Impact of wastewater treatment plants on receiving surface waters and a tentative risk evaluation: the case of estrogens and beta blockers

Five estrogenic hormones (unconjugated?+?conjugated fractions) and 10 beta blockers were analyzed in three wastewater treatment plant (WWTP) effluents and receiving river waters in the area of Lyon, France. In the different samples, only two estrogens were quantified: estrone and estriol. Some beta blockers, such as atenolol, acebutolol, and sotalol, were almost always quantified, but others, e.g., betaxolol, nadolol, and oxprenolol were rarely quantified. Concentrations measured in river waters were in the nanogram per liter range for estrogens and between 0.3 and 210 ng/L for beta blockers depending on the substance and the distance from the WWTP outfall. The impact of the WWTP on the receiving rivers was studied and showed a clear increase in concentrations near the WWTP outfall. For estrogens, the persistence in surface waters was not evaluated given the low concentrations levels (around 1 ng/L). For beta blockers, concentrations measured downstream of the WWTP outfall were up to 16 times higher than those measured upstream. Also, the persistence of metoprolol, nadolol, and propranolol was noted even 2 km downstream of the WWTP outfall. The comparison of beta blocker fingerprints in the samples collected in effluent and in the river also showed the impact of WWTP outfall on surface waters. Finally, a tentative environmental risk evaluation was performed on 15 sites by calculating the ratio of receiving water concentrations to predicted non-effect concentrations (PNEC). For estrogens, a total PNEC of 5 ng/L was considered and these substances were not linked to any potential environmental risk (only one site showed an environmental risk ratio above 1). Unfortunately, few PNECs are available and risk evaluation was only possible for 4 of the 10 beta blockers studied: acebutolol, atenolol, metoprolol, and propranolol. Only propranolol presented a ratio near or above 1, showing a possible environmental risk for 4 receiving waters out of 15.     

The release of lindane from contaminated building materials

The release of the organochlorine pesticide lindane (γ-hexachlorocyclohexane) from several types of contaminated building materials was studied to assess inhalation hazard and decontamination requirements in response to accidental and/or intentional spills. The materials included glass, polypropylene carpet, latex-painted drywall, ceramic tiles, vinyl floor tiles, and gypsum ceiling tiles. For each surface concentration, an equilibrium concentration was determined in the vapour phase of the surrounding air. Vapor concentrations depended upon initial surface concentration, temperature, and type of building material. A time-weighted average (TWA) concentration in the air was used to quantify the health risk associated with the inhalation of lindane vapors. Transformation products of lindane, namely α-hexachlorocyclohexane and pentachlorocyclohexene, were detected in the vapour phase at both temperatures and for all of the test materials. Their formation was greater on glass and ceramic tiles, compared to other building materials. An empiric Sips isotherm model was employed to approximate experimental results and to estimate the release of lindane and its transformation products. This helped determine the extent of decontamination required to reduce the surface concentrations of lindane to the levels corresponding to vapor concentrations below TWA.     

Dynamic extreme values modeling and monitoring by means of sea shores water quality biomarkers and valvometry

Water quality can be evaluated using biomarkers such as tissular enzymatic activities of endemic species. Measurement of molluscs bivalves activity at high frequency (e.g., valvometry) during a long time period is another way to record the animal behavior and to evaluate perturbations of the water quality in real time. As the pollution affects the activity of oysters, we consider the valves opening and closing velocities to monitor the water quality assessment. We propose to model the huge volume of velocity data collected in the framework of valvometry using a new nonparametric extreme values statistical model. The objective is to estimate the tail probabilities and the extreme quantiles of the distribution of valve closing velocity. The tail of the distribution function of valve closing velocity is modeled by a Pareto distribution with parameter ??_t,τ, beyond a threshold τ according to the time t of the experiment. Our modeling approach reveals the dependence between the specific activity of two enzymatic biomarkers (Glutathione-S-transferase and acetylcholinesterase) and the continuous recording of oyster valve velocity, proving the suitability of this tool for water quality assessment. Thus, valvometry allows in real-time in situ analysis of the bivalves behavior and appears as an effective early warning tool in ecological risk assessment and marine environment monitoring.     

