Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products: application to ethinylestradiol and chlorination water treatment

The detection and structural elucidation of micropollutants treatment by-products are major issues to estimate efficiencies of the processes employed for drinking water production versus endocrine disruptive compounds contamination. This issue was mainly investigated at the laboratory scale and in high concentration conditions. However, potential by-products generated after chlorination can be influenced by the dilution factor employed in real conditions. The present study proposes a new methodology borrowed to the metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination by-products of ethinylestradiol in spiked real water samples at the part-per-billion level (5 μg L⁻¹). Conventional targeted measurements first demonstrated that chlorination with sodium hypochlorite (0.8 mg L⁻¹) led to removals of ethinylestradiol over 97%. Then, the developed differential global profiling approach permitted to reveal eight chlorination by-products of EE2, six of them being described for the first time. Among these eight halogenated compounds, five have been structurally identified, demonstrating the potential capabilities of this new methodology applied to environmental samples.     

Effect of dissolved oxygen concentration on nitrite accumulation in nitrifying sequencing batch reactor.

A mathematical model based on Activated Sludge Model No. 3 (International Water Association, London) and laboratory-scale experiments were used to investigate ammonia conversion by nitrification in a sequencing batch reactor (SBR). The purpose of the study was to assess the effect of dissolved oxygen concentration on nitrite accumulation in the SBR. As the dissolved oxygen concentration in the SBR depends on the balance between oxygen consumption and oxygen transfer rates, ammonium conversion was measured for different air flowrate values to obtain different dissolved oxygen concentration profiles during the cycle. The ammonia concentration in the feeding medium was 500 mg ammonium as nitrogen (N-NH4(+))/L, and the maximum nitrite concentration achieved during a cycle was approximately 50 mg nitrite as nitrogen (N-NO2)/L. The air flow supplied to the reactor was identified as a suitable parameter to control nitrite accumulation in the SBR. This identification was carried out based on experimental results and simulation with a calibrated model. At a low value of the volumetric mass-transfer coefficient (kLa), the maximum nitrite concentration achieved during a cycle depends strongly on k(L)a, whereas, at a high value of k(L)a, the maximum nitrite concentration was practically independent of kL(a).     

Evaluation of the phytotoxicity of contaminated sediments deposited "on soil". I. Impact of water draining from the deposit on the germination of neighbouring plants

As part of a study of the phytotoxic risk of spreading of contaminated sediments "on soil", we carried out a laboratory experiment assessing the impact of water draining from sediments in a deposit scenario on the peripheral vegetation. The plant tested were the Chinese cabbage (Brassica campestris L. var. chinensis), maize (Zea mays L.) and ryegrass (Lolium perenne L.). The draining water samples (A1, B1 and C1) were obtained after decantation in laboratory of the sediments. The classification of the water sampled in decreasing order of cumulative contamination was C1 > A1 > B1. The B1 and C1 water samples inhibited the germination of seeds tested to various extents. The percentage of seeds that did not germinate was 1.3-fold times higher for Chinese cabbage with B1 than for the control and 2.3-fold times higher for ryegrass with C1 than for the control. Seeds watered with B1 had lower moisture contents than the control: 10% lower for ryegrass and maize and 50% lower for Chinese cabbage. An increase (about 1.5 microg/ml) in total soluble protein (versus the control) was observed for all three plant species tested in the presence of C1. Glutamine synthetase activity was significantly (1.35 times) higher in ryegrass seeds in the presence of C1 than in the control. We also observed changes in the specific activity of phosphoenolpyruvate carboxylase, which increased for ryegrass and decreased for maize as the concentration of contaminants in the water increased. The results show (i) the necessity to use different plant species to evaluate the toxic effect of sediment deposited on soil on the vegetation, and (ii) that soon as on germination an evaluation of an impact is possible.     

Impact of sewage sludge treatment processes on the removal of the endocrine disrupters nonylphenol ethoxylates

Several treatment processes of mixed sludge naturally contaminated with nonylphenol ethoxylates (NPE) were compared in order to evaluate their efficiency for the removal of these endocrine disrupters. Anaerobic and aerobic treatments were carried out in continuous stirred tank reactors, operated separately or combined together, at mesophilic and thermophilic temperatures and with or without ozone post-treatment. Anaerobic mesophilic removal of NPE consisted of complete removal of nonylphenol diethoxylate, incomplete removal of nonylphenol monoethoxylate and non stoechiometric production of nonylphenol, with consequently a NPE removal of 25%. At thermophilic temperature, anaerobic digestion led to an increase of the total solids removal efficiency, while improving NPE degradation (30%). Under thermophilic aerobic condition, the three compounds were removed simultaneously with a NPE removal efficiency higher than under anaerobic condition (39%). This removal is always well correlated to the total solids removal meaning that bioavailability remains the main limiting factor. Combination of either thermophilic aerobic-mesophilic anaerobic or mesophilic anaerobic-ozonation treatments enhanced the NPE removal by comparison to single systems (45% and 48%, respectively). These results confirm the high potential of existing and up-grading sewage sludge treatments to degrade such refractory and aged compounds.     

