Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Extractive Spectrofluorometric Determination of Quinalphos Using Fluorescein in Environmental Samples

A simple, sensitive, convenient and low cost spectrofluorometric technique for determination of quinalphos is described. Quinalphos is decomposed with sodium ethoxide. Resultant sodium diethyl thiophosphate (Na-DETP) is extracted with a cationic fluorescein as ion pair complex into 1-chloro-2-nitrobenzene. The fluorescence of the ion pair, fluorescein-DETP is measured at 530 nm after excitation at 490 nm. This technique is applicable for the determination of quinalphos in water, food grains and vegetable samples up to ng level with Amberlite XAD-4.     

A Spatial Model to Estimate Habitat Fragmentation and Its Consequences on Long-Term Persistence of Animal Populations

The increasing use of the landscape by humans has led to important diminutions of natural surfaces. The remaining patches of wild habitat are small and isolated from each other among a matrix of inhospitable land-uses. This habitat fragmentation, by disabling population movements and stopping their spread to new habitats, is a major threat to the survival of numerous plant and animal species. We developed a general model, adaptable for specific species, capable of identifying suitable habitat patches within fragmented landscapes and investigating the capacity of populations to move between these patches. This approach combines GIS analysis of a landscape, with spatial dynamic modeling. Suitable habitat is identified using a threshold area to perimeter ratio. Potential movement pathways of species between habitat patches are modeled using a cellular automaton. Habitat connectivity is estimated by overlaying habitat patches with movement pathways. The maximum potential population is calculated within and between connected habitat patches and potential risk of inbreeding within meta-populations is considered. The model was tested on a sample map and applied to scenario maps of predicted land-use change in the Peoria Tri-county region (IL). It (1) showed area of natural area alone was insufficient to estimate the consequences on animal populations; (2) underscored the necessity to use approaches investigating the effect of land-use change spatially through the landscape and the importance of considering species-specific life history characteristics; and (3) highlighted the model's potential utility as an indicator of species likelihood to be affected negatively by land-use scenarios and therefore requiring detailed investigation.     

Higher Plants As Bioindicators Of Sulphur Dioxide Emissions In Urban Environments

The evaluation of certain vascular plants that grow in the city of Madrid as biomonitors of SO₂ air pollution in urban environments has been carried out. Total concentration of sulphur in leaves of the chosen higher plants as well as other parameters in close relation to this contaminant (visible injury symptoms, chlorophyll a- and b-content and peroxidase activity) have been determined in order to study the spatial distribution and temporal changes in SO₂ deposition. Results obtained show that coniferous species such as Pinus pinea, were more sensitive to SO₂ atmospheric concentration than leafy species as Quercux ilex subspecies ballota and, in the same way, bush species, such asPyracantha coccinea and Nerium oleander, were more sensitive than wooded species, such as Cedrus deodaraandPinus pinea, respectively. There is a higher accumulation of sulphur in vegetable species located near highways and dense traffic incidence roads and near areas with high density of population. The minimum values for accumulation of SO₂ were registered in winter and spring seasons (from January to April) due to the vegetative stop; while maximum values are obtained during the summer season (from June to September), due to the stoma opening. The highest increments in sulphur concentration, calculated as the difference between two consecutive months, are obtained in May and June for all considered species except forCedrus deodara and Pyracantha coccinea, both species have few seasonal changes during the whole year. Some species are more sensitive to natural washing than others, showing a decrease in sulphur concentration after rainfall periods.     

Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.     

Influence of aluminium on the restoration potential of a terrestrial vascular plant,Portulaca Oleracea L. as a biomonitoring tool of fresh water aquatic environments

In the present study, the influence of aluminium on the regeneration potential of leaf and stem-cuttings of Portulaca oleracea was studied in order to identify a terrestrial plant species as an alternate biomonitoring toolof fresh water environment. The leaves and stem cuttings of theterrestrial plant, P. oleracea grew well in the distilled water producing adventitious and lateral roots. The aluminium treated leaves and stem cuttings showed a reduction in the growthof the adventitious and lateral roots and increase in the decay of leaves and stem cuttings with increasing aluminium concentration. The tolerance index calculated for the leaves and the stem cuttings showed that the leaves were more sensitivethan stems to aluminium. Since all the parameters studied showedconcentration dependent changes, the terrestrial plant, P. oleracea can be considered a suitable biomonitoring tool of fresh water environment besides its usage in the Al toxicity testing.     

Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.