Derivation of ecotoxicity thresholds for uranium

Assessment of the risk of impact from most radionuclides is based on the total radiological dose rate to the organism of concern. However, for uranium (U) there can be greater risk from chemical toxicity than radiological toxicity (depending on the isotopic composition). Chemical ecotoxicity of U is dependent on several environmental parameters. The most important are carbonate content, because of the formation of soluble carbonate complexes, and divalent cation content (Ca++ and Mg++), because of their competitive interaction with the uranyl ion (UO2++). This study summarizes the literature available to set PNECs (predicted no-effect concentrations) for chemical toxicity of U to non-human biota. The corresponding radiological doses were estimated, and as expected chemical toxicity proved to be the greater concern. There were limited data from some types of biota; however, PNECs for the types of biota of interest were as follows: terrestrial plants--250 mg U kg(-1) dry soil; other soil biota--100 mg U kg(-1) dry soil; freshwater plants--0.005 mg U L(-1) water; freshwater invertebrates--0.005 mg U L(-1) water; freshwater benthos--100 mg U kg(-1) dry sediment; freshwater fish at water hardnesses of: <10 mg CaCO3 L(-1) (very soft water)--0.4 mg U L(-1) water; 10-100 mg CaCO3 L(-1) (soft water)--2.8 mg U L(-1) water; and >100 mg CaCO3 L(-1) (hard water)--23 mg U L(-1) water; or as a function of hardness--0.26 (hardness as mg CaCO3 L(-1); mammals--0.1 mg U kg(-1) body weight d(-1).     

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.     

Effects of seven organic pollutants on soil nematode Caenorhabditis elegans

Caenorhabditis elegans is a free-living soil nematode that is commonly used as a model for toxicity tests. The aim of this study was to investigate the toxicity of seven organic pollutants: four azaarenes (quinoline, acridine, phenazine, and 1,10-phenanthroline), short-chain chlorinated paraffins, and two organochlorinated pesticides (toxaphene and hexachlorobenzene). The exposure to all chemicals was carried out in three test media (soil, agar, and aquatic medium), and adult mortality was evaluated after 24 and 48 h. Toxaphene was the most toxic substance with LC(50) (48 h) of 379 mg/kg in the soil and 0.2 mg/L in the aquatic medium. Quinoline was the most toxic chemical in agar test with LC(50) (48 h) of 10 mg/L. HCB showed a very low toxicity in all tests, maybe due to its very low water solubility. Longer than 24-h test duration was found necessary for getting more correct data on toxicity. In comparison with other studies, C. elegans was less sensitive than other soil invertebrates. Different response might be attributed to different exposure routes and shorter test duration. Equilibrium partitioning theory was used to calculate K(oc) from results of soil and aquatic tests but this approach was found not working. Our results suggest that the tests with nematode C. elegans should be included to the battery of tests for risk assessment of POPs in soil.     

Fate, behavior and effects of surfactants and their degradation products in the environment

Surfactants are widely used in household and industrial products. After use, surfactants as well as their products are mainly discharged into sewage treatment plants and then dispersed into the environment through effluent discharge into surface waters and sludge disposal on lands. Surfactants have different behavior and fate in the environment. Nonionic and cationic surfactants had much higher sorption on soil and sediment than anionic surfactants such as LAS. Most surfactants can be degraded by microbes in the environment although some surfactants such as LAS and DTDMAC as well as alkylphenols may be persistent under anaerobic conditions. LAS were found to degrade in sludge amended soils with a half-lives of 7 to 33 days. Most surfactants are not acutely toxic to organisms at environmental concentrations and aquatic chronic toxicity of surfactants occurred at concentrations usually greater than 0.1 mg/L. However, alkylphenols have shown to be capable of inducing the production of vitellogenin in male fish at a concentration as low as 5 microg/L. More toxicity data are needed to assess the effects on terrestrial organisms such as plants.     

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.     

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.     

Porewater as a matrix in toxicity bioassays with sea urchins and bivalves: evaluation of applicability to the Venice lagoon (Italy)

Porewater plays an important role in sediment toxicity assessment using bioassays, but the most reliable extracting method and the potential contribution of confounding factors to the real toxicity need to be studied. The applicability of bioassays with the early life stages of Paracentrotus lividus, Mytilus galloprovincialis and Crassostrea gigas on porewaters extracted by centrifugation from the Venice Lagoon (Italy) is evaluated and demonstrated: toxicity tests can discriminate the toxicity of porewaters from sites with different kinds and levels of pollution and, using toxicity scores, data are classified in five toxicity classes. Sulphides do not represent a confounding factor in porewater toxicity; in contrast ammonia exhibited some concentrations above the toxicity threshold for sea urchin embryos.     

