upstream industrial site for more than a century. Sampling sites were classified by means of comparing chemical concentrations with effect-based target values (threshold and probable effect concentrations). The level of each contaminant and the combined toxic pressure were used to rank sites into three categories: (i) uncontaminated (8 sites), (ii) mildly contaminated (4) and (iii) heavily contaminated (19). In heavily contaminated sediments, an environmental risk index (EnvRI) was determined by means of integrating chemical data with ecotoxicological and ecological parameters (triad approach). In addition a sediment risk index (SedRI) was computed from combining chemical and ecotoxicological data. Eight sites exhibited EnvRI values ≥ 0.25, the safety threshold level (range of EnvRI values: 0.14–0.31) whereas SedRI exceeded the safety threshold level at 6 sites (range of SedRI values: 0.16–0.36). At sites classified as mildly contaminated, sublethal biomarkers were integrated with chemical data into a biological vulnerability index (BVI), which exceeded the safety threshold level at one site (BVI value: 0.28). Finally, potential human risk was assessed in selected stations (11 sites) by integrating genotoxicity biomarkers (GTI index falling in the range 0.00–0.53). General conclusions drawn from the EDSS data include: (i) in sites classified as heavily contaminated, only a few exhibited some significant, yet limited, effects on biodiversity; (ii) restrictions in re-using sediments from heavily contaminated sites found little support in ecotoxicological data; (iii) in the majority of the sites classified as mildly contaminated, tested organisms exhibited low response levels; (iv) preliminary results on genotoxicity biomarkers indicate possible negative consequences for humans if exposed to river sediments from target areas.     

Sediment toxicity assessment in the Lagoon of Venice (Italy) using Paracentrotus lividus (Echinodermata: Echinoidea) fertilization and embryo bioassays

The capacity of two toxicity bioassays (fertilization and embryo toxicity tests) to discriminate sediment toxicity using the sea urchin Paracentrotus lividus was tested in five stations with different levels of pollution in the Lagoon of Venice. Two stations were located in estuarine sites, two in the industrial zone, and one in a site at the top of our quality gradient (reference). Elutriate was chosen as sediment matrix to assess the potential effects of bioavailable pollutants in the water column as a consequence of sediment resuspension (dredging and dumping, fishing gear, etc.). An experimental design based on Quality Assurance/Quality Control procedures (QA/QC) was adopted in order to set the methodological basis for an effective use of these bioassays in monitoring programs. Results revealed both higher embriotoxicity than spermiotoxicity in all stations and the efficacy of combined use of both toxicity bioassays in discriminating differing pollution/bioavailability between stations and periods. The good representativeness of the integrated sampling scheme and the standardization of all experimental phases yielded high precision of results. Clear Toxicity Fingerprints were evidenced for the investigated sites through the combined use of both bioassays. A good fit between ecotoxicological data and chemical contamination levels was found, except for unnatural sediment texture.     

A review on advantages of implementing luminescence inhibition test (Vibrio fischeri) for acute toxicity prediction of chemicals

Evaluation of biological effects using a rapid, sensitive and cost effective method can indicate specific information on toxicity/ecotoxicity. Since assays based on animals, plants and algae are expensive, time consuming and require large sample volume, recent studies have emphasized the benefits of rapid, reproducible and cost effective bacterial assays for toxicity screening and assessment. This review focuses on a bacterial assay, i.e., Vibrio fischeri bioluminescence inhibition assay, which is often chosen as the first test in a test battery based on speed and cost consideration. The test protocol is simple and was originally applied for aqueous phase samples or extracts. The versatility of the assay has increased with subsequent modification, i.e., the kinetic assay for turbid and colored samples and the solid phase test for analyzing sediment toxicity. Researchers have reported the Vibrio fischeri bioluminescence assay as the most sensitive across a wide range of chemicals compared to other bacterial assays such as nitrification inhibition, respirometry, ATP luminescence and enzyme inhibition. This assay shows good correlations with other standard acute toxicity assays and is reported to detect toxicity across a wide spectrum of toxicants.     

Predictive abilities of numerical sediment quality guidelines in Sydney Harbour, Australia, and vicinity

Matching chemical and toxicological data of surficial sediments from Sydney Harbour, Australia, and vicinity, were collected to evaluate predictive abilities of Effects Range-Low (ERL), Effects Range-Median (ERM) and other sediment quality guidelines (SQGs). Samples (n=103) containing a wide range of chemicals and concentrations were subjected to a battery of 4-6 toxicity tests. ERLs and functionally equivalent low-range SQGs were highly predictive of non-toxicity when not exceeded, as incidences of toxicity were 0-8%. ERMs and other mid-range SQGs were predictive of toxicity in combined test data with > or = 80% of toxic samples with one or more SQG exceeded. Predictive abilities of mid-range SQGs were low for amphipod survival tests (generally < 20% toxic samples), but the incidence of toxicity increased with increasing numbers of SQGs exceeded and increasing mean SQG quotients. Predictive abilities of SQGs generally matched their narrative intent when outcomes of multiple toxicity tests were considered, and were consistent with North American data. Functionally equivalent SQGs gave comparable results (except where developed for single chemical classes), indicating that predictive abilities were primarily influenced by sensitivities of test species and/or the bioavailability of contaminants.     

Sediment quality in Rio Guadiamar (SW, Spain) after a tailing dam collapse: contamination, toxicity and bioavailability

An integrated assessment of sediment quality in the Guadiamar River after a mining spill was conducted. The concentration of different metals and other conventional parameters were measured in sediments located along the river. Four sediment toxicity tests (Hyalella azteca 28-day survival and growth test; Chironomus riparius 10-day survival and growth test; Hexagenia spp. 21-day survival and growth test; and Tubifex tubifex 28-day reproduction and survival test) were carried out to determine the effects associated with the accidental spill. The geochemical fractions of 6 metals (Fe, Mn, Zn, Cu, Pb, and Cd) were determined to establish the bioavailability of the metals. The relationship found in the concentrations of metals associated with the mobile fractions of the sediments in the sites studied is similar to the toxic mud from tailing pond and confirms that the toxic effects are associated with the metals Zn and Cd originating from the spill.     

Partition of iodine (¹²⁹I and ¹²⁷I) isotopes in soils and marine sediments

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope ¹²⁹I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its environmental mobility is strongly linked to organic matter.Due to its long half-life (15.7 million years), ¹²⁹I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different types of organic matter in soil and sediment is rarely explored. Here we present a sequential extraction of ¹²⁹I and ¹²⁷I chemical forms encountered in a Danish soil, a soil reference material (IAEA-375), an anoxic marine sediment from Southern Norway and an oxic sediment from the Barents Sea. The different forms of iodine are related to water soluble, exchangeable, carbonates, oxides as well as iodine bound to humic acid, fulvic acid and to humin and minerals. This is the first study to identify ¹²⁹I in humic and fulvic acid and humin. The results show that 30-56% of the total ¹²⁷I and 42-60% of the total ¹²⁹I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0-5.5, ¹²⁷I and ¹²⁹I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 ¹²⁹I was mostly found to be bound to fulvic acid. Anoxic conditions seem to increase the mobility and availability of iodine compared to oxic, while subaerial conditions (soils) reduces the availability of water soluble fraction compared to subaqueous (marine) conditions.