Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Brain glutathione redox system significance for the control of silica-coated magnetite nanoparticles with or without mercury co-exposures mediated oxidative stress in European eel (Anguilla anguilla L.)

This in vitro study investigates the impact of silica-coated magnetite particles (Fe₃O₄@SiO₂/SiDTC, hereafter called IONP; 2.5 mg L^?1) and its interference with co-exposure to persistent contaminant (mercury, Hg; 50 μg L^?1) during 0, 2, 4, 8, 16, 24, 48, and 72 h on European eel (Anguilla anguilla) brain and evaluates the significance of the glutathione (GSH) redox system in this context. The extent of damage (membrane lipid peroxidation, measured as thiobarbituric acid reactive substances, TBARS; protein oxidation, measured as reactive carbonyls, RCs) decreased with increasing period of exposure to IONP or IONP + Hg which was accompanied with differential responses of glutathione redox system major components (glutathione reductase, GR; glutathione peroxidase, GPX; total GSH, TGSH). The occurrence of antagonism between IONP and Hg impacts was evident at late hour (72 h), where significantly decreased TBARS and RC levels and GR and glutathione sulfo-transferase (GST) activity imply the positive effect of IONP + Hg concomitant exposure against Hg-accrued negative impacts [vs. early (2 h) hour of exposure]. A period of exposure-dependent IONP alone and IONP + Hg joint exposure-accrued impact was perceptible. Additionally, increased susceptibility of the GSH redox system to increased period of exposure to Hg was depicted, where insufficiency of elevated GR for the maintenance of TGSH required for membrane lipid and cellular protein protection was displayed. Overall, a fine-tuning among brain glutathione redox system components was revealed controlling IONP + Hg interactive impacts successfully.     

The combined effects of urea application and simulated acid rain on soil acidification and microbial community structure

Our aim was to test the effects of simulated acid rain (SAR) at different pHs, when applied to fertilized and unfertilized soils, on the leaching of soil cations (K, Ca, Mg, Na) and Al. Their effects on soil pH, exchangeable H⁺ and Al³⁺ and microbial community structure were also determined. A Paleudalfs soil was incubated for 30 days, with and without an initial application of urea (200 mg N kg^?1soil) as nitrogen (N) fertilizer. The soil was held in columns and leached with SAR at three pH levels. Six treatments were tested: SAR of pH 2.5, 4.0 and 5.6 leaching on unfertilized soil (T1, T2 and T3), and on soils fertilized with urea (T4, T5 and T6). Increasing acid inputs proportionally increased cation leaching in both unfertilized and fertilized soils. Urea application increased the initial Ca and Mg leaching, but had no effect on the total concentrations of Ca, Mg and K leached. There was no significant difference for the amount of Na leached between the different treatments. The SAR pH and urea application had significant effects on soil pH, exchangeable H⁺ and Al³⁺. Urea application, SAR treated with various pH, and the interactions between them all had significant impacts on total phospholipid fatty acids (PLFAs). The highest concentration of total PLFAs occurred in fertilized soils with SAR pH5.6 and the lowest in soils leached with the lowest SAR pH. Soils pretreated with urea then leached with SARs of pH 4.0 and 5.6 had larger total PLFA concentrations than soil without urea. Bacterial, fungal, actinomycete, Gram-negative and Gram-positive bacterial PLFAs had generally similar trends to total PLFAs.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

Degree of phosphorus saturation of an Oxisol amended with biosolids in a long-term field experiment

When applied to agricultural soils, phosphate fertilizers and the mineral or organic compounds present in solid and/or liquid waste may raise phosphorus (P) content and increase soil P saturation. The degree of phosphorus saturation (DPS) is a good indicator of potential P loss from agricultural soils. The purpose of this study was to calculate the DPS of samples from an Oxisol amended for 5 years with biosolids and mineral fertilizer. DPS was calculated based on P, iron, and aluminum extracted by ammonium oxalate and oxalic acid (DPS_ox) or by Mehlich-1 solution (DPS_M1). Treatments included NPK mineral fertilization (175 kg ha^?1 of P), B1?=?19.02 t ha^?1 of biosolids (350 kg ha^?1 of P), B2?=?38.17 t ha^?1 of biosolids (703 kg ha^?1 of P), B3?=?76.26 t ha^–1 of biosolids (1,405 kg ha^?1 of P), and a control (no P added). Water-extractable P (WEP) was also measured. Critical levels of DPS_ox and DPS_M1 (21 and 24 %, respectively) were only achieved in the topsoil (0–0.1 m) at the highest biosolid dose. Concentration of WEP was positively correlated to DPS_ox and DPS_M1. The DPS_M1 method may be an alternative to DPS_ox for assessing the environmental risk of P loss from soil into surface runoff.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Electrochemical advanced oxidation processes: today and tomorrow. A review

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (^?OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which ^?OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which ^?OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

Salt marsh plants as key mediators on the level of cadmium impact on microbial denitrification

The fate of excess nitrogen in estuaries is determined by the microbial-driven nitrogen cycle, being denitrification a key process since it definitely removes fixed nitrogen as N₂. However, estuaries receive and retain metals, which may negatively affect this process efficiency. In this study, we evaluated the role of salt marsh plants in mediating cadmium (Cd) impact on microbial denitrification process. Juncus maritimus and Phragmites australis from an estuary were collected together with the sediment involving their roots, each placed in vessels and maintained in a greenhouse, exposed to natural light, with tides simulation. Similar non-vegetated sediment vessels were prepared. After 3 weeks of accommodation, nine vessels (three per plant species plus three non-vegetated) were doped with 20 mg/L Cd²⁺ saline solution, nine vessels were doped with 2 mg/L Cd²⁺ saline solution and nine vessels were left undoped. After 10 weeks, vessels were dissembled and denitrification potential was measured in sediment slurries. Results revealed that the addition of Cd did not cause an effect on the denitrification process in non-vegetated sediment but had a clear stimulation in colonized ones (39 % for P. australis and 36 % for J. maritimus). In addition, this increase on denitrification rates was followed by a decrease on N₂O emissions and on N₂O/N₂ ratios in both J. maritimus and P. australis sediments, increasing the efficiency of the N₂O step of denitrification pathway. Therefore, our results suggested that the presence of salt marsh plants functioned as key mediators on the degree of Cd impact on microbial denitrification.