Agricultural soil as a potential source of input of organochlorine pesticides into a nearby pond

A study was conducted in the southeastern region of Buenos Aires province, Argentina, to assess an agricultural soil as a potential source of organochlorine (OC) pesticides for the aquatic biota of a nearby pond. We analyzed gamma-HCH (lindane), still in use, and the following banned compounds: DDT, DDE, DDD heptachlor, heptachlor epoxide, aldrin, dieldrin and endrin in soil, bulrush, grass shrimp and fish using gas chromatography with electron capture detection (GC-ECD). Among the OC pesticides, lindane was most dominant in the soil (32.6 ng/g dry wt in the upper and 173.9 ng/g dry wt in the lower horizon) and bulrush (1.9 pg/g lipid). Macrophyte also accumulated high levels of heptachlor epoxide (1.5 pg/g lipid). Heptachlor, although present in the soil, was below the detection limit in all aquatic biota studied. Its primary degradation product, heptachlor epoxide, was found in both soil and biota samples. DDT was found at low levels in the surface soil (6.8 ng/g dry wt), but at higher concentrations in fish (3.6 pg/g lipid), although levels were still below permissible levels for human consumption. Since most of the compounds were found in both soil and aquatic biota, our study suggests that agricultural soil could be an important source for OC pesticides in the nearby pond.     

Evaluation of heavy metal availability in polluted soils by two sequential extraction procedures using factor analysis

Superficial soil and grass samples from 13 locations affected by several anthropogenic sources (mining, metal factory, traffic emissions) were collected in Gipuzkoa, northern Spain. The more labile metal fractions, the mobile (extracted by 0.01 mol l(-1) CaCl(2)) and the mobilisable (extracted by 0.005 mol l(-1) DTPA), were evaluated using a short sequential procedure with two steps. From the results a short-medium term potential lability of Cd, Cu, Zn and Pb can be concluded. The labile levels were compared with the results obtained using the Tessier sequential procedure. Factor analysis was used to check the associations between the total metal contents in soil and grass, as well as between the levels of the different sequential fractions and the total content in grass. Cd, Cu and Zn labile levels were related to total metal grass contents indicating its suitability for the availability studies in polluted soil-plant system.     

Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.     

Analyses of ozone in urban and rural sites in Málaga (Spain)

Ozone concentrations were measured at two (urban and a rural) sites near the city of Málaga (Spain). The aim of this study was to determine the daily, monthly and seasonal variation patterns of ozone concentrations at both sites and to study the possible regional influences. The daily variations mostly have the usual features with the afternoon maximum and the night minimum being more pronounced in the urban area. The average monthly concentrations throughout the year start to increase in March reaching their maximum values in July for the urban site. However, in the rural area, the monthly variations are smaller reaching their maximum value in June. The hourly evolution of the ozone concentrations in both sampling sites is well defined in spring and summer and not so well defined in autumn and winter. Taking into account the four seasons, the rural concentrations are higher than the urban ones. Summer is the season when there are similar concentrations at both sampling sites. Average hourly summer afternoon ozone for the hours 12:00-20:00 LST exceeded the 110 microg m(-3) European Union guidelines for human health for 8 h ozone exposure at the urban and rural sites.     

Structure-activity relationships for association of linear alkylbenzene sulfonates with activated sludge

Sorption of linear alkylbenzene sulfonates (LAS) on sludge particles from wastewater treatment plants was studied. The effect of alkyl chain length and the water hardness were investigated. Sorption on sludge increases with increasing alkyl chain length in the LAS molecules. The results are interpreted in terms of a hydrophobic bonding mechanism being the critical micelle concentration a good index of the surfactant hydrophobicity. The increase in free energy of adsorption for the addition of successive methylene groups to the alkyl chain was estimated as 2.4 kJ/mol. Water hardness clearly enhances the sorption of LAS homologues on sludge and seems to promote cooperative sorption at high surfactant and calcium ion concentrations. An empirical equation was provided that allow to estimate the partition coefficient between aqueous and solid phases for LAS homologues as a function of the alkyl chain length and the water hardness.     

