Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4 h whereas its lifetime with respect to the photolysis is higher than 1 d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.     

Heavy metal content of edible plants collected close to an area of intense mining activity (southern Portugal)

The Neves-Corvo mining complex (MC) situated in southern Portugal exploits one of the most world’s important copper deposits. Agricultural soils surrounding the MC, used by the inhabitants for crop production, contain excessive amounts of As, Cu, Pb, and Zn. Thus, a potential risk to human consumption exists if edible plants grow on these substrata. Arsenic and Pb were not detected in edible samples collected near the MC and 5 km away, but in the leaves—structural or adsorbed onto the surface. In general, Zn was the most mobile element in both contaminated and reference areas as seen by the bioaccumulation factors (BAF). The tolerable upper intake (TUI) values for Cu are a reason of concern, since in 57.1% of the cases, the TUI values are above the recommended upper limit of 5 mg/day, in the case of Ficus carica, Cucurbita pepo, and Phaseolus vulgaris, whereas in 28.6% of the cases, the TUI values are near this limit (C. pepo and Citrus x sinensis). The consumption of such vegetables from these areas must be banned or strongly reduced, since long-term accumulation of Cu can cause a chronic toxicity in humans.     

Using multivariate techniques as a strategy to guide optimization projects for the surface water quality network monitoring in the Velhas river basin,Brazil

Surface water quality monitoring networks are usually deployed and rarely re-evaluated with regard to their effectiveness. In this sense, this work sought to evaluate and to guide optimization projects for the water quality monitoring network of the Velhas river basin, using multivariate statistical methods. The cluster, principal components, and factorial analyses, associated with non-parametric tests and the analysis of violation to the standards set recommended by legislation, identified the most relevant water quality parameters and monitoring sites, and evaluated the sampling frequency. Thermotolerant coliforms, total arsenic, and total phosphorus were considered the most relevant parameters for characterization of water quality in the river basin. The monitoring sites BV156, BV141, BV142, BV150, BV137, and BV153 were considered priorities for maintenance of the network. The multivariate statistical analysis showed the importance of a monthly sampling frequency, specifically the parameters considered most important.     

The use of multivariate statistical methods for optimization of the surface water quality network monitoring in the Paraopeba river basin,Brazil

This study sought to evaluate and propose adjustments to the water quality monitoring network of surface freshwaters in the Paraopeba river basin (Minas Gerais, Brazil), using multivariate statistical methods. A total of 13,560 valid data were analyzed for 19 water quality parameters at 30 monitoring sites, over a period of 5 years (2008–2013). The cluster analysis grouped the monitoring sites in eight groups based on similarities of water quality characteristics. This analysis made it possible to detect the most relevant monitoring stations in the river basin. The principal components analysis associated with non-parametric tests and the analysis of violation of the standards prescribed by law, allowed for identifying the most relevant parameters which must be maintained in the network (thermotolerant coliforms, total manganese, and total phosphorus). The discharge of domestic sewage and industrial wastewater, that from mining activities and diffuse pollution from agriculture and pasture areas are the main sources of pollution responsible for the surface water quality deterioration in this basin. The BP073 monitoring site presents the most degraded water quality in the Paropeba river basin. The monitoring sites BP094 and BP092 are located geographically close and they measure similar water quality, so a possible assessment of the need to maintain only one of the two in the monitoring network is suggested. Therefore, multivariate analyses were efficient to assess the adequacy of the water quality monitoring network of the Paraopeba river basin, and it can be used in other watersheds.     

Parabens abatement from surface waters by electrochemical advanced oxidation with boron doped diamond anodes

The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-doped diamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO ⁻. The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

     

Assessment of Water Supply as an Ecosystem Service in a Rural-Urban Watershed in Southwestern Mexico City

Studies from the ecosystem services perspective can provide a useful framework because they allow us to fully examine the benefits that humans obtain from socio-ecological systems. Mexico City, the second largest city in the world, has faced severe problems related to water shortages, which have worsened due to increasing population. Demand for space has forced changes in land cover, including covering areas that are essential for groundwater recharge. The city has 880 km² of forest areas that are crucial for the water supply. The Magdalena River Watershed was chosen as a model because it is a well-preserved zone within Mexico City and it provides water for the population. The general aim of this study was to assess the ecosystem service of the water supply in the Magdalena River Watershed by determining its water balance (SWAT model) and the number of beneficiaries of the ecosystem services. The results showed that the watershed provides 18.4 hm³ of water per year. Baseflow was dominant, with a contribution of 85%, while surface runoff only accounted for 15%. The zone provides drinking water to 78,476 inhabitants and could supply 153,203 potential beneficiaries. This work provides an example for understanding how ecosystem processes determine the provision of ecosystem services and benefits to the population in a rural–urban watershed in Mexico City.     

Contents and sources of DDT impurities in dicofol formulations in Turkey

Background, aim, and scope  Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods  Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p′ and o,p′ isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p′-Cl-DDT concentrations. Results  The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p′-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p′-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p’-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion  It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions  All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives  DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.     

The effect of EURO-0 vehicle substitution on polycyclic aromatic hydrocarbon and carbon monoxide concentrations in an urban area

From 1994 to 2003, daily air concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and carbon monoxide (CO) were regularly monitored at two traffic-oriented sampling sites (A and B) in urban Genoa, Italy. The data were used to estimate effects on air quality in real situations due to progressive substitution of EURO-0 vehicles, started in 1993, with less-polluting vehicles (EURO-1, EURO-2), mainly gasoline vehicles with a catalyst. PAH profile classification and diagnostic PAH ratios were used to identify 345 samples of predominantly traffic origin. At both sites, CO and PAH daily concentrations decreased exponentially with time and the apparent half-life values calculated were 6.3 and 5.5 for CO and 3.7 and 3.5 years for PAHs at sites A and B, respectively. At site A, monitored for traffic intensity, multiple regression analyses confirmed that daily PAH and CO concentrations were positively correlated with the number of non-catalytic vehicles estimated to cross this site during sampling and negatively correlated with seasonal variables (air temperature, ozone concentration, relative air humidity). The reduction in air pollution estimated for complete substitution of non-catalytic gasoline vehicles was 89% for BaP, 85% for total PAHs and 69% for CO.     

Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process

The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.