An integrated approach to the toxicity assessment of Irish marine sediments: validation of established marine bioassays for the monitoring of Irish marine sediments

This paper describes the ecotoxicological evaluation of marine sediments from three sites around Ireland representative of a range of contaminant burdens. A comprehensive assessment of potential sediment toxicity requires the consideration of multiple exposure phases. In addition to the evaluation of multi-exposure phases the use of a battery of multi-trophic test species has been advocated by a number of researchers as testing of single or few organisms may not detect toxicants with a specific mode of action. The Microtox(R) solid phase test (SPT) and the 10-d acute amphipod test with Corophium volutator were used to assess whole sediment toxicity. Porewater and elutriates were assessed with the Microtox(R) acute test, the marine prasinophyte Tetraselmis suecica, and the marine copepod Tisbe battagliai. Solvent extracts were assayed with the Microtox(R) and T. battagliai acute tests. Alexandra Basin was identified as the most toxic site according to all tests, except the Microtox(R) SPT which identified the Dunmore East site as being more toxic. However, it was not possible to correlate the observed ecotoxicological effects with a specific and/or class of contaminants based on sediment chemistry alone. Therefore porewaters found to elicit significant toxicity (Dunmore East and Alexandra Basin) with the test battery were selected for further TIE assessment with T. battalgiai and the Microtox(R) system. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

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.     

Irreversible sorption of pentachlorophenol to sediments: experimental observations

The partitioning behavior of pentachlorophenol (PCP) in five sediments was studied using equilibrium sorption experiments and multiple cycles of sorption and desorption experiments. The results of the equilibrium sorption experiments showed that the isotherms of PCP on five sediments were linear and the partitioning coefficients (Kd) were proportional to the organic carbon content of the sediments. The average organic carbon content normalized partitioning coefficient (logK oc) of five sediments was 2.83 +/- 1.48. In multiple cycles of sorption and desorption experiments, the five sediments were found to exhibit statistically significant sorption-desorption hysteresis, and the hysteresis indices (HI) varied over a wide range (0.72 - 11.82). Correlations between the HI value and the percentage of lipid in the total organic matter in the sediment indicated that lipid was the main fraction to affect the hysteresis phenomenon, i.e., the higher the lipid percentage the greater the HI value. The hysteresis phenomenon was mostly caused by irreversible sorption of PCP on lipids, including entrapment by lipids, which induced the slow desorption rate from the sediment. Because of hysteresis in the sorption and desorption, the PCP ecological toxicity would be lower than expected.     

Geochemistry and bioavailability of metals in sediments from northern San Francisco Bay

In this study, metals (Be, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb and Hg) in the fine-grained fraction (<63 microm) from 12 sites at different locations in northern San Francisco Bay over a year period from March 2000 to March 2001 were analyzed after acid extraction. The results showed that metal concentrations in the sediments varied from site to site, whereas some of them were found elevated with respect to the sediment of Tomales Bay, CA, which has little contamination history, indicating an enrichment of the metals in the sediment samples analyzed. Sediment toxicity and bioaccumulation evaluation by a clam species, Macoma nasuta, exposed to the sediment samples collected from the six sampling sites was carried out. The results showed that the sediment samples tested significantly reduced clam survival. Toxicity of the sediments to the clam was, in part, related to elevated metal concentrations in the sediments. In order to examine geochemistry of the metals and to understand potential correlations between metal concentrations and geochemical matrix elements of the sediments, bioavailability and toxicity of the metals, detailed analysis of metal concentrations associated with total organic carbon and the Fe-oxy-hydroxides in the sediment samples was performed. The analysis showed that sediment geochemistry appeared to influence metal bioavailability and may have important impacts on the toxicity of these metals to the clam.     

Toxicokinetics/toxicodynamics of arsenic for farmed juvenile milkfish Chanos chanos and human consumption risk in BFD-endemic area of Taiwan

This paper presents a toxicokinetic/toxicodynamic analysis to appraise arsenic (As) bioaccumulation in farmed juvenile milkfish Chanos chanos at blackfoot disease (BFD)-endemic area in Taiwan, whereas probabilistic incremental lifetime cancer risk (ILCR) and hazard quotient (HQ) models are also employed to assess the range of exposures for the fishers and non-fishers who eat the contaminated fish. We conducted a 7-day exposure experiment to obtain toxicokinetic parameters, whereas a simple critical body burden toxicity model was verified with LC50(t) data obtained from a 7-day acute toxicity bioassay. Acute toxicity bioassay indicates that 96-h LC50 for juvenile milkfish exposed to As is 7.29 (95% CI: 3.10-10.47) mg l(-1). Our risk analysis for milkfish reared in BFD-endemic area indicates a low likelihood that survival is being affected by waterborne As. Human risk analysis demonstrates that 90%-tile probability exposure ILCRs for fishers in BFD-endemic area have orders of magnitude of 10(-3), indicating a high potential carcinogenic risk, whereas there is no significant cancer risk for non-fishers (ILCRs around 10(-5)). All predicted 90%-tiles of HQ are less than 1 for non-fishers, yet larger than 10 for fishers which indicate larger contributions from farmed milkfish consumptions. Sensitivity analysis indicates that to increase the accuracy of the results, efforts should focus on a better definition of probability distributions for milkfish daily consumption rate and As level in milkfish. Here we show that theoretical human health risks for consuming As-contaminated milkfish in the BFD-endemic area are alarming under a conservative condition based on a probabilistic risk assessment model.     

