Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air

In this project, a sampling device and an analytical method have been developed to simultaneously analyse the most frequently found low molecular weight amines, including aliphatic, aromatic and alcohol amines. These amines are diethanolamine, ethanolamine, methylamine, isopropylamine, morpholine, dimethylamine, and aniline. A sampling device was developed using a 37 mm cassette with glass fibre filters impregnated with sulfuric acid. Immediately after sampling, the filter was transferred to vials containing a solution of dansyl chloride. Dansyl chloride was used for derivatisation because it forms aromatic sulfonamides that are fluorescent and easy to protonate for MS detection. The effect of using an internal standard made with the dansylated derivative of 1-(2-methoxyphenyl)piperazine (MOPIP) on the uncertainty and efficiency of the method was also evaluated. This internal standard was spiked directly onto filters. The coupling of HPLC/ESI-MS was used for the simultaneous analysis of all the derivatives. This method showed detection limits of about 0.03 microg mL(-1) to 0.3 microg mL(-1) of amine with an average expanded uncertainty of 3% to 6% depending on the amine. The methodology recoveries are close to 100% for all the amines, and the overall estimated expanded uncertainties vary between 10% and 13% depending on the amine. This new strategy will be useful in evaluating workplace air since a unique sampling system will be used, independent of the amine to be quantified.     

Metal speciation in sediment and bioaccumulation in <Emphasis Type="Italic">Meretrix lyrata</Emphasis> in the Tien Estuary in Vietnam

The concentrations of seven toxic metals (cadmium (Cd), nickel (Ni), chromium (Cr), arsenic (As), lead (Pb), copper (Cu), and zinc (Zn)) were determined in sediments and the soft tissues of a bivalve species (Meretrix lyrata) collected from the Tien Estuary in Tien Giang Province, South Vietnam. The total metal concentrations in sediments (mg/kg dry weight) increased as Cd (0.06) < Cu (5.0) < Pb (13.9) < As (16.3) < Ni (24) < Cr (50) < Zn (62). Speciation analysis revealed that these metals existed mainly in the residual fraction (43–94%), followed by the Fe-Mn oxide-bound (5–35%) and organic/sulfide-bound (0.6–9.2%) fractions. The metal concentrations in M. lyrata (mg/kg dry weight) were in the ranges of 1.3–1.9 (Cd), 1.5–2.8 (Ni), 1.8–3.4 (Cr), 11–16 (As), 0.3–0.6 (Pb), 6.9–8.7 (Cu), and 95–128 (Zn), which are safe for human consumption. The order of the mean biota-sediment accumulation factor (BSAF) of the metals in the non-residual fractions of the sediment for M. lyrata was Cd > Cu > As > Zn > Cr > Ni > Pb. The Risk Assessment Codes (RACs) suggest that the highest mobility of Cd (with RAC = 37%) poses greater environmental risk to aquatic biota. Correlation analysis results show that M. lyrata can be used as a biomonitor of Cd and Cu pollution in the exchangeable, acid-soluble, and non-residual sediment fractions.     

Assessment of human exposure to benzene through foods from the Belgian market

Benzene is a volatile organic compound known to be carcinogenic to humans (Group 1) and may be present in food. In the present study, 455 food samples from the Belgian market were analyzed for benzene contents and some possible sources of its occurrence in the foodstuffs were evaluated. Benzene was found above the level of detection in 58% of analyzed samples with the highest contents found in processed foods such as smoked and canned fish, and foods which contained these as ingredients (up to 76.21 μg kg⁻¹). Unprocessed foods such as raw meat, fish, and eggs contained much lower concentrations of benzene. Using the benzene concentrations in food, a quantitative dietary exposure assessment of benzene intake was conducted on a national representative sample of the Belgian population over 15 years of age. The mean benzene intake for all foods was 0.020 μg kg bw d⁻¹ according to a probabilistic analysis. These values are below the minimum risk level for oral chronic exposure to benzene (0.5 μg kg bw d⁻¹).     

