Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.     

Acute effects of 3,4-dichloroaniline on biomarkers and spleen histology of the common goby Pomatoschistus microps

The aromatic amine 3,4-dichloroaniline (DCA) is a model environmental contaminant, precursor for synthesis and degradation product of several herbicides, which is commonly found in European estuarine ecosystems. In this work, the possibility of using biochemical and histological markers to assess sub-lethal effects of DCA in natural populations of Pomatoschistus microps juveniles was investigated. Alterations on the activities of the enzymes acetylcholinesterase (AChE), lactate dehydrogenase (LDH) and glutathione S-transferase (GST) and histological alterations on spleen were investigated after 96 h of exposure to sublethal concentrations of DCA (0.50-1.49 mg/l). At the concentrations tested, DCA had no effect on AChE activity. LDH and GST activities were significant altered in treated animals when compared to control groups. As already described for mammals, DCA induced splenic histological alterations in P. microps, including expansion of red pulp and deposition of hemosiderin granules in a concentration-dependent manner. This suggests that DCA is a xenobiotic of concern in estuaries receiving agricultural effluents.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Washing as a remediation technology applicable in soils heavily polluted by mining-metallurgical activities

A permanent solution in order to remediate a heavily contaminated soil is washing it utilizing the appropriate reagents. The study presented in this paper deals with the washing of a soil highly polluted by mining and metallurgical activities. Pollution consists of slags, sulphur compound waste and various low grade lead condensates, all rich in heavy metals and metalloids (Pb, As, Cu, Zn, Mn and Fe). Soil was washed with deionized water, 6, 3, 2 and 1 M HCl, 6 M H(2)SO(4), 6 M HNO(3) and 0.1 M Na(2)EDTA. High extraction efficiency was achieved with respect to hydrochloric acid even at the lowest concentration; the solubility of pollutants in nitric acid was low, while sulphuric acid was proven to be problematic with respect to lead. Mobilization of metals and metalloids under DI water effect was minimal indicating that the elements fraction that is weakly bound to soil particles is insignificant. Furthermore, a kinetic study was undertaken, utilizing 1 M HCl and 0.1 M Na(2)EDTA. Results illustrated that 1 M HCl was more effective for intermediate mixing times (up to 4 h) while 0.1 M Na(2)EDTA was better applicable to short mixing times (<1 h) and low pH values (pH < 7.1). 1 M HCl was proven to be very effective for the removal of pollutants from contaminated soil but the high metal content of the resulting solution necessitates further treatment for the retention of metals.     

Breakdown products on metabolic pathway of degradation of benz[a]anthracene by a ligninolytic fungus

Cultures of the ligninolytic fungus Irpex lacteus incubated in a nutrient liquid medium degraded more than 70% of the initially applied benz[a]anthracene within 14 days. At the first step of metabolization, benz[a]anthracene was transformed via a typical pathway of ligninolytic fungi to benz[a]anthracene-7,12-dione (BaAQ). The product was further transformed by at least two ways, whereas one is complied with the anthracene metabolic pathway of I. lacteus. Benz[a]anthracene-7,12-dione was degraded to 1,2-naphthalenedicarboxylic acid and phthalic acid that was followed with production of 2-hydroxymethyl benzoic acid or monomethyl and dimethylesters of phthalic acid. Another degradation product of BaAQ was identified as 1-tetralone. Its transformation via 1,4-naphthalenedione, 1,4-naphthalenediol and 1,2,3,4-tetrahydro-1-hydroxynaphthalene resulted again in phthalic acid. None of the intermediates were identified as dead-end metabolites. Metabolites produced by ring cleavage of benz[a]anthracene using the ligninolytic fungus are firstly presented in this work.     

Prediction of ozone concentrations in Oporto city with statistical approaches

The performance of three statistical methods: time-series, multiple linear regression and feedforward artificial neural networks models were compared to predict the daily mean ozone concentrations. The study here reported was based on data from one urban site with traffic influences and one rural background site. The studies were performed for the year 2002 and the respective four trimesters separately. In the multiple linear regression and feedforward artificial neural network models, the concentrations of ozone, the concentrations of its precursors (nitrogen oxides) and some meteorological variables for one and two days before the prediction day were used as predictors. For the application of these models in the validation step, the inputs of ozone concentration for one and two days before were replaced by the ozone concentrations predicted by the models. The results showed that time-series modelling was not profitable. In the development step, similar performances were obtained with multiple linear regression and feedforward artificial neural network. Better performance indexes were achieved with feedforward artificial neural network models in validation step. Concluding, feedforward artificial neural network models were more efficient to predict ozone concentrations.     

Cadmium and zinc bioaccumulation and metallothionein response in two freshwater bivalves (Corbicula fluminea and Dreissena polymorpha) transplanted along a polymetallic gradient

This study was designed to compare the metallothionein (MT) response capacity of two freshwater bivalves, Corbicula fluminea and Dreissena polymorpha, along an environmental gradient of polymetallic pollution. The bivalves were transplanted into 4 stations in southwestern France, with a cadmium and zinc pollution gradient. MT and metal concentrations were measured in the soft bodies of the clams and mussels over 2.5 months. In the zebra mussels, variations in MT concentrations were strictly correlated to progressive Cd and Zn bioaccumulation. In contrast, the faster response in the clams appeared positively correlated to Cd accumulation only, with the activation of efficient detoxification mechanisms which limited Cd bioaccumulation and reduced Zn concentrations over time. Nevertheless, despite stronger metal accumulation factors in D. polymorpha, C. fluminea revealed higher sensitivity of MT response along the pollution gradient.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Importance of cholinesterase kinetic parameters in environmental monitoring using estuarine fish

The aim of the present study was to determine the kinetic parameters and cholinesterase (ChE) activity in two teleost fish, the white mouth croaker Micropogonias furnieri (Scianidae) and the Madamango sea catfish Cathorops spixii (Ariidae), to verify their suitability as sentinel species of aquatic pollution by anticholinergic compounds. Individuals of each species were captured in one reference and one polluted site in the Southern Brazilian coast. Brain tissue was used as enzyme source. Inhibition kinetic parameters indicated that ChE from C. spixii collected at the reference site showed more affinity (Ka) for eserine that from those collected at the polluted site. The opposite was observed for the carbamylation constants (Kc). Thus, similar inhibition constants (Ki) were observed. M. furnieri brain showed an extremely low sensitivity to in vitro inhibition by eserine, indicating that it is not a suitable biomarker to be employed in environmental monitoring of anticholinergic compounds. Results from the present study also point to the need for considering kinetic analysis when cholinesterase activity is employed as a biomarker.