Dissipation of racemic mecoprop and dichlorprop and their pure R-enantiomers in three calcareous soils with and without peat addition

Two racemic herbicides, mecoprop (R,S-MCPP) and dichlorprop (R,S-DCPP), as well as their enantiopure R-forms, were incubated in three calcareous soils at 15 degrees C and 80% of their field capacity to try to elucidate their behaviour in soil and compare the dissipation rates when racemic and enantiopure compounds are used. Quantitation of pesticides is made by HPLC and the R/S ratio by GC-MS. The inactive S-enantiomer from the racemic forms persists longer than the R-forms in silt and sandy loam soils, but for shorter time in the clay loam soil. The pure R-enantiomers, both for MCPP and DCPP, after incubation in soil, are partially converted into their S-forms. In all cases, the dissipation of racemic and pure enatiomeric forms is lower in the clay loam soil than in the silt and sandy loam soils. The R-forms' peristence, in the three soils, is approximately two times lower when they are incubated alone than when they are incubated as racemic compounds. When peat is added, the persistence of these herbicides in the silt and sandy loam soils increases, while in the clay loam soil it decreases. Besides, in the clay loam soil, the enantiomeric ratio (ER) changes from its S-preferential degradation to a preferential degradation of its R-form, so an increase in the persistence of the inactive S-form occurs.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Study of the degradation of dyes by MnP of Phanerochaete chrysosporium produced in a fixed-bed bioreactor

The production of ligninolytic enzymes by the fungus Phanerochaete chrysosporium in a fixed-bed tubular bioreactor, filled with cubes of nylon sponge, operating in semi-solid-state conditions, was studied. Maximum individual manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of 1293 and 225 U/l were detected.The in vitro decolourisation of two structurally different dyes (Poly R-478, crystal violet) by the extracellular liquid obtained in the above-mentioned bioreactor was monitored in order to determine its degrading capability. The concentration of some compounds (sodium malonate, manganese sulphate) from the reaction mixture was optimised in order to maximise the decolourisation levels. A percentage of Poly R-478 decolourisation of 24% after 15 min of dye incubation was achieved.On the other hand, a methodology for a long treatment of these dyes based on the continuous addition of MnP enzyme and H(2)O(2) was developed. Moreover, this enzymatic treatment was compared with a photochemical decolourisation process. The former allowed to maintain the degradation rate almost constant for a long time, resulting in a decolourisation percentage of 70% and 30% for crystal violet and Poly R-478, respectively, after 2 h of treatment. As for the latter, it was not able to degrade Poly R-478, whereas crystal violet reached a degradation of 40% in 2 h.     

Identification of some plasticizers compounds in landfill leachate

In this work it was described a simple method for extraction of plasticizer compounds (mainly phthalate esters and bisphenol A (BPA)) from landfill leachate samples. The samples were submitted to an extraction procedures based on precipitation, solid phase extraction (SPE) and ionic exchange chromatography (IEC). Firstly the landfill leachate sample was acidified by addition of HCl concentrated, in order to precipitate the organic compounds that are less soluble in water. The precipitate was washed with several solvents. The aqueous phase was then submitted to SPE with XAD-4 resin and IEC with Amberlyst A-27 resin. The instrumental analysis was performed by gas chromatography with mass spectrometer detector (GC/MSD) and the compounds were identified by the GC/MSD library (Wiley) and by using some standard substances. These methodologies allow the isolation and identification of the following compounds: dioctylphthalate, diisobutilphthalate, BPA, benzoic acid, palmitic acid and diisopentylphthalate. The methods are very simple, rapid and selective, for plasticizers extraction from landfill leachate matrices.     

Biomarkers of a native fish species (Cnesterodon decemmaculatus) application to the water toxicity assessment of a peri-urban polluted river of Argentina

Environmental monitoring by means of biomarker parameters assessed in different species is a useful tool. It has the advantage of providing a quantitative response as well as valuable information of ecological relevance on the chronic adverse effects caused by water pollution. The aim of this study was to assess the response of biochemical and physiological parameters of Cnesterodon decemmaculatus, a native teleost, simultaneously caught in two sites of Reconquista river, a highly polluted peri-urban river. This study compared the measured parameters with that of specimens of the same species captured in an unpolluted body water, and correlated the detected changes with the physicochemical profile of the water at each site. A comparison was made of selected parameters of gill, brain and liver and of somatic indices of fish collected from polluted and reference sites. The main parameters whose changes allowed to discriminate between sampling sites were gill (Na(+),K(+))-ATPase, brain acetylcholinesterase (AChE) and liver aminotransaminases activities; tissues' protein content and liver somatic index (LSI) were also sensitive biomarkers in brain and liver, respectively. The results showed that the response of the measured biomarkers allowed for the differentiation of sampling sites according to their water quality and confirmed that Cnesterodon decemmaculatus may be a useful test organism for the biomonitoring of freshwater environments. In addition, the simultaneous measurement of the physicochemical parameters of the water samples showed a good correspondence between the biomarkers responses and the environmental chemical stress conditions.