Atmospheric influence on the distribution of organic pollutants in the Guadalquivir River estuary, SW Spain

In the lower Guadalquivir river basin, a system stressed by a wide variety of anthropogenic activities, eight pesticides (four triazines, two chloroacetanilide herbicides, one organochlorine, and one organophosphorus insecticide); and four emerging pollutants (two personal care products, one organophosphorous flame retardant, and one xanthine alkaloid) were analyzed in river water during a 2-year monitoring program, and after rain episodes. Samples were extracted using the solid phase extraction (SPE) technique prior to determination of compounds using gas chromatograph coupled to a mass spectrometer detector. Except for caffeine, recoveries were mostly above 80 %, while limits of detection and quantification were in the low nanograms per liter level (except for dimethoate). Terbuthylazine, simazine (triazine herbicides), and dimethoate (organophosphorus insecticide), present in agrochemicals, were predominant in the river water, although concentrations were below the quality standards established by the EU Water-Framework-Directive. A general trend to increase concentration was observed after rain events, in particular for pesticides, possibly as a consequence of surface runoff.     

Degradation of endosulfan in a clay soil from cotton farms of western Queensland.

The persistence and degradation of endosulfan isomers and their primary degradation product, endosulfan-sulfate, were studied in a clay soil from cotton farms of western Queensland. Endosulfan degradation in relation to soil moisture, temperature, day and night temperature fluctuation, waterlogging and re-application were studied. The results show that the degradation rates of both endosulfan isomers were greatly affected by changes in soil water content and temperature. Under a high water content-high temperature regime the concentration of alpha-endosulfan in the soil fell rapidly during the first 4 weeks of application, followed by a prolonged period of slower rate of degradation. Alpha endosulfan showed a bi-exponential form of degradation for all water content-temperature experiments except for extremes in both these two factors. In the submerged soils (and also in low-water content, low temperature, non-submerged experiments) no such rapid initial degradation of alpha-endosulfan was observed, and a single first-order rate equation describes the data. Degradation of beta-endosulfan was significantly slower than for the alpha-isomer under all conditions studied. A half-life of more than a year was recorded for the beta-isomer when both water content and temperature were low. The degradation of beta-endosulfan showed no sign of the bi-exponential function observed for alpha-isomer, and a single first order rate equation described the data obtained for each factor studied. Endosulfan-sulfate was the major degradation product in all non-submerged experiments. Its build up in the soil very closely followed the disappearance of alpha-endosulfan. Its highest build-up was in the high water content-low temperature experiments, but its persistence was primarily influenced by soil temperature. Both alpha and beta-isomers, and endosulfan sulfate, persisted longer in the submerged soil. Re-application of endosulfan, and day and night fluctuation of temperature had contrasting effects on the degradation of the two isomers. Both factors slowed down the degradation of alpha-endosulfan and enhanced that of beta-endosulfan, but their net effect was to prolong the overall persistence of this chemical in the soil. Submerged conditions reduced the net formation of endosulfan-sulfate and enhanced its degradation rate.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Metal extractability patterns to evaluate (potentially) mobile fractions in periurban calcareous agricultural soils in the Mediterranean area—analytical and mineralogical approaches

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO₃·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.     

Study of the solubility and stability of polystyrene wastes in a dissolution recycling process

Dissolution with suitable solvents is one of the cheapest and more efficient processes for polystyrene waste management. In this work the solubility of polystyrene foams in several solvents benzene, toluene, xylene, tetrahydrofuran, chloroform, 1,3-butanediol, 2-butanol, linalool, geraniol, d-limonene, p-cymene, terpinene, phellandrene, terpineol, menthol, eucalyptol, cinnamaldheyde, nitrobenzene, N,N-dimethylformamide and water has been determined.Experimental results have shown that to develop a “green process” the constituents of essential oils, d-limonene, p-cymene, terpinene, phellandrene, are the most appropriate solvents. The action of these solvent does not produce any degradation of polymer chains. The solubility of the polymer in the mentioned solvents at different temperatures has been investigated. The solvent can be easily recycled by distillation.     

Impact of biofumigation with solarization on degradation of pesticides and heavy metal accumulation

A greenhouse study was conducted to evaluate the effect of biofumigation (with sheep and chicken manure) combined with solarization on the dissipation of pesticides (pyrifenox, DDT and dieldrin), and on soil metals accumulation. The treatments consisted of a control, and soil disinfestations by biofumigation combined with solarization (B+S) for two, four, five, six consecutive years. B+S enhanced the dissipation of pyrifenox with regard to control treatment. Significant differences were not detected among plots disinfected with B+S for consecutive years. On the other hand, B+S had no effect on the dissipation of DDT and dieldrin, probably due to the resistance of these pesticides to microbial degradation and/or high temperatures. Biofumigation is considered to be an environmentally safe practice, since no accumulation of heavy metals such as Cd, Co, Cu, Cr, Pb, Ni, or Zn was observed after the subsequent application of organic matter through the treatments.     

Comparison of inorganic and composite ferric oxide sorbents for arsenic removal

Three different sorbents based on hydrated ferric oxide (GEH, ArsenX^np and Lewatit FO 36) were compared from the viewpoints of their column operation. Particle size distribution, pressure drop across the column and ferric oxide content were measured. Sorption capacities under the presence of accompanying ions were measured in batch wise and column experiments.