New Evidence for the presence of arsenocholine in shrimps (Pandalus borealis) by use of pyrolysis gas chromatography — atomic absorption spectrometry/mass spectrometry

An analytical method for the structure elucidation of quarternary organoarsenic compounds in trace amounts in fish and crustaceans has been developed in this laboratory. The two major organoarsenicals found in shrimps have been separated by ion-exchange chromatography and their stucture has been studied by the use of pyrolysis gas chromatography. Their degradation in the pyrolyzer unit has been studied by the use of atomic absorption spectrophotometer or mass spectrometer as detectors. A comparison of the analytical data of these substances and data from synthetic reference substances show complete agreement. The structures of reference compounds have been confirmed by use of nuclear magnetic resonance spectrometry and fast atom bombardment (FAB) mass spectrometry. It is demonstrated that both of the organoarsenic compounds in shrimps have a trimethylarsonio moiety e.g. the compounds have a quarternary structure. Furthermore, the more basic organoarsenic compound has a mass spectrometric fragmentation pattern similar to synthetic arsenocholine and acetylarsenocholine. Treatment of arsenobetaine with hot base produces trimethylarsineoxide in a high yield (96%). Arsenocholine, however, remains unchanged during this treatment. Treatment with sodium benzenethiolate does not result in chemical demethylation, which shows that this method together with gas chromatography-mass spectrometry is not feasible for confirmation of its structure.     

Identification of arsenobetaine in sole,lemon sole,flounder, dab,carb and shrimps by field desorption and fast atom bombardment mass spectrometry

Organo-arsenic has been isolated from sole, lemon sole, flounder, dab, crab and shrimps by extraction or ion-exchange in combination with thin-layer chromatography. An alkaline digestion of the samples, followed by a reduction with sodiumborohydride leads to the formation of trimethylarsine. The behaviour of the organo-arsenic compound was very similar to that of synthesized arsenobetaine. Field desorption mass spectrometry (FDMS) can be used to identify arsenobetaine in the isolates. Sufficient purification by thin-layer chromatography is found to be a prerequisite for the detection of a protonated molecular ion of arsenobetaine. If this situation is not met acid enhanced FDMS or Fast Atom Bombardment mass spectrometry in high resolution can be used successfully.     

Effects of ozone on yield, growth, and root starch concentrations of two alfalfa (Medicago sativ A L.) cultivars

Ozone (O3) is considered to be a major air pollutant that affects the yield of several sensitive crop species. Its concentration may reach phytotoxic levels several times during the growing season in Eastern Canada. This study was initiated to evaluate the O3 effects on alfalfa, a major crop species. The objective was to compare the yield and growth parameters of the main alfalfa cultivar used in Québec, Apica, to a cultivar more tolerant to O3, Team. Effects on root starch concentrations were also examined as this parameter is an important indicator of alfalfa perennity. The results obtained have shown that the forage yield of Apica was more reduced by O3 during two growing seasons than the yield of Team. For O3 concentrations of 20 to 40 nl liter(-1), yield reductions were 14-26% for Apica and 0-20% for Team. Whereas Apica could be considered more susceptible to O3 than Team, the latter has shown contrasting responses from year to year. This fact suggests that the mechanisms involved in O3-tolerance could be modulated by environmental conditions. At low O3 levels, Apica has shown reduced root growth in terms of dry matter and length. However, contrary to the current hypothesis that O3 would affect more root than shoot growth, we were unable to show a consistent alteration of the biomass allocation between the two. Ozone seems to reduce globally the growth of the whole plants. The greater O3-tolerance of Team could partly be associated to its capacity to maintain more leaves, to delay their senescence, or to keep a larger leaf:stem ratio under increasing levels of O3. At the end of the two growing seasons, the amount of starch reserves stored below ground was shown to be reduced by the current O3 levels. This reduction was mainly associated with a decrease in root biomass under O3 stress. This result support the hypothesis that O3 may accelerate alfalfa decline under field conditions.     

