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.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

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.     

Pollen allergy related to the area of residence in the city of Córdoba,south-west Spain

The aim of this study was to analyse the relationship between the distribution of hay-fever patients in the city of Córdoba, south-western Iberian Peninsula, and the specific atmospheric biological content originating from local sources. Four different districts were established in the metropolitan area of the city, according to vegetational and urbanistic characteristics. Air samples were taken in each area using portable Hirst-type samplers (Lanzoni VPPS 1000) and the spectrum of biological content was defined. Patients attending the Allergy Unit at Córdoba Teaching Hospital in 2000 with allergic rhinitis and/or asthma, and displaying a positive reaction to aeroallergen extracts, were distributed within the areas as a function of their district of residence. Aerobiological results revealed differences in pollen content between areas, in terms of both quantity and number of pollen types recorded. These differences were largely due to proximity to rural areas, prevalence of pollen from typically urban species and the possible effect of urban architecture as a barrier to the dispersal/ concentration of particles and other pollutants. Patients were not uniformly distributed within the city. The majority lived in districts in which pollen from rural species was mixed with pollen from ornamentals. Patients living in typically urban districts displayed a higher prevalence of allergy to pollen from ornamentals. It is concluded that a high degree of exposure to the same environment may influence the development of sensitisation to the particular pollen load associated with that area.     

Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Spatial properties of nutrient concentrations in the Baltic Sea

Using existing monitoring data, the present study attempts to characterize spatial patterns of surface water nutrients in the Baltic Sea. The analysis was made for two different spatial scales, differences between and within sub-basins.Non-parametric methods were chosen to reduce problems with the distributional properties of the data. By dividing the data into four seasons care was taken as to seasonality. To avoid bias due to different laboratory analysis, only data from Nordic countries were used, whose results did not apparently depart from each other. Bias due to different sampling frequency was another problem. This was reduced by using only the last observation in each season for every station and year.The results suggested differences in the nutrient concentrations between basins. The two northernmost basins (Bothnian Bay and Bothnian Sea) had lower phosphate concentrations and higher silicate concentrations compared to the rest of the Sea. Bothnian Bay and the Gulf of Finland had higher nitrate concentrations.The concentration structure within basins was studied using transects in both latitudinal and longitudinal direction. A gradient for phosphate and nitrate was found in the Gulf of Finland, with lower concentrations at the mouth. The Bothnian Sea showed lower concentrations in the middle of the basin compared to the coasts. The highest concentrations of phosphate were found close to the Finnish coast and for silicate the highest concentrations were located near the Swedish coast. It was not possible to study variation in the west-east direction within the Baltic proper, due to data shortage. For the transects in the north-south direction no differences were detected for nitrate and silicate. Phosphate gave one significant result during autumn for the transect in the eastern part of the Baltic proper.This study revealed several problems associated with the data available. Uneven sampling in space and time put severe constraints on the study. A better design of the monitoring program is suggested, where spatial properties are considered explicitly. Revision of the program in this direction is needed for reasonable calculation of total amounts and concentrations representative for a basin.