Characterization of sorption processes for the development of low-cost pesticide decontamination techniques.

The adsorption/desorption behavior of four pesticides (atrazine, alachlor, endosulfan sulfate and trifluralin) in aqueous solutions onto four adsorbents (sunflower seed shells, rice husk, composted sewage sludge and soil) was investigated. Pesticide determination was carried out using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. Maximum removal efficiency (73.9%) was reached using 1 g of rice husk and 50 mL of pesticide solution (200 µg L(-1)). The pseudo adsorption equilibrium was reached with 0.6 g organic residue, which was used in subsequent experiments. The pseudo-first-order, pseudo-second-order kinetics and the intra-particle diffusion models were used to describe the kinetic data and rate constants were evaluated. The first model was more suitable for the sorption of atrazine and alachlor while the pseudo-second-order best described endosulfan sulfate and trifluralin adsorption, which showed the fastest sorption rates. 4h was considered as the equilibrium time for determining adsorption isotherms. Experimental data were modeled by Langmuir and Freundlich models. In most of the studied cases both models can describe the adsorption process, although the Freundlich model was applicable in all cases. The sorption capacity increased with the hydrophobic character of the pesticides and decreased with their water solubility. Rice husk was revealed as the best adsorbent for three of the four studied pesticides (atrazine, alachlor and endosulfan sulfate), while better results were obtained with composted sewage sludge and sunflower seed shell for the removal of trifluralin. Although desorption percentages were not high (with the exception of alachlor, which reached a desorption rate of 57%), the Kfd values were lower than the Kf values for adsorption and all H values were below 100, indicating that the adsorption was weak.

Effectiveness of acid-treated agricultural stones used in biopurification systems to avoid pesticide contamination of water resources caused by direct losses: part I. Equilibrium experiments and kinetics.

Several recent publications report the use of low-cost and locally available adsorbents in biopurification systems to eliminate pesticides from water. Nonetheless, the literature is insufficient to cover this problem, and more investigations are needed in this field to evaluate the possible application of economical adsorbents to prevent pesticide water resources contamination caused by direct losses. This study focuses on the fate of endosulfan metabolites, in small-scale biopurification systems, using as adsorbents treated and untreated organic agricultural stones (date, olive and avocado). The effects of sorbent particle size, adsorbent dose, contact time, concentration of pesticide solution and temperature on the adsorption processes were systematically studied in batch experiments. Pesticide determination was carried out using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. Maximum removal efficiency (94.8%) was reached for endosulfan sulfate (0.1 mg L(-1)) using the acid-treated date stones (ATOS) fraction <125 microm (solid/liquid ratio: 1 g L(-1)). According to the general behavior of the adsorption mechanism, date stones show the higher removal efficiency followed by olive and avocado stones, respectively. The analyses of the results reveal that the thermo chemical treatment improves notably the pesticides adsorption efficiency of the studied sorbents and that the adsorption decreases when the pesticide solubility rises. Experimental adsorption data were analyzed according to various kinetic models. Lagergren and Morris-Weber equations were applied to fit the kinetic results. The second order model was the most suitable and intra-particle diffusion was found to be the rate controlling the adsorption process.

Adsorptive features of acid-treated olive stones for drin pesticides: equilibrium, kinetic and thermodynamic modeling studies.

The adsorption behavior of drin pesticides from aqueous solution onto acid treated olive stones (ATOS) was investigated using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. The effects of sorbent particle size, adsorbent dose, contact time, concentration of pesticide solution and temperature on the adsorption processes were systematically studied in batch shaking sorption experiments. Maximum removal efficiency (94.8%) was reached for aldrin (0.5 mg L(-1)) using the fraction 63-100 microm of ATOS (solid/liquid ratio: 1 g L(-1)). Experimental data were modeled by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The Freundlich isotherm model (R(2)=0.98-0.99) fitted the equilibrium data better than the Langmuir and D-R isotherm models, with low sum of error values (SE=1.4-9.2%). The mean adsorption free energy derived from the D-R isotherm model (R(2)=0.95-0.99) showed that the adsorption of drin pesticides was taken place by weak physical forces, such as van der Waals forces and hydrogen bonding. The calculated thermodynamic parameters, DeltaH, DeltaS and DeltaG prove that drin pesticides adsorption on ATOS was feasible, spontaneous and exothermic under examined conditions. The pseudo first order, pseudo second order kinetic and the intra-particle diffusion models were used to describe the kinetic data and rate constants were evaluated.