Contributions of Acid Deposition and Natural Processes to Cation Leaching from Forest Soils: A Review

Methods of quantifying the roles of atmospheric acid inputs and internal acid generation by carbonic, organic, and nitric acids are illustrated by reviewing data sets from several intensively studied sites in North America. Some of the sites (tropical, temperate deciduous, and temperate coniferous) received acid precipitation whereas others (northern and subalpine) did not. Natural leaching by carbonic acid dominated soil leaching in the tropical and temperate coniferous sites, nitric acid (caused by nitrification) dominated leaching In an N-fixing temperate deciduous site, and organic acids dominated surface soil leaching in the subalpine site and contributed to leaching of surface soils in several other sites. Only at the temperate deciduous sites did atmospheric acid input play a major role in soil leaching. In no case, however, are the annual net losses of cations regarded as alarming as compared to soil exchangeable cation capital.

These results were used to illustrate the methods of quantifying the effects of atmospheric inputs and internal processes on soil leaching rates, not to draw broad generalizations as to acid rain effects on soils. However, there are predictable patterns in natural soil leaching processes which relate to climate, soil properties, and vegetation that may help in predicting the relative importances of natural vs. atmospheric acid inputs to soil leaching.     

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

The effects of the herbicide atrazine on the gill of the freshwater fish Prochilodus lineatus were evaluated after exposure of fish to 2, 10 and 25 μg L⁻¹ atrazine during 48 h (acute exposure) and 14 d (subchronic exposure). Ions and osmolality were measured in plasma and gill samples were taken to determine the Na⁺/K⁺-ATPase (NKA) and carbonic anhydrase (CA) activities and for morphological analysis. Plasma osmolality and Na⁺ and Cl⁻ ions changed depending on atrazine concentration, but atrazine exposure had no effect on the Na⁺/Cl⁻ ratio. NKA activity did not change after atrazine exposure, but CA activity decreased in fish exposed to 25 μg L⁻¹ for 14 d. Gill MRC density decreased after acute exposure but did not change in fish exposed to the subchronic treatment. The MRC density at the epithelial surface increased in fish exposed to 25 μg L⁻¹, and the MRC fractional area (MRCFA) increased in fish exposed to 10 μg L⁻¹. The changes in MRCs provide evidence of morphological adjustments to maintain ionic homeostasis in spite of the inhibition of CA activity at the highest atrazine concentration.     

Uranium uptake by hydroponically cultivated crop plants

Hydroponicaly cultivated plants were grown on medium containing uranium. The appropriate concentrations of uranium for the experiments were selected on the basis of a standard ecotoxicity test. The most sensitive plant species was determined to be Lactuca sativa with an EC₅₀ value about 0.1 mM. Cucumis sativa represented the most resistant plant to uranium (EC₅₀ = 0.71 mM). Therefore, we used the uranium in a concentration range from 0.1 to 1 mM.Twenty different plant species were tested in hydroponic solution supplemented by 0.1 mM or 0.5 mM uranium concentration. The uranium accumulation of these plants varied from 0.16 mg/g DW to 0.011 mg/g DW. The highest uranium uptake was determined for Zea mays and the lowest for Arabidopsis thaliana. The amount of accumulated uranium was strongly influenced by uranium concentration in the cultivation medium. Autoradiography showed that uranium is mainly localized in the root system of the plants tested. Additional experiments demonstrated the possibility of influencing the uranium uptake from the cultivation medium by amendments. Tartaric acid was able to increase uranium uptake by Brassica oleracea and Sinapis alba up to 2.8 times or 1.9 times, respectively. Phosphate deficiency increased uranium uptake up to 4.5 times or 3.9 times, respectively, by Brassica oleracea and S. alba. In the case of deficiency of iron or presence of cadmium ions we did not find any increase in uranium accumulation.     

