Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.     

Behaviour of different lichen species as biomonitors of air pollution by PAHs in natural ecosystems

Six different species of lichens (Parmelia sulcata Tayl., Evernia prunastri (L.) Ach., Ramalina farinacea, Pseudevernia furfuracea (L.) Zopf., Usnea sp. and Lobaria pulmonaria (Schreb.) Hoffm.) were collected in two mountain valleys in Central Pyrenees: the Aspe and Aragon valleys. Two multivariate techniques have been applied with different purposes, ANOVA and Discriminant Analysis (DA), to evaluate the data. The PAHs spatial distribution was studied in the three more abundant and widespread species in the area: P. sulcata, E. prunastri (L.) Ach. and R. farinacea in terms of total PAHs, PAHs related to the combustion processes and toxicity. Different behaviour of each lichen species to trap PAHs was found, being P. sulcata the best one to monitor the most persistent PAHs of pyrogenic origin and E. prunastri the most appropriate to provide information about pyrogenic and petrogenic PAHs. Traffic was the most relevant influence in PAHs bioaccumulation in lichen species.     

Identification of heavy metal pollutants using multivariate analysis and effects of land uses on their accumulation in urban soils in Beijing, China

In order to evaluate the current state of the environmental quality of soils in Beijing, we investigated contents of 14 metals in Beijing urban soils inside the 5th ring road by even grids sampling. Statistic analyses were conducted to identify possible heavy metal pollutants, as well as the effects of land uses on their accumulation. Our results revealed that the urban soils in Beijing were contaminated by Cd, Pb, Cu, and Zn. Land uses and urbanization ages affected the accumulation of the four heavy metals in soils significantly. Soils in industrial areas have the highest average Cu and Zn contents, while Pb contents in park areas and Cd in agricultural areas are the highest. The accumulations of Pb and Zn in urban soils increase significantly with sampling plots approaching the city center. And Pb, Cd, and Zn contents in soils in traffic areas also tend to increase in the city center. However, residential areas have the lowest contents of all the four heavy metals.     

Organochlorine contaminants in hair of adolescents from Iassy, Romania

Human hair samples (n=42) from Iassy county (Eastern Romania) collected in 2002-2003 from adolescents were analyzed for hexachlorocyclohexane (HCH) isomers, p,p'-DDT and its metabolites, hexachlorobenzene (HCB), chlordane and metabolites and 5 polychlorinated biphenyl (PCB) congeners. Very low levels were found for HCB and oxychlordane (0.8 and 2.5 ng g(-1)) indicating a low usage of these pesticide formulations in the studied area. In case of HCHs, gamma-HCH isomer was measured at higher median concentrations (79 ng g(-1) hair) compared to the beta-HCH isomer (55 ng g(-1)), which generally is the most prevalent from HCHs. The DDTs profile consisted in p,p'-DDE and p,p'-DDT which levels correspond to 81% of sum DDTs. Very high median concentrations measured for p,p'-DDT (192 ng g(-1)) combined with lower values for p,p'-DDE/p,p'-DDT of 0.4 (from 0.20 to 2.0) in all hair samples suggest recent exposure to "fresh" DDT. When gender was considered, significantly higher concentrations for most of the investigated contaminants were found in girls hair compared to boys. Very high levels were found in the present study for HCHs and DDTs compared to samples from Greece, Western Europe and China. In case of PCBs, the levels found in Romanian samples were found to be in the same range compared to other previously published data.     

Nitrogen export from an agriculture watershed in the Taihu Lake area, China

Temporal changes in nitrogen concentrations and stream discharge, as well as sediment and nitrogen losses from erosion plots with different land uses, were studied in an agricultural watershed in the Taihu Lake area in eastern China. The highest overland runoff loads and nitrogen losses were measured under the upland at a convergent footslope. Much higher runoff, sediment and nitrogen losses were observed under upland cropping and vegetable fields than that under chestnut orchard and bamboo forest. Sediment associated nitrogen losses accounted for 8-43.5% of total nitrogen export via overland runoff. N lost in dissolved inorganic nitrogen forms (NO(3-)-N + NH4+-N) accounted for less than 50% of total water associated nitrogen export. Agricultural practices and weather-driven fluctuation in discharge were main reasons for the temporal variations in nutrient losses via stream discharge. Significant correlation between the total nitrogen concentration and stream discharge load was observed. Simple regression models could give satisfactory results for prediction of the total nitrogen concentrations in stream water and can be used for better quantifying nitrogen losses from arable land. Nitrogen losses from the studied watershed via stream discharge during rice season in the year 2002 were estimated to be 10.5 kg N/ha using these simple models.     

Relationships among multiple trace elements in coastal Casuarina equisetifolia ecosystems on Hainan Island, South China

Forty-six trace elements in coastal Casuarina equisetifolia plant–soil systems at nine sampling sites on Hainan Island were analyzed using ICP-MS. The relationships among the trace elements of the same group or the same periodicity of the Periodic Table in the plants and soils were complex and no consistent patterns were found. More combinations of elements occurred with high positive correlation coefficients within the same periodicity than within the same group of the Periodic Table, and there were more high positive correlations in soils than in plants. However, there were many element combinations in Block d (transition elements) with high positive correlation coefficients in plants. Markedly high positive correlation coefficients between individual rare earth elements and Y and among Zr, Nb, Cd existed in both plants and soils. The dendrograms obtained by cluster analysis show that rare earth elements had very similar occurrence and distribution in both soils and plants. Thus, they behaved as a coherent group of elements both geochemically and biogeochemically. The transition elements were more coherent in plants than in soils.     

Effect of chromium on the fatty acid composition of two strains of Euglena gracilis

The effect of hexavalent chromium on fatty acid composition was studied in two strains of Euglena gracilis; UTEX 753 (from the Culture Collection of Algae of Texas University, USA) and MAT (isolated from a highly polluted River). Both were grown in photoauxotrophic and photoheterotrophic conditions and exposed to two metal concentrations, one below and one above IC50. The high malondialdehyde (MDA) levels (3 to 7-fold) obtained with chromium concentration above IC50, suggested the existence of metal-induced lipid peroxidation. Total lipid content increased only with concentration below IC50, whereas it was inhibited by higher metal concentration. Photoheterotrophic control strains exhibited a significantly higher proportion of saturated and polyunsaturated fatty acids. Polyunsaturated acids were most affected by chromium, especially those related to chloroplast structures. Ultra-structure studies showed clear thylakoid disorganization in all treated cells. The results indicate that hexavalent chromium affects levels of fatty acids, especially those related to photosynthetic activity.     

Distribution of fission products in dust samples from the region of Thessaloniki, Greece, after the Chernobyl nuclear accident

The distribution of the fission products (95)Zr, (95)Nb, (103)Ru, (106)Ru (determined through (106)Rh), (125)Sb, (129m)Te, (134)Cs, (137)Cs, (140)Ba, (140)La, (141)Ce and (144)Ce has been determined in dust samples from the region of Thessaloniki, Greece, after the nuclear accident at Chernobyl. The samples studied also included (110m)Ag, not belonging to the products of (235)U fission. Samples showing higher concentrations of radionuclides also show a higher content in clay minerals, whereas samples having low concentrations of radionuclides usually contain large amounts of quartz and feldspars. Desorption and leaching experiments using solutions of chlorides of sodium, potassium, calcium and magnesium (0.5 N), as well as distilled and tap water, were also performed. Sodium and potassium chloride solutions were found to be efficient in desorbing and/or leaching of caesium and ruthenium isotopes to an extent of about 30%.     

Dissolved organic matter fractions formed during composting of winery and distillery residues: evaluation of the process by fluorescence excitation-emission matrix

The aim of the present paper is to assess the maturity degree reached by different samples of several mixtures from winery and distillery residues composted using the Rutgers composting system, by means of excitation-emission matrix (EEM) fluorescence spectroscopy. The composts were sampled once a week for about 200d. EEM spectra indicate the presence of different fluorophores. The fluorescence intensities of these peaks show trends related to the maturity of the composting samples selected. The "contour density" of EEM maps is strongly modified through time. We have used the quantitative method of fluorescence regional integration (FRI). The EEMs were delineated into five excitation-emission regions. The degree of compost maturity could be correlated with the percentage of the volumetric integration under the EEM within each region. Further refinement of these techniques should provide a relatively rapid method for assessing the suitability of the compost to soil application.