A general integrated ecotoxicological method for marine sediment quality assessment: application to sediments from littoral ecosystems on Southern Spain's Atlantic coast.

In the last few decades, several integrated methods for marine sediment quality evaluation have been developed and applied to many coastal sites. This paper describes the development of a general integrated method based on the determination of organic and inorganic sediment contamination, lethal and sublethal toxicity assessments, in situ benthonic community structure alteration and bioaccumulation of contaminants. The proposed method was applied to sediments from Southern Spain's Atlantic coast where six rivers (Guadiana, Carreras, Piedras, Tinto, Odiel and Guadalquivir) drain pollutants from various anthropogenic sources. A series of experiments was conducted to determine the characteristics of the sediments: granulometry, organic matter content, etc. (1); metal contamination of sediments and Chamelea gallina (bivalves widely distributed in the area studied) (2); lethal and sublethal toxicity by a series of biological tests (3); and macrofauna distribution at the 16 stations included in the study (4). Ratio-to-reference values (RTR) calculated for each parameter were used to determine the organic and inorganic contamination indices, the lethal and sublethal toxicity indices, the index of bioavailability of metals in the organisms analyzed and the macrobenthic alteration index. The data were plotted on six-axis plots to describe better the relations between the physical, chemical and biological properties studied. A general integrated sediment quality index (ISQI) was determined and used as an indicator of pollution-induced degradation. The ISQI values summarize the main characteristics of the environmental situation at each sampling point and can be used for purposes of comparison.

Endosulfan sulfate sorption on natural organic substances.

This work proposes a viable remediation method based on the use of natural organic substances (NOSs) that characterize the Mediterranean region to improve the ecological system. A series of experiments, including variable conditions, such as temperature, pH, contact time, and pesticide concentration, were performed to demonstrate the efficiency of endosulfan sulfate removal from water by NOSs. Experimental results showed that the pH and temperature of pesticide solutions negatively affect the adsorption process. The maximum adsorption capacity for a specific initial concentration of endosulfan sulfate (0.5 microg/L) was achieved with Origanum compactum (75%), followed by Cistus ladaniferus and Raphanus raphanistrum (72 and 68%, respectively). The adsorption tests gave very satisfying results and point to the possible application of these supports as a remediation technique to prevent pesticide contamination of aquatic ecosystems.

Endosulfan sulfate mobility in soil columns and pesticide pollution of groundwater in Northwest Morocco.

Groundwater pollution from agricultural practices is a serious environmental and health problem. In this work, stir bar sorptive extraction (SBSE) and gas chromatography (GC) with mass spectrometry (MS) detection were used to determine phytosanitary products in groundwater samples from the Loukkos perimeter in Northwest Morocco. Some pesticides--in particular, endosulfan and its metabolites--were found in water destined for human consumption. Analyses of soil samples were also carried out, and the results showed endosulfan sulfate and endosulfan ether in abundance. Endosulfan sulfate leaching was also performed in undisturbed soil columns to obtain more information on the vertical migration of pesticides used in the perimeter. The kinetic study showed a high recovery rate (73%) after 10 days of experimental work.

Electrochemical analysis of endosulfan using a C18-modified carbon-paste electrode.

Successful applications of different analytical procedures to determine quantitatively endosulfan and its metabolites in aqueous media can be found in recent literature. Fundamentally, they have made use of solid-phase extraction (SPE) and gas (GC) or liquid chromatography (LC), sometimes coupled to mass spectrometry (MS). In this paper, a new and alternative methodology to determine quantitatively endosulfan in aqueous media is reported. A C18-modified carbon-paste electrode has been used to determine voltammetrically endosulfan, despite its unfavourable electrochemical properties and behaviour. The methodology proposed is based on the decrease experienced by the peak intensity corresponding to voltammetric signals of Cu(II) when successive and constant additions of endosulfan are carried out. This decrease is directly proportional to the concentration of endosulfan what allows to perform an indirect quantification of the pesticide. The detection limit obtained is 40 ng l(-1), this value being under the limits specified by European norms and EPA reports.