Tissue radionuclide concentrations in water birds and upland birds on the Hanford Site (USA) from 1971-2009

Historical operations at the Hanford Site (Washington State, USA) have released a wide array of non-radionuclide and radionuclide contaminants into the environment. As a result, there is a need to characterize contaminant effects on site biota. Within this framework, the main purpose of our study was to evaluate radionuclide concentrations in bird tissue, obtained from the Hanford Environmental Information System (HEIS). The database was sorted by avian group (water bird vs. upland bird), radionuclide (over 20 analytes), tissue (muscle, bone, liver), location (onsite vs. offsite), and time period (1971-1990 vs. 1991-2009). Onsite median concentrations in water birds were significantly higher (Bonferroni P < 0.05) than those in onsite upland birds for Cs-137 in muscle (1971-1990) and Sr-90 in bone (1991-2009), perhaps due to behavioral, habitat, or trophic species differences. Onsite median concentrations in water birds were higher (borderline significance with Bonferroni P = 0.05) than those in offsite birds for Cs-137 in muscle (1971-1990). Onsite median concentrations in the earlier time period were significantly higher (Bonferroni P < 0.05) than those in the later time period for Co-60, Cs-137, Eu-152, and Sr-90 in water bird muscle and for Cs-137 in upland bird muscle tissue. Median concentrations of Sr-90 in bone were significantly higher (Bonferroni P < 0.05) than those in muscle for both avian groups and both locations. Over the time period, 1971-2009, onsite median internal dose was estimated for each radionuclide in water bird and upland bird tissues. However, a meaningful dose comparison between bird groups was not possible, due to a dissimilar radionuclide inventory, mismatch of time periods for input radionuclides, and lack of an external dose estimate. Despite these limitations, our results contribute toward ongoing efforts to characterize ecological risk at the Hanford Site.     

The application of a simplified method to map the aerobic acetate mineralization rates at the groundwater table of the Netherlands

A simplified method is used to assess the microbial activity of subsoils and soils across a broad geographic scale. Acetate was selected because it is a major intermediate in catabolic biochemical pathways. In order to get minimal disturbance, only a small amount of tritium labelled acetate and water is added to the subsoil material. After an incubation time, the subsoil material is separated from the water by centrifugation and the formed tritium labelled water is separated from the remaining acetate by evaporation. The data of 128 locations in the Netherlands were plotted in a soil map and were also compared with the depth, dry weight, electric conductivity, pH and nitrate concentration. The peat areas consisted of limed meadows with a high groundwater level whereas the sand areas often showed deeper groundwater levels and a lower pH. The subsoils at the groundwater table of the peat areas, which are in contact with soil air, showed a higher mineralization rate compared with the surface soils in our study. In contrast, the mineralization rate of the subsoil at the groundwater table of sandy soils showed on average a factor 30 lower rate. Nevertheless, the self purification capacity of the subsoil can be vital under weather conditions where the surface soil becomes less active.     

Consistent interpretation of the results of through-, out-diffusion and tracer profile analysis for trace anion diffusion in compacted montmorillonite

Literature data for anion diffusion in compacted swelling clays contain systematic inconsistencies when the results of through-diffusion tests are compared with those of out-diffusion or tracer profile analysis. In the present work we investigated whether these inconsistencies can be explained by taking into account heterogeneities in the compacted samples; in particular increased porosities at the clay boundaries. Based on the combined results of out-diffusion, tracer profile analysis and the spatial distribution of the electrolyte anion in the clay, we conclude that the inconsistencies can indeed be resolved by taking into account a heterogeneous distribution of the total and the anion-accessible porosity. This, by definition, leads to a position dependence of the effective diffusion coefficient. Neglecting these effects results in a rather subordinate systematic error in the determination of effective diffusion coefficients of anions from through-diffusion tests with clay thicknesses in the centimetre range. However, stronger errors in terms of absolute values and conceptual interpretation may be introduced in out-diffusion tests and profile analyses of the diffused tracer. We recommend that anion diffusion tests should be accompanied by measurements of the total and anion-accessible porosity as a function of position in the direction of diffusion.     

The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.