Optimisation of pressurised liquid extraction for elimination of sulphur interferences during determination of organotin compounds in sulphur-rich sediments by gas chromatography with flame photometric detection

A simple method for species-selective analysis of organotin compounds (OTCs) (butyl and phenyl) in sediments was developed. The sample preparation procedure was specifically optimised for sulphur-rich sediments to eliminate interferences from elemental sulphur and organosulphur compounds. Tin species were extracted from sediment samples using pressurised liquid extraction technique (PLE), ethylated - with simultaneous extraction to isooctane - in aqueous phase with sodium tetraethylborate (NaBEt(4)) and separated/detected by gas chromatography with flame photometric detection (GC-FPD). PLE operational variables (extraction temperature and pressure, solvent composition and number of static extraction steps) and extract handling routine were fine-tuned to minimise the amount of extracted interferents while keeping OTCs recovery at an acceptable level. Best results were obtained after extraction of sediment samples with methanol/water (75% v/v methanol) solution of acetic acid/sodium acetate with tropolone addition (0.6 g l(-1)). Derivatisation of low temperature, high-pressure (50 degrees C, 13.8 MPa) extracts gives isooctane extracts which are clean enough to be directly analysed by GC-FPD without any further cleanup. Interferences from elemental sulphur were completely eliminated while concentrations of other interferents were reduced to the level not impairing quantitation of OTCs under the study. No negative effects in terms of chromatographic column deterioration were observed after repeated injections of such extracts. Two certified reference materials, BCR646 and PACS-2, were analysed to assess performance of the method. Recoveries of all OTCs under the study, except MBT, were in the range of 91-114%. MBT extraction efficiency was low (34-47%) therefore the method is unsuitable for precise determinations of this compound.     

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.     

Evaluation of natural and anthropogenic influences on the Guadalquivir River (Spain) by dissolved heavy metals and nutrients

To evaluate both the natural and anthropogenic influences on surface waters of Guadalquivir River (SW-Spain), concentrations of dissolved trace metals (Mn, Co, Ni, Cu, Cd, Zn, and Pb), inorganic nutrients (N-NH(4)(+), N-NO(3)(-), N-NO(2)(-), and P-PO(4)(3-)) and other variables as conductivity, pH, dissolved oxygen (DO) and suspended solids (SS) were measured during a three-years period (2001-2003). Samples were taken at 26 stations twice a year, during rain and dry periods. The analysis of variance (ANOVA) suggested that temporal variations within the period of study were statistically negligible. Spatial distributions identified three different zones, mainly influenced by sewage (Eastern Zone), agriculture runoffs (Central Zone), and estuarine processes (Western Zone), respectively. Principal Component and Cluster Analysis allowed to identify the variables controlling the water quality of each zone as: N-NH(4)(+), N-NO(2)(-), Mn, and Co, (Eastern Zone), SS, and P-PO(4)(3-) (Central Zone), and Cd, pH and conductivity (Western Zone). Other variables such as Ni, Cu, Zn or N-NO(3)(-), influenced two different zones, while Pb presented a singular behavior.     

Electrochemical and FTIR studies of the mutual influence of lead(II) or iron(III) and phenol on their adsorption from aqueous acid solution by modified activated carbons

Cyclic voltammetry and spectral FTIR studies of the influence of activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol from aqueous acidic solution were carried out. The diversity in surface chemical structure was achieved by applying different procedures of inorganic matter removal and by modifying the carbon samples in various ways: heating under vacuum, aminoxidation in an ammonia-oxygen atmosphere, oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb(2+) or Fe(3+)) and phenol from solutions containing cation or phenol separately or in a mixture were determined. The adsorption capacity from acidic aqueous acidic solution depends on the chemical properties of the activated carbon surface (e.g., decrease in phenol adsorption with relative lower basicity of the adsorbent). The electrochemical parameters of electrodes made from the carbon samples were estimated, and some possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte solution containing adsorbed species (separately or as a mixture). Relationships were found between metal ion adsorption and electrochemical behavior of Pb(2+)/Pb(4+) and Fe(3+)/Fe(2+) couples on the one hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption and/or coupling phenol molecules are discussed.     

Biodegradability and ecotoxicity of amine oxide based surfactants

The aerobic and anaerobic biodegradability as well as the aquatic toxicity of two fatty amine oxides and one fatty amido amine oxide were investigated. Aerobic biodegradation was evaluated using the CO(2) headspace test (ISO 14593) and biodegradation under anaerobic conditions was assessed employing a standardised batch test. The three amine oxide based surfactants tested were readily biodegradable under aerobic conditions but only the alkyl amido amine oxide was found to be easily biodegradable under anaerobic conditions. Toxicity to Photobacterium phosphoreum and Daphnia magna was evaluated. Bacteria (EC(50) from 0.11 to 11 mg l(-1)) proved to be more sensitive to the toxic effects of the amine oxide based surfactants than crustacea (IC(50) from 6.8 to 45 mg l(-1)). The fatty amido amine oxide showed the lowest aquatic toxicity.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Bioaccumulation of lead, mercury, and cadmium in the greater white-toothed shrew, Crocidura russula, from the Ebro Delta (NE Spain): sex- and age-dependent variation

We quantified bioaccumulation of lead, mercury, and cadmium in bones from 105 greater white-toothed shrews (Crocidura russula) collected at the Ebro Delta, a polluted area, and the Medas Islands, a control site. Lead and mercury levels varied with site, age, and sex, although statistical significances depended on each factor. Globally, shrews from the polluted area exhibited significantly higher concentrations of Pb and Hg. Increment of Pb with age was particularly remarkable in wetland animals and was interpreted in relation to human activities, namely hunting. Unlike males, females from the Ebro Delta maintained low Hg levels, which were associated with gestation and lactation. Cadmium levels did not differ between sites, sexes, or ages. This study provides the first data on heavy metals in mammals from this wetland and suggests that C. russula is a good bioindicator of metal pollution. We concluded that sex and age may represent an important source of variation in the bioaccumulation of these metals in wild populations.     

Estrogenic activity associated with organochlorine compounds in fish extracts from European mountain lakes

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hin?ovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'(W)) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb(T)) in pure water. Experimental breakthrough volumes (Vb(E)) were first determined using purified and deionized water as the matrix for selected compounds having Vb(T) < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4-5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb(E) curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5-6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb(E) in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.