Fingerprints of dioxin from thermal industrial processes

PCDD/F homologue profiles and 2,3,7,8 chlorine-substituted congener patterns are studied using principal component analysis and hierarchical cluster analysis. Measurement data from different industrial metallurgical processes such as iron and steel manufacturing, copper smelters and aluminium plants are compared. It appears that the PCDD/F homologue profiles from industrial metallurgical processes are similar to those from municipal solid waste incinerators. The 2,3,7,8 chlorine-substituted congener pattern from copper smelters is also very similar to that of municipal solid waste incinerators. However, the 2,3,7,8 chlorine-substituted congener pattern from an aluminum plant is very different, 2,3,7,8-TCDF being by far the most important TCDF congener.     

Pesticide residues in sediments and aquatic species in Lake Nokoué and Cotonou Lagoon in the Republic of Bénin

Lake Nokoué and Cotonou Lagoon are the most important and most productive continental freshwaters in Bénin, with an estimated fish production of over 2 tonnes per hectare in Lake Nokoué. Organochlorine pesticides are used in agriculture and to repel tsetse flies, malaria mosquitoes and other diseases raised. Sediment, fish, shrimp and oyster species were collected in Lake Nokoué and Cotonou Lagoon for pesticide residues analysis. The main pesticides identified in sediment were pp′-DDT and its metabolites pp-DDE and pp′-DDD, with residue levels between the detection limit and 24.4 μg/kg dry weight. Fish species commonly consumed such as Elops lacerta, Podamasys jubelini, Gobbienellus occidentalis, Ethmalosa fimbriata, Mugil cephalus and Hemichromis fasciatus were contaminated with residues of seven to nine pesticides, including pp-DDE, op′-DDD, pp′-DDD, op′-DDT, pp′-DDT, α-endosulfan, aldrin, dieldrin and γ-hexachlorocyclohexane. The levels ranged from detection limit to 289 ng/g lipid. The same pesticides were also detected in other aquatic species, such as shrimp and oysters. A summed risk assessment, comparing pesticide intake levels through fish consumption with tolerable daily intake levels proposed by the World Health Organization, showed in all cases a low risk for human health.     

In vitro Methylation of Arsenite in Flemish giant rabbit Cytosol

The formation of ⁷⁴As‐monomethyIarsonic acid and ⁷⁴As‐dimethylarsinic acid from carrier‐free radiolabelled ⁷⁴As‐arsenite was evaluated in an assay mixture containing 17.6% liver cytosol from the Flemish Giant rabbit. The optimal incubation temperature and pH were respectively, 39°C and 7.6. After a 2h incubation about 90% of ⁷⁴As was protein bound. Protein bound ⁷⁴As was released by hot 2 M HNO₃ (1 min, 110°C). The treatment did not destroy methylated As‐species. Up to 70% of the carrier‐free ⁷⁴As‐arsenite was methylated. Liver cytosol was stored, without loss of activity, in liquid nitrogen in the presence of 2 mM glutathione. The optimal s‐adenosyl‐methionine concentration was 1.7mM. Formation of ⁷⁴As‐monomethylarsonic acid and ⁷⁴As‐dimethylarsinic acid increased up to a glutathione concentration of respectively 10 and 20 mM. Methylation also went through in the presence of other reducing agents and proved to be ATP dependent.     

Enchytraeus crypticus as model species in soil ecotoxicology

Enchytraeids are ecologically relevant soil organisms, due to their activity in decomposition and bioturbation in many soil types worldwide. The enchytraeid reproduction test (ERT) guidelines ISO 16387 and OECD 220 are exclusive to the genus Enchytraeus and recommend using the species E. albidus with a 6-week test period. The suggested alternative, E. crypticus has a shorter generation time which may enable the ERT to be twice as fast. To confirm the suitability of a 3-week test period for E. crypticus, the toxicity of five chemicals, with distinct properties and modes of action, was assessed in LUFA 2.2 soil. In all controls the validity criteria were met, as survival of E. crypticus was above 92% and more than 772 juveniles were produced. The good performance supports its appropriateness as model species. Reproduction was more sensitive than survival, with only cadmium and 3,5-dichloroaniline causing significant lethal effects in the tested concentration ranges. The effect concentration causing 50% reduction in the number of juveniles (EC50) was 35 mg kg⁻¹ for cadmium, <1.0 mg kg⁻¹ for carbendazim, 145 mg kg⁻¹ for phenanthrene, 275 mg kg⁻¹ for pentachloroaniline and 102 mg kg⁻¹ for 3,5-dichloroaniline. To evaluate the sensitivity of E. crypticus, the present results were compared to literature data for E. albidus. In conclusion, E. crypticus is a suitable model species in soil ecotoxicology, with advantages such as good control performance and speed, leading to a reliable and faster ERT.     

QSAR development and bioavailability determination: The toxicity of chloroanilines to the soil dwelling springtail Folsomia candida

Quantitative structure–activity relationships (QSARs) are an established tool in environmental risk assessment and a valuable alternative to the exhaustive use of test animals under REACH. In this study a QSAR was developed for the toxicity of a series of six chloroanilines to the soil-dwelling collembolan Folsomia candida in standardized natural LUFA2.2 soil. Toxicity endpoints incorporated in the QSAR were the concentrations causing 10% (EC10) and 50% (EC50) reduction in reproduction of F. candida. Toxicity was based on concentrations in interstitial water estimated from nominal concentrations in the soil and published soil–water partition coefficients. Estimated effect concentrations were negatively correlated with the lipophilicity of the compounds. Interstitial water concentrations for both the EC10 and EC50 for four compounds were determined by using solid-phase microextraction (SPME). Measured and estimated concentrations were comparable only for tetra- and pentachloroaniline. With decreasing chlorination the disparity between modelled and actual concentrations increased. Optimisation of the QSAR therefore could not be accomplished, showing the necessity to move from total soil to (bio)available concentration measurements.     

