Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Ecosystem Viable Yields

The World Summit on Sustainable Development (Johannesburg, 2002) encouraged the application of the ecosystem approach by 2010. However, at the same summit, the signatory States undertook to restore and exploit their stocks at maximum sustainable yield (MSY), a concept and practice without ecosystemic dimension, since MSY is computed species by species, on the basis of a monospecific model. Acknowledging this gap, we propose a definition of “ecosystem viable yields” (EVY) as yields compatible (a) with biological safety levels (over which biomasses can be maintained for all times) and (b) with an ecosystem dynamics. The difference from MSY is that this notion is not based on equilibrium but on viability theory, which offers advantages for robustness. For a generic class of multispecies models with harvesting, we provide explicit expressions for the EVY. We apply our approach to the anchovy–hake couple in the Peruvian upwelling ecosystem.     

Assessing the impact of chloroacetanilide herbicides and their metabolites on periphyton in the Leyre River (SW France) via short term growth inhibition tests on autochthonous diatoms

The Leyre River is the main tributary to the Bassin d'Arcachon lagoon. Herbicides belonging to the chloroacetanilide class have been found in the river (S-metolachlor and acetochlor) as well as some of their metabolites at higher concentrations. As the environmental toxicity of these molecules is not well known, ecotoxicological tests have been carried out on river periphyton at different levels of biological diversity: from the clone of one diatom species (Nitzschia nana) to the population of the same species (several clones) up to the multi-specific species community dominated by diatoms. Moreover, tests were performed on diatoms coming from an unpolluted upstream site and from a contaminated downstream site, in order to investigate possible tolerance acquisition to pollutants. The method consisted in measuring diatom growth inhibition at different doses of each substance from the increase of chlorophyll-a concentration after 4 days. It resulted that acetochlor was clearly more toxic than S-metolachlor at all levels of biological diversity. EC(50) values estimated from the tests suggest no effect of contaminants on diatom growth or biomass in the river. The toxicity of the metabolites appeared very low compared to that of their parent compounds. No difference in tolerance to the herbicides was demonstrated between summer diatom communities from the two sites in spite of different specific compositions. However, concerning the populations of N. nana isolated in winter following the highest herbicide concentrations in the river (about 0.5 μg L(-1)), the downstream population showed a higher tolerance to acetochlor but there was no co-tolerance to S-metolachlor. Thus, it appeared that acetochlor represents the highest toxic pressure on periphyton among the other contaminants in the Leyre River.     

Road traffic impact on urban water quality: a step towards integrated traffic,air and stormwater modelling

Methods for simulating air pollution due to road traffic and the associated effects on stormwater runoff quality in an urban environment are examined with particular emphasis on the integration of the various simulation models into a consistent modelling chain. To that end, the models for traffic, pollutant emissions, atmospheric dispersion and deposition, and stormwater contamination are reviewed. The present study focuses on the implementation of a modelling chain for an actual urban case study, which is the contamination of water runoff by cadmium (Cd), lead (Pb), and zinc (Zn) in the Grigny urban catchment near Paris, France. First, traffic emissions are calculated with traffic inputs using the COPERT4 methodology. Next, the atmospheric dispersion of pollutants is simulated with the Polyphemus line source model and pollutant deposition fluxes in different subcatchment areas are calculated. Finally, the SWMM water quantity and quality model is used to estimate the concentrations of pollutants in stormwater runoff. The simulation results are compared to mass flow rates and concentrations of Cd, Pb and Zn measured at the catchment outlet. The contribution of local traffic to stormwater contamination is estimated to be significant for Pb and, to a lesser extent, for Zn and Cd; however, Pb is most likely overestimated due to outdated emissions factors. The results demonstrate the importance of treating distributed traffic emissions from major roadways explicitly since the impact of these sources on concentrations in the catchment outlet is underestimated when those traffic emissions are spatially averaged over the catchment area.     