Evaluation of large-scale CO2 storage on fresh-water sections of aquifers: An example from the Texas Gulf Coast Basin

Large-scale injections of CO₂ into subsurface saline aquifers have been proposed to remediate climate change related to buildup of green house gases in the atmosphere. The pressure buildup caused by such injections may impact a volume of the basin significantly larger than the CO₂ plume itself. In areas with hydrological settings similar to the Gulf Coast Basin, the perturbation of the flow-field in deep parts of the basin could result in brines or brackish water being pushed up-dip into unconfined sections of the same formations or into the capture zone of fresh-water wells. The premise of the current study is that the details of multiple-phase flow processes necessary to model the near field evolution of the CO₂ plume are not necessary to describe the impact of the pressure anomaly on up-dip aquifers. This paper quantitatively explores conditions under which shallow groundwater would be impacted by up-dip displacement of brines, utilizing an existing carefully calibrated flow model. Modeling an injection of water, arguably equivalent to 50 million tons of CO₂/year for 50 years resulted in an average water-table rise of 1 m, with minor increase in stream baseflow and larger increase in ground water evapotranspiration, but no significant change in salinity.     

Evaluation of the phytotoxicity of contaminated sediments deposited "on soil": II. Impact of water draining from deposits on the development and physiological status of neighbouring plants at growth stage

As part of a study of the phytotoxic risk of spreading contaminated sediments "on soil", a laboratory experiment was carried out to assess the impact of water draining from sediments on peripheral vegetation. Drainage water was obtained in the laboratory by settling three sediments with different pollutants levels, and the supernatant solutions (respectively A1, B1, C1 drainage waters) were used as soaking water for maize (Zea ma?s L.) and ryegrass (Lolium perenne L.). The physicochemical characteristics of the supernatant water, particularly metal contents, showed a pattern of contamination, with C1>A1>B1. The plants tested were grown on soil for 21 days, before being soaked for another 21-day period with drainage water (treatments) and distilled water (control). Biomass parameters (fresh weight, length, etc.), enzymatic activity [glutamine synthetase (GS), phosphoenolpyruvate carboxylase (PEPc)] and Zn, Cu, Cd and Cr contents were measured on both the shoots and roots of each plant. Biomass parameters were stimulated by C1, not affected by A1 and decreased with B1 for maize, whereas they increased for ryegrass in all the treatments. Compared to the control, GS activity was stimulated by C1 in the shoots of both plants and inhibited by treatments B1 and C1 in maize roots. PEPc activity in ryegrass was 1.5-5 times higher with contaminated water treatment, while contrasting effects were observed in maize plants. Both plants showed greater accumulation of chromium and zinc than cadmium and copper. Treatment A1 was found to be less active on plant growth and have a lower impact on the physiological status (enzymatic activities) of both plants. Treatment C1 stimulated the growth and physiological status of the plants, especially in shoots, with higher metal accumulation values in both plants. Treatment B1 was found to show more variable effects on growth indices, enzymatic activity and metal accumulation according to plant species.     

Isolation of Humic and Non-Humic NOM Fractions: Structural Characterization

The combination of RO concentration and XAD-8/XAD-4 resin adsorption techniques was used to isolate the different constituents of the Natural Organic Matter (NOM) from inorganic salts. NOM fractions i.e. colloids, hydrophobic NOM (HPO humic substances), transphilic NOM (TPI) and hydrophilic NOM (HPI) fractions isolated from different surface waters were characterized using 13C NMR and FT-IR spectroscopy and HPLC/Size Exclusion Chromatography coupled with UV and DOC detection. Results showed that the isolation procedure was suitable to quantitatively isolate the different fractions of NOM.     

经合组织关于志愿思路在环境政策中的作用的工作

背景 志愿协议(VAs)在能源等若干个部门中被使用,但看来尤其要应用于环境领域.例如,在欧盟,已经记录到300多项志愿协议.这些协议已经吸引了颇大兴趣,而且已经实施了很多不同形式的志愿协议.1996年,欧洲委员会进行了一项关于在欧盟成员国中使用志愿协议的实践的广泛调查,并在同年11月公布一份关于环境协议的通报[COM(96)561/最终报告],提供了其使用的指导准则.