Chronic toxicity of ZnO nanoparticles, non-nano ZnO and ZnCl2 to Folsomia candida (Collembola) in relation to bioavailability in soil

The chronic toxicity of zinc oxide nanoparticles (ZnO-NP) to Folsomia candida was determined in natural soil. To unravel the contribution of particle size and free zinc to NP toxicity, non-nano ZnO and ZnCl₂ were also tested. Zinc concentrations in pore water increased with increasing soil concentrations, with Freundlich sorption constants K_f of 61.7, 106 and 96.4 l/kg (n = 1.50, 1.34 and 0.42) for ZnO-NP, non-nano ZnO and ZnCl₂ respectively. Survival of F. candida was not affected by ZnO-NP and non-nano ZnO at concentrations up to 6400 mg Zn/kg d.w. Reproduction was dose-dependently reduced with 28-d EC50s of 1964, 1591 and 298 mg Zn/kg d.w. for ZnO-NP, non-nano ZnO and ZnCl₂, respectively. The difference in EC50s based on measured pore water concentrations was small (7.94-16.8 mg Zn/l). We conclude that zinc ions released from NP determine the observed toxic effects rather than ZnO particle size.     

Time profile of abamectin and doramectin excretion and degradation in sheep faeces

We studied abamectin and doramectin excretion and their degradation in sheep faeces under field conditions on pasture after a single subcutaneous dose (0.2mg/kg body weight). In the excretion experiment, maximal abamectin concentration (1277 ng/g dry faeces) was detected on day 3, while doramectin concentration showed two peaks (2186 and 1780 ng/g dry faeces on days 2 and 5, respectively). Both avermectins were excreted at approximately the same rate (k=0.23 day(-1) for abamectin and 0.19 day(-1) for doramectin). In the field, a rapid loss of abamectin and doramectin from sheep faeces was seen during the first 32 days after which concentrations remained constant at approximately 77 ng/g and 300 ng/g, respectively. The half life values (DT(50)) for abamectin and doramectin dissipation from sheep faeces were 23 and 22 days, respectively, during the first 32 days. Dissipation of both avermectins was strongly correlated with moisture content of the faeces.     

Ecotoxicological assessment of metal-polluted urban soils using bioassays with three soil invertebrates

This study aimed at assessing the quality of urban soils by integrating chemical and ecotoxicological approaches. Soils from five sites in downtown Naples, Italy, were sampled and characterized for physical-chemical properties and total and water-extractable metal concentrations. Bioassays with Eisenia andrei, Enchytraeus crypticus and Folsomia candida were performed to assess toxicity of the soils, using survival, reproduction and growth as the endpoints. Metal bioaccumulation in the animals was also measured. The properties and metal concentrations of the soils strongly differed. Metal bioaccumulation was related with total metal concentrations in soil and was highest in E. crypticus, which was more sensitive than E. andrei and F. candida. Responses of the three species to the investigated soils seemed due to both metal contamination and soil properties.     

Sensitivity of the zebrafish (Danio rerio) early life stage test for compounds with different modes of action

The sensitivity of the early life stage (ELS) toxicity test for two compounds with different modes of action was determined, and related to other toxicity tests with the same compounds. The zebrafish. Danio rerio, was used as a test organism, and the two model compounds were 1,2,3-trichlorobenzene (123TCB), a non-polar narcotic, and parathion, an acetylcholinesterase (AChE) inhibitor. Hatching and survival after 28 days were significantly reduced in the highest 123TCB treatment (263 microg/l), but not in any of the parathion treatments. Growth of the larvae was negatively affected at parathion concentrations above 20 microg/l, while AChE was only significantly inhibited at the highest concentration, 93 microg/l. No effects on growth were found in the 123TCB treatments. In comparison with acute and chronic studies with both compounds, the ELS test turned out to be less sensitive than chronic studies and more sensitive than acute studies. The difference in sensitivity between the tests systems seems however, to depend on the mode of action of the compound.     

Grid lysimeter study of steady state chloride transport in two Spodosol types using TDR and wick samplers.

Solute transport in soils is affected by soil layering and soil-specific morphological properties. We studied solute transport in two sandy Spodosols: a dry Spodosol developed under oxidizing conditions of relatively deep groundwater and a wet Spodosol under periodically reducing conditions above a shallow groundwater table. The wet Spodosol is characterized by a diffuse and heterogeneous humus-B-horizon (i.e., Spodic horizon), whereas the dry Spodosol has a sharp Spodic horizon. Drainage fluxes were moderately variable with a coefficient of variation (CV) of 25% in the wet Spodosol and 17% in the dry Spodosol. Solute transport in 1-m-long and 0.8-m-diameter soil columns was investigated using spatial averages of solute concentrations measured by a network of 36 Time Domain Reflectometry (TDR) probes. In the dry Spodosol, solute transport evolves from stochastic-convective to convective-dispersive at a depth of 0.25 m, coinciding with the depth of the Spodic horizon. Chloride breakthrough at the bottom of the soil columns was adequately well predicted by a convection-dispersion model. In the wet Spodosol, solute transport was heterogeneous over the entire depth of the column. Chloride breakthrough at 1 m depth was predicted best using a stochastic-convective transport model. The TDR sampling volume of 36 probes was too small to capture the heterogeneous flow and concomitant transport in the wet Spodosol.