Prenatal diagnosis of congenital adrenal hyperplasia (CAH) due to 21-hydroxylase deficiency by steroid analysis in the amniotic fluid of mid-pregnancy: Comparison with HLA typing in 17 pregnancies at risk for CAH

Amniotic fluid (AF) levels of 17-hydroxyprogesterone (17OHP) and testosterone (T) were determined at 16–17 weeks in 17 pregnancies at risk for CAH and results compared to 75 normal controls. The fetus was predicted to be unaffected in 12 cases on the findings of normal AF levels of both 17OHP and T and the latter allowed a correct prediction of fetal sex in all instances. HLA typing confirmed normality in 12 cases revealing 5 carriers, 5 homozygous normal and 2 indeterminate. Steroid levels of the 2 groups were similar. Three fetuses were predicted to be CAH affected on unambiguously high levels of 17OHP and T (in female only). HLA typing was in agreement, and the diagnosis was confirmed in 2 abortuses and a female newborn by physical and hormonal studies. In the last 2 cases AF levels of OHP and T were normal but HLA (A/B/C) genotypes were identical to the CAH affected siblings. Normal physical and hormonal findings in the 2 aborted fetuses would exclude the possibility of an in utero virilizing form of CAH. The discrepancy could be explained on the basis that the fetuses had an allelic form of 21-hydroxylase deficiency or on the basis of recombination (not fully tested). It is concluded that a fully informative prenatal diagnosis of CAH should not rely entirely on HLA typing but on hormonal studies.     

Variations of periphytic diatom sensitivity to the herbicide diuron and relation to species distribution in a contamination gradient: implications for biomonitoring

Diatoms are commonly used as bioindicators of trophic and saprobic pollution in rivers. However, more knowledge is needed concerning their sensitivity to toxicants such as agricultural herbicides. In this study, seven species of periphytic diatoms were isolated from the Morcille River (Beaujolais area, France) which presents a streamward contamination gradient by pesticides and particularly diuron. The sensitivity of these species to diuron was assessed through ecotoxicological tests based on short-term growth inhibition of monospecific cultures. After application of an appropriate toxicological model, EC50 were determined and the species were ranked according to their tolerance. EC50 values ranged from 4.5 to 19 μg L(-1). Finally, the results were related to field periphyton samples from an upstream and a downstream site in order to check if variations in specific relative abundance between sites are consistent with differences in tolerance to diuron. Species distribution between sites was only partially in accordance with toxicological results suggesting that other factors (toxic or trophic) have an important influence on diatom communities in the river. Nevertheless, diatoms showed their potential to indicate water contamination by pesticides and toxic indices could be developed in complement to existing trophic indices.     

PBDEs and PCBs in the liver of the St Lawrence Estuary beluga (Delphinapterus leucas): a comparison of levels and temporal trends with the blubber

Due to their lipophilic properties, persistent organic pollutants (POPs) are commonly assessed using the blubber of marine mammals. However, these chemicals are also accumulating in other tissues including the liver. Some pollutants, namely perfluorinated alkyl acids, are found predominately in the liver and blood of marine mammals, and thus monitored in those tissues. This raises the question whether any tissue would represent an identical trend of POPs in the SLE beluga. The current study reports the first temporal trends of PBDEs and PCBs in the liver of 65 SLE belugas. Neither ∑?PBDEs nor major individual PBDE-homolog group concentrations showed significant trends between 1993 and 2007. Also, ∑??PCBs did not change over years, although, tetra-, penta- and hepta-PCB decreased by 7.1, 6.8 and 8.5%, respectively, in males, whereas tetra-, penta- and octa-PCBs declined by 11, 12 and 12.9%, respectively, in females. In order to compare the distribution of POPs between liver and blubber, a lipid normalised concentration ratio R (blubber/liver) for PBDEs and PCBs was calculated for each individual beluga. For all PBDE and several PCB homolog groups, mean R values were not statistically different from unity indicating that the partitioning of these POPs is governed by the tissue lipid-content. Temporal trends of R ratios of PBDEs and PCBs were also examined. There were generally no significant temporal trends except for PBDEs in males where R increased in average by 12.7 ± 2.9% yearly. The stratification of the blubber into a metabolically active (inner) and less active layers (outer blubber) may result in a slower response time of the blubber (full depth) than the liver to the recent change of contamination in the environment and explain the time trend differences between both tissues. This study suggests that the liver is more representative of recent exposure to lipophilic contaminants.     

Rational pricing of groundwater with a growing population

When population is increasing, characterizing the optimal water consumption path is complicated by the fact that the underlying dynamics of the water stock is contingent on the level of the stock itself. We propose a method of constructing the optimal path in this case. Since population is increasing, the optimal consumption path may involve refraining at times from consuming the totality of the surface water flow in order to restock in groundwater for future consumption. The aquifer then serves as a means to achieve welfare increasing intertemporal transfers of surface water. Therefore the aquifer itself, as distinct from the stock of water it serves to store, may have value and the marginal valuation of water when groundwater stocks are being drawn upon should, for this reason, differ at times from the marginal valuation of water when it is drawn strictly from surface water.