Application of multivariate statistical analyses in the interpretation of geochemical behaviour of uranium in phosphatic rocks in the Red Sea,Nile Valley and Western Desert,Egypt

Factor and cluster analyses as well as the Pearson correlation coefficient have been applied to geochemical data obtained from phosphorite and phosphatic rocks of Duwi Formation exposed at the Red Sea coast. Nile Valley and Western Desert. Sixty-six samples from a