Combined photo-Fenton and biological oxidation for pesticide degradation: effect of photo-treated intermediates on biodegradation kinetics

Biodegradability of a partially photo-oxidized pesticide mixture is demonstrated and the effect of photo-Fenton treatment time on growth and substrate consumption of the bacteria Pseudomonas putida CECT 324 is shown. Four commercial pesticides, laition, metasystox, sevnol and ultracid, usually employed in citric orchards in eastern Spain, were chosen for these experiments. The active ingredients are, respectively, dimethoate, oxydemeton-methyl, carbaryl and methidathion. Judging by biomass measurements, dissolved organic carbon measurements and biodegradation efficiency, it may be concluded that 90min相似文献   

Enhancement of the CO(2) retention capacity of X zeolites by Na- and Cs-treatments

Adsorption of carbon dioxide on alkaline modified X zeolites was investigated by temperature programmed desorption (TPD) analysis of these materials previously saturated with CO(2) at 50, 100 and 200 degrees C. Parent X zeolite (in its sodium form) was treated with different sodium and cesium aqueous solutions, using both carbonates and hydroxides as precursors. The resulting materials were characterised by nitrogen physisorption, XRD, and NH(3)-TPD, in order to determine their morphological, crystallographic and chemical properties. Slight desilication phenomena were observed using hydroxides as precursors, whereas the treatment with Cs salts lead to higher crystallinity losses. Several successive adsorption-desorption cycles were carried out in order to check the regenerability of the adsorbents. Cesium-treated zeolites present higher carbon dioxide retention capacities than the sodium treated and than the parent material. When working with these Cs-modified materials, the desorption takes place mainly at temperatures between 250 and 400 degrees C, results of great practical interest, since it allows the use these kinds of materials for adsorption-desorption cycles. The evolution of the retention capacity with temperature is also markedly more positive for Cs-treated zeolite, especially when carbonate is used as the precursor. These materials maintain high retention capacities at 100 degrees C (10mg g(-1)) and even at 200 degrees C (3mg g(-1)), temperatures at which the most of the adsorbents are inactive.     

Comparison of arsenic resistance in Mediterranean woody shrubs used in restoration activities

Myrtus communis, Arbutus unedo and Retama sphaerocarpa are Mediterranean shrubs widely used in revegetation of semiarid degraded soils. The aim of this work is to study the resistance of these plants to arsenic under controlled conditions, in order to evaluate their potential use in revegetation and/or phytoremediation of As-polluted soils. R. sphaerocarpa showed higher resistance to As than M. communis or A. unedo according to its higher EC50, P status and P/As molar ratio in both, roots and shoots, and the lower increases in lipid peroxidation and decrease of chlorophyll levels in response to arsenic, while the highest arsenate sensitivity was obtained for A. unedo. Arsenic was mainly retained in roots, and, although M. communis accumulated higher arsenic amounts than the other two species, R. sphaerocarpa showed the highest root to shoot transfer. Most of the studied parameters (chlorophylls, MDA and total thiols) showed significant correlation with arsenic concentration in roots and leaves of plants, so they can be useful indexes in the diagnosis of arsenic toxicity in these species. According to our results, both M. communis and R. sphaerocarpa could be used in the revegetation of moderately arsenic contaminated sites.     

Adsorption of chloridazon from aqueous solution on modified kerolite-rich materials

The adsorption of chloridazon (5-amine-4-chloro-2-phenylpyridazin-3(2H)-one) on kerolite samples heated at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400), 600 degrees C (K-600) and acid-treated with H(2)SO(4) solutions of two different concentrations (0.25 and 0.5 M) (K-0.25 and K-0.5, respectively) from pure water at 25 degrees C has been studied by using batch and column experiments. The adsorption experimental data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values ranged from 184.7 mg kg(-1) (K-0.5) up to 2253 mg kg(-1) (K-600). This indicated that the heat treatment given to the kerolite greatly increases its adsorption capacity for the herbicide whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) was also calculated; R values ranging from 52.8% (K-0.5) up to 88.3% (K-600). Thus, the results showed that the 600 degrees C heat-treated kerolite was more effective in relation to adsorption of chloridazon and it might be reasonably used in removing this herbicide from water.     

Preparation of a porous clay heterostructure and study of its adsorption capacity of phenol and chlorinated phenols from aqueous solutions.

A porous clay heterostructure (PCH) from a Mexican clay was prepared and characterized, and its aqueous phenol and dichlorophenols (DCPs) adsorption capacities were studied using a batch equilibrium technique. The PCH displayed a surface area of 305.5 m2/g, 37.2 A average porous diameter, and a basal space of 23.2 A. The adsorption capacity shown by the PCH for both phenol and DCPs from water (14.5 mg/g for phenol; 48.7 mg/g for 3,4-DCP; and 45.5 mg/g for 2,5-DCP) suggests that the PCH has both hydrophobic and hydrophilic characteristics, as a result of the presence of silanol and siloxane groups formed during the pillaring and calcination of the PCH. The values of maximal adsorption capacity for dichlorophenols were higher than those reported for aluminum pillared clays and some inorgano-organo clays and comparable with some ionic exchange resins.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.     

The Predatory Bird Monitoring Scheme: identifying chemical risks to top predators in Britain

The Predatory Bird Monitoring Scheme (PBMS) is a long term (>40 y), UK-wide, exposure monitoring scheme that determines the concentration of selected pesticides and pollutants in the livers and eggs of predatory birds. This paper describes how the PBMS works, and in particular highlights some of the key scientific and policy drivers for monitoring contaminants in predatory birds and describes the specific aims, scope, and methods of the PBMS. We also present previously unpublished data that illustrates how the PBMS has been used to demonstrate the success of mitigation measures in reversing chemical-mediated impacts; identify and evaluate chemical threats to species of high conservation value; and finally to inform and refine monitoring methodologies. In addition, we discuss how such schemes can also address wider conservation needs.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

New metallothionein assay in Scrobicularia plana: heating effect and correlation with other biomarkers

Metallothionein (MT) and other biomarker levels were measured in Scrobicularia plana clams to assess pollution of the Guadalquivir Estuary possibly affected by metals released from Aznalcóllar pyrite mine in 1998. After optimizing reagent concentrations for monobromobimane derivatization, MT levels were quantified by reversed-phase high-performance liquid chromatography coupled to fluorescence detection (RP-HPLC-FD) in heated or unheated digestive gland extracts and compared to those obtained by differential pulse polarography (DPP). MT content assayed by RP-HPLC-FD in unheated samples was higher than that obtained by DPP and correlated better with metals and anti-oxidant activities. MT assay by RP-HPLC-FD in unheated extracts would be preferable for assessing metal pollution, due to its greater sensitivity and specificity. In addition to MT induction, glyoxalase II inhibition was well correlated with metal contents. Our results suggest that metals at the estuary do not originate from Aznalcóllar spill, but from those carried along by the river and deposited at its concave bank.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 micro g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.