Extent of sonochemical degradation and change of toxicity of a pharmaceutical precursor (triphenylphosphine oxide) in water as a function of treatment conditions

The degradation of triphenylphosphine oxide (TPPO) in water, a toxic compound typically found in effluents from the pharmaceutical industry, by means of ultrasonic irradiation at 20 kHz has been investigated with emphasis on the effect of various parameters on conversion and acute toxicity. Experiments were carried out at liquid volumes of 50 and 80 ml, electric power outputs of 125, 187.5 and 250 W, initial TPPO concentrations of 10, 100 and 350 mg/L and temperatures of 5, 20, 35, 50 and 70 degrees C. TPPO conversion was found to increase with increasing power output and decreasing initial concentration and temperature. Measurements of dissolved total carbon showed that liquid-phase degradation by-products were more stable to ultrasonic irradiation than TPPO. Addition of t-butanol as a radical scavenger at a concentration of 1000 mg/L nearly completely suppressed TPPO degradation. Conversely, addition of radical promoters (Fe(2+) ions or H(2)O(2)) had a positive effect on degradation. Acute toxicity to marine bacteria vibrio fischeri was measured before and after ultrasonic irradiation. At the conditions employed in this study, irradiated TPPO samples were always more toxic than TPPO itself with toxicity levels being a function of treatment conditions.     

A bioassay approach to determine the dioxin-like activity in sediment extracts from the Danube River: ethoxyresorufin-O-deethylase induction in gill filaments and liver of three-spined sticklebacks (Gasterosteus aculeatus L.)

Sediment samples from the upper Danube River in Germany have previously been characterized as ecotoxicologically hazardous and contaminants in these sediments may contribute to the observed decline of fish populations in this river section. For the investigation of sediment toxicity there is a need for development, standardization and implementation of in vivo test systems using vertebrates. Therefore, the main objective of this study was to apply and evaluate a recently established fish gill EROD assay as a biomarker in sediment toxicity assessment by using extracts of well characterised sediment samples from the upper Danube River. This to our knowledge is the first application of this novel assay to sediment extracts. Sediments from four different sites along the upper Danube River were Soxhlet-extracted with acetone and dissolved in DMSO. Three-spined sticklebacks (Gasterosteus aculeatus L.) were exposed for 48 h to various concentrations of the extracts, to the positive control beta-naphthoflavone or to the solvent. Measurements of EROD activity in gill filaments and liver microsomes followed the exposure. Concentration-dependent induction of EROD in both gill and liver was found for all sediment extracts. The highest EROD-inducing potency was determined for extracts of sediments from the sites "Opfinger See" and "Sigmaringen" and the EROD activities in gill and liver correlated well. The results from the gill and liver assays were in accordance with in vitro results of previous investigations. The EROD activities measured in the present study corresponded with the concentrations of PAHs, PCBs and PCDD/Fs in the sediment samples derived in a previous study. The sticklebacks in this study were in the reproductive phase and a stronger EROD induction was obtained in the females than in the males. Implementation of the EROD assay in testing of sediment extracts gave highly reliable results which make this assay an ecotoxicologically relevant method for assessment of contamination with Ah receptor agonists in sediments.     

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.     

Sediment integrative assessment of the Bay of Cádiz (Spain): An ecotoxicological and chemical approach

This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p  < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone.     

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.     

Cumulative health risk assessment of 17 perfluoroalkylated and polyfluoroalkylated substances (PFASs) in the Swedish population

Humans are simultaneously exposed to a multitude of chemicals. Human health risk assessment of chemicals is, however, normally performed on single substances, which may underestimate the total risk, thus bringing a need for reliable methods to assess the risk of combined exposure to multiple chemicals. Per- and polyfluoroalkylated substances (PFASs) is a large group of chemicals that has emerged as global environmental contaminants. In the Swedish population, 17 PFASs have been measured, of which the vast majority lacks human health risk assessment information. The objective of this study was to for the first time perform a cumulative health risk assessment of the 17 PFASs measured in the Swedish population, individually and in combination, using the Hazard Index (HI) approach. Swedish biomonitoring data (blood/serum concentrations of PFASs) were used and two study populations identified: 1) the general population exposed indirectly via the environment and 2) occupationally exposed professional ski waxers. Hazard data used were publicly available toxicity data for hepatotoxicity and reproductive toxicity as well as other more sensitive toxic effects. The results showed that PFASs concentrations were in the low ng/ml serum range in the general population, reaching high ng/ml and low μg/ml serum concentrations in the occupationally exposed. For those congeners lacking toxicity data with regard to hepatotoxicity and reproductive toxicity read-across extrapolations was performed. Other effects at lower dose levels were observed for some well-studied congeners. The risk characterization showed no concern for hepatotoxicity or reproductive toxicity in the general population except in a subpopulation eating PFOS-contaminated fish, illustrating that high local exposure may be of concern. For the occupationally exposed there was concern for hepatotoxicity by PFOA and all congeners in combination as well as for reproductive toxicity by all congeners in combination, thus a need for reduced exposure was identified. Concern for immunotoxicity by PFOS and for disrupted mammary gland development by PFOA was identified in both study populations as well as a need of additional toxicological data for many PFAS congeners with respect to all assessed endpoints.