Polar organic chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater effluent and surface water

In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters.     

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.     

Evaluation of the field dissipation of fungicides and insecticides used on fruit bearing trees in northern Italy

The dissipation of the fungicides captan, cyprodinil, fludioxonil, dithianon, and tebuconazole and of the insecticides chlorpyrifos, fenitrothion, and malathion was studied, following a single treatment of different cultivars of pears, apples, and peaches. The study was conducted in northern Italy, over two successive growing seasons (2004 and 2005). The treatments were performed by the farmers involved, in line with their usual practice. At various time intervals from treatment to harvest, representative samples of fruit were collected and analyzed for pesticide residues. In some cases, concentrations lower than the maximum residue levels (MRLs) were found immediately after treatment. In all trials a rapid decline in pesticide concentrations was observed leading to residues at harvest greatly below the MRLs.     

Removal of fenhexamid and pyrimethanil from aqueous solutions by clays and organoclays

The ability of a sodium montmorillonite (CLONa) and two commercial available organoclays having interlayer organic cations possessing different functional groups (CLO20A and CLO30B) was investigated for adsorbing two pesticides namely fenexamid (FEX) and pyrimethanyl (PMT). The two organoclays displayed a higher affinity with the pesticides than the unmodified clay, but the improvement in adsorption capacity varied according to the characteristics of the pesticide and the interlayer organic cation. FEX was adsorbed to a greater extent than PMT by both organoclays, which may be due to the higher hydrophobicity of FEX thereby indicating considerable hydrophobic interaction between the adsorbent/adsorbate systems. Our findings may find application in the removal of water-soluble pesticides from aquifers.     

Biliary PAH metabolites, EROD activity and DNA damage in dab (Limanda limanda) from Seine Estuary (France)

The Seine Estuary is well known to be widely contaminated by organic pollutants and especially by polycyclic aromatic hydrocarbons (PAHs). Fish are known to metabolize PAHs, leading to different toxic effects at both cellular and sub-cellular levels. In this work, we studied the relationships between the 7-ethoxyresorufin-O-deethylase (EROD) activity in the liver, the level of DNA strand breaks in blood cells and the concentration of PAH metabolites in the bile of the sentinel flatfish species Limanda limanda. Muscle and liver samples were analysed for parent PAH levels. Female and male dabs of two size classes (juveniles and adults) were collected by trawling in two sites with different degrees of pollution during March and September 2005 and 2006. Significant effects of sex, age, site and season were demonstrated on EROD activity and the level of strand breaks. Parent PAH concentrations in dabs did not allow discriminating of the two sampling sites. However, for PAH metabolites, significant differences were observed with sites and seasons. Dabs collected at the mouth of the estuary appeared to be the most impacted when looking at the results obtained with the three selected markers. The significant correlations observed between the level of PAH metabolites and the level of DNA lesions showed the importance of a combined analysis of chemical and biochemical markers to correctly assess the contribution of chemical contamination to the toxic effects measured in situ in fish.     

Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris

This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP₁EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP₁EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.     

Agricultural practices in grasslands detected by spatial remote sensing

The major decrease in grassland surfaces associated with changes in their management that has been observed in many regions of the earth during the last half century has major impacts on environmental and socio-economic systems. This study focuses on the identification of grassland management practices in an intensive agricultural watershed located in Brittany, France, by analyzing the intra-annual dynamics of the surface condition of vegetation using remotely sensed and field data. We studied the relationship between one vegetation index (NDVI) and two biophysical variables (LAI and fCOVER) derived from a series of three SPOT images on one hand and measurements collected during field campaigns achieved on 120 grasslands on the other. The results show that the LAI appears as the best predictor for monitoring grassland mowing and grazing. Indeed, because of its ability to characterize vegetation status, LAI estimated from remote sensing data is a relevant variable to identify these practices. LAI values derived from the SPOT images were then classified based on the K-Nearest Neighbor (KNN) supervised algorithm. The results points out that the distribution of grassland management practices such as grazing and mowing can be mapped very accurately (Kappa index?=?0.82) at a field scale over large agricultural areas using a series of satellite images.