Topsoil (0-5 cm) composition in eight arctic catchments in northern Europe (Finland, Norway and Russia)

Frozen topsoil samples (0-5 cm) were collected during March/April 1994 in eight Arctic catchments in northern Europe (four in Russia, three in Finland, one in Norway), at different distances and in different wind directions from the emissions of the Russian mining, roasting and smelting industry on the Kola Peninsula. Between 14 and 25 sites were sampled in each of the eight catchments ranging in size from 12 to 35 km2. Results show that close to the smelters in Monchegorsk and Nikel, topsoil is clearly enriched in Ag, As, Bi, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, Se, Te and V. Cu and Ni median contents in topsoils collected close to Monchegorsk are about 600 times higher than in the Finnish catchments. The effect of open-cast mining and waste dumps of alkaline rocks from the nephelinite industry near Kirovsk can be seen in the elevated contents of Al, Ba, K, La, Mn, Na, Sr, Ti, Y and Zn in topsoil collected in a nearby catchment. For many elements, however, variations observed in single catchments are as great as the total regional variation. Several elements (e.g. Cd, Hg, Cu, Ni, Pb, S, Zn) show strong positive correlation between the organic content of the sample and the element content observed. Thus it is necessary to determine the organic content of the samples and correct the element levels when using depth-related soil samples (here, the 0-5 cm topsoil layer) for regional mapping.     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.     

The influence of particle surface characteristics on pollutant metal uptake by cells

The phosphatic mineral, hydroxyapatite, and two ion exchange resins have been used as artificial sediment particles. The surface properties of these materials have been studied using the Langmuir adsorption isotherm to calculate the binding capacity (B(max)) and the adsorption constant (K(L)) for zinc and cadmium ions. Mussels (Mytilus edulis) were fed on the particles and their digestive glands were subsequently removed and subjected to cell fractionation. The supernatant fraction was used to determine cytosol metal levels as a measure of the materials absorbed from the ingested particles. The level of cytosol zinc and cadmium was correlated with the K(L) values of the artificial sediments. It is suggested that phagocytosis of sediment particles plays an important part in transferring pollutants into benthic organisms and that the efficiency of this process is related to the adsorption coefficient of the particle surfaces.     

Biomonitoring environmental contaminants near a municipal solid-waste combustor

Tetrachlorodibenzo-p-dioxin (TCDD), tetrachlorodibenzofuran (TCDF) and selected metal concentrations were measured in eggs and nestlings of anhingas (Anhinga anhinga) and white ibises (Eudocimus albus) collected from a colony next to a municipal solid-waste (MSW) combustor and ash landfill. Most of the measured residues, including TCDD, TCDF, arsenic, beryllium, cadmium and nickel, remained at pre-operational levels during the first five years of facility operation. Selenium (in anhingas) and mercury (in both anhingas and ibises) occurred at their lowest concentrations in samples collected during the fifth year of facility operation (Year-5). Alternatively, concentrations of lead in ibis nestlings were highest in Year-1 and Year-5 compared to Year-0. The MSW combustor could neither be ruled out nor confirmed as the source of this lead.     

Do aquatic effects or human health end points govern the development of sediment-quality criteria for nonionic organic chemicals ?

The equilibrium partitioning theory may be used to describe the partitioning of nonionic organic chemicals between water, sediment, and aquatic biota. This paradigm was employed to compare the relative magnitudes of organic carbon-normalized sediment-quality criteria that are intended to protect either benthic organisms from the direct toxic effects of sediment-associated chemicals or humans from the indirect health effects posed by the ingestion of contaminated aquatic animals. Comparison of calculated sediment-quality criteria for a variety of hydrophobic chemicals suggests that human health-based end points often result in more restrictive criteria than aquatic effects-based values. Review of published field data indicates that the equilibrium partitioning paradigm may, depending on contaminant class, either over- or underestimate the extent to which sediment-associated contaminations are bioaccumulated. Despite the limitations of adopting this simple theory for criteria development, calculations reveal that regulatory decisions involving sediments contaminated with such chemicals may be dictated by human health concerns if current risk assessment methodologies are applied.     

Analysis of gaseous diisocyanates in air using chemosorption sampling

A sampling procedure for 2,4- and 2,6-toluenediisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI) in the range 0.007-0.7 mg/m³ in a 15 L air sample is described. The sampling is performed with 9-(N-methylaminomethyl)-anthracene (MAMA) adsorbed on a solid sorbent, Amberlite XAD-2. The recoveries are 80–100% in this chemosorption reaction. The urea derivatives are desorbed with N,N-dimethylformamide and analysed by high performance liquid chromatography (HPLC). Samples and prepared chemosorption tubes are stable for at least two weeks if stored in the dark. To complete the investigation, field measurements of TDI were performed in an industrial atmosphere.