Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Chromium redox speciation in natural waters

Dissolved hexavalent chromium concentrations were determined in river, estuarine and coastal waters of the Humber catchment in north-east England. Samples were collected, filtered, extracted on site and after storage for up to eight days. Hexavalent chromium concentrations did not change by more than 0.05 microg l(-1) (not significant, p = 0.05) over this period. Total chromium concentrations in the catchment were less than 1.0 microg l(-1). This is low in relation to the proposed Environmental Quality Standard. Hexavalent chromium accounted for between 27% and 100% of the total dissolved concentration, with an average of approximately 50%. The proportion of Cr(III) and Cr(VI) in the rivers and estuary were of the same range as previously measured in 1993. The addition of Cr(III) and Cr(VI) to fresh and saline water samples illustrates the complexity of the factors controlling chromium speciation in natural waters. The presence of oxidisable organic matter and the stabilising role of complexing organic ligands are proposed as the main controlling influences of redox speciation in filtered samples.     

Organotin compounds in the marine environment of the Bay of Piran,northern Adriatic Sea

In the year 2000, organotin pollution was investigated in the Bay of Piran, Slovenia, at the northern extremity of the Adriatic Sea. Gas chromatography-mass spectrometry with single ion monitoring GC/MS-SIM was applied for speciation analysis of pentylated organotin compounds in water and mussels. Sampling of marine waters was performed in summer and autumn at 8 locations. Mussels Mytilus galloprovincialis were collected only in summer at 3 locations. The highest concentrations of tributyltin (TBT) in marine water ranged from 500 to 630 ng L(-1) (as Sn) in summer and from 180 to 230 ng L(-1) (as Sn) in autumn. TBT concentration in mussels varied from 500 to 3500 ng g(-1) dry weight (d.w.) (as Sn). The study indicated remarkable butyltin pollution of the Slovenian coastline. Accuracy of the analytical procedure was verified by BCR CRM 477.     

Atrazine and Alachlor Inputs to Surface and Ground Waters in Irrigated Corn Cultivation Areas of Castilla-Leon Region, Spain

The inputs of atrazine and alachlor herbicides to surface and ground waters from irrigated areas dedicated to corn cultivation in the Castilla-León (C-L) region (Spain) as related to the application of both herbicides were studied. Enzyme-linked immunosorbent assays (ELISA) were used for monitoring the atrazine and alachlor concentrations in 98 water samples taken from these areas. Seventy-nine of the samples were of ground waters and 19 were of surface waters. The concentration ranges of the herbicides detected in the study period (October 1997–October 1998) were 0.04–25.3 g L^–1 in the surface waters and 0.04–3.45 g L^–1 in the ground waters for atrazine, and 0.06–31.9 g L^–1 in the surface waters and 0.05–4.85 g L^–1 in the ground waters in the case of alachlor. The highly significant correlation observed between the concentrations of both herbicides in the surface waters (r = 0.89, p < 0.001) pointed to a parallel transport of atrazine and alachlor to these waters. A study was made of the temporal evolution of the concentrations of both herbicides, and it was found a maximum recharge of atrazine in the ground waters for April 1998 and of alachlor in October 1997 and October 1998. The temporal evolution of the concentrations of both herbicides in surface waters was parallel. The highly significant correlations observed between atrazine concentrations determined by ELISA and by HPLC (r = 0.92, p < 0.001) and between alachlor concentrations also determined by both methods (r = 0.96, p < 0.001) confirmed the usefulness of ELISA for monitoring both herbicides in an elevated number of samples. Using HPLC, the presence in some waters of the alachlor ethanesulfonate (ESA) metabolite was found at a concentration range of 0.52–4.01 g L^–1. However the interference of ESA in the determination of alachlor by ELISA was negligible. The inputs of atrazine and alachlor to waters found in this study, especially the inputs to ground waters, could pose a risk for human health considering that some waters, though sporadically, are even used for human consumption.     

IMPACTS OF VISITORS ON SOIL AND VEGETATION OF THE RECREATIONAL AREA “NACIMIENTO DEL RÍO MUNDO” (CASTILLA-LA MANCHA, SPAIN)

This study examines the effects of recreational use on the soil and vegetation at a site of ecological importance (Nacimiento del Río Mundo, Albacete, Spain). The most visited sites showed increased soil compaction of approximately 50%, bare ground increase to 61 ± 10% and a decrease in richness (from 25 ± 2 to 15 ± 2 species), diversity (from 4.0 ± 0.1 to 2.7 ± 0.4) and stratification of plant species (from 80 ± 11 to 21 ± 4%). The most visited sites had 90% less plant species as compared to the least visited. Intense use was associated with the presence of nitrophilous plant and vegetal species with a morphology adapted to heavy trampling. The recreational areas showed a distribution pattern of impact radiating outwards from the most used and degraded point. At the most visited point, Los Chorros (the spring of the river), the impact radiated outwards for about 20 m. A pilot experiment examining the effects of one-year restriction to visitors for access to a formerly impacted area showed a plant cover increase by anthropic and not by native species of 57 percent units.     

Pool of Dust Particles over the Asian Continent: Balloon-borne Optical Particle Counter and Ground-based Lidar Measurements at Dunhuang, China

Measurements of aerosols were made in 2001 and 2002 at Dunhuang (40 degrees 00'N, 94 degrees 30'E), China to understand the nature of atmospheric particles over the desert areas in the Asian continent. Balloon-borne measurements with an optical particle counter suggested that particle size and concentration had noticeable peaks in super micron size range not only in the boundary mixing layer but also in the free troposphere. Super-micron particle concentration largely decreased in the mid tropopause (from 5 to 10 km; above sea level, a.s.l.). Lidar measurements made during August 2002 at Dunhuang suggested the possibility that mixing of dust particles occurred from near the ground to about 6 km even under calm weather conditions, and a large depolarization ratio of particulate matter was found in the aerosol layer. The top of the aerosol layer was found at heights of nearly 6 km (a.s.l.). It is strongly suggested that nonspherical dust particles (Kosa particles) frequently diffused in the free atmosphere over the Taklamakan desert through small-scale turbulences and are possible sources of dust particles of weak Kosa events that have been identified in the free troposphere not only in spring but also in summer over Japanese archipelago. Electron microscopic experiments of the particles collected in the free troposphere confirmed that coarse and nonspherical particles observed by the mineral particle were major components of coarse mode (diameter larger than 1 microm) below about 5 km over Dunhuang, China.     

Estimating the change of carbon in the terrestrial biosphere from 18 000 BP to present using a carbon cycle model

The authors used a global High Resolution Biosphere Model (HRBM), consisting of a biome model and a carbon cycle model, to estimate the changes of carbon storage in the major pools of the terrestrial biosphere from 18 000 BP to present. The climate change data to drive the biosphere for 18 000 BP were derived from an Atmospheric General Circulation Model. Using the AGCM anomalies interpolated to a 0.5 degrees grid, the HRBM data base of the present climate was recalculated for 18 000 BP. The most important processes which influenced the carbon storage include (1) climate-induced changes in biospheric processes and vegetation distribution, (2) the CO(2) fertilization effect, (3) the inundation of lowland areas resulting from the sea level rise of 100 m. Two scenarios were investigated. The first scenario, which ignored the CO(2) fertilization effect, led to total carbon losses from the terrestrial biosphere of -460 x 10(9) t. Scenario 2, which assumed that the model formulation of the CO(2) fertilization effect as used for preindustrial to present could be extrapolated to the glacial 200 microl litre(-1) (ppmv, parts per million per volume), gave a carbon fixation in the terrestrial biosphere of +213 x 10(9) t. The two scenarios were compared with CO(2) concentration data and isotopic ratios from air in ice cores. The results of Scenario 1 are not in agreement with the data. Scenario 2 gives realistic delta(13)C shifts in the atmosphere but the biospheric carbon storage at the end of the glacial period seems too large. The authors suggest that the low atmospheric CO(2) concentration may have favoured the C-4 plants in ice age vegetation types. As a consequence the influence of the low CO(2) concentration was eventually reduced and the glacial carbon storage in vegetation, litter, and soil was increased.     

Responses of Gammarus pulex (Amphipoda, Crustacea) to metalliferous effluents: identification of toxic components and the importance of interpopulation variation

This study was designed to evaluate the ability of an in-situ bioassay to assess the impact of complex effluents on freshwaters and to identify toxic components. Reductions in the feeding rate of Gammarus pulex proved to be a sensitive indicator of the impact of metalliferous effluents on receiving water quality. The effluents contained a mixture of five potentially toxic metals. By combining information on feeding rates with bioaccumulation data, two metals, iron and manganese, were identified as the probable toxic agents. Laboratory experiments validated the conclusions reached from the field study and confirmed that iron was a major toxicant. The sensitivities of Gammarus pulex from a metal-contaminated site and a clean site were compared during both the field and laboratory studies. Interpopulation differences in the response of G. pulex to toxicants were detected in the field study but not in the laboratory experiments. Possible reasons for this are discussed.     

Effects of acid rain on growth and nutrient concentrations in Scots pine and Norway spruce seedlings grown in a nutrient-rich soil

The effects of artificially applied acid precipitation on growth and nutrient concentrations of Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst.) seedlings were investigated in a long-term acid irrigation experiment in field conditions. Seedlings of northern and southern origin were planted in boxes containing peat and composted soil rich in nutrients, and sprinkler irrigated with water acidified with nitric and sulphuric acids to pH 3 or pH 4 for periods varying from two to three and a half growing seasons during 1986-1989. Water irrigated (pH 5.4-7.6) and non-irrigated groups of seedlings were also included in the experiment. At the end of the experiment needles, main and lateral shoots and roots were collected from the seedlings for the determination of height growth and biomass partitioning, and for the analysis of S, N, Mg, P, K, Ca, Mn and Fe concentrations. The treatment effects compared to the irrigated control were studied using multivariate analyses of variance and covariance. In the pine seedlings the total dry matter production increased by 25-70% compared with the irrigated controls when the total wet deposition to the seedlings exceeded 67 kg S ha(-1) and 36 kg N ha(-1) (e.g. after two growing seasons' exposure of the pH 3 treatment). The increase was mainly due to an increase in needle dry weight (54-72% greater at pH 3) and root weight (20-65% greater at pH 3), whereas the height growth or shoot weight growth were less affected. The northern provenance pine seedlings responded more clearly to the pH 3 irrigation than the southern ones. The treatments had no consistent effects on any of the growth variables studied in the spruce seedlings, however. The pines had higher root and foliage Ca concentrations as a result of the acid irrigation, whereas in spruce, acid rain decreased the Ca concentration in needles and shoots. Root Mn and Fe concentrations were higher in both species as a result of the pH 3 treatment. A higher soil conductivity and Ca concentration resulted from the prolonged pH 3 treatment. The results strongly support the hypothesis that the long-term growth and nutrient allocation response of conifers to acid precipitation is dependent both on the tree species and on the nutritional status of the soil.     

利用铕的氧化态作为氧逸度的一种指示剂

由于大部份三价稀土元素具有类似的、规律变化的电子性质,它们在自然界构成一个相互密切关联的地球化学元素族。但在一定的物理条件下,某些稀土元素却显示特异的行为,因为这些稀土元素在非3+价态下具有有重要意义的稳定性。铕的这种特异行为最为显著,在岩浆的氧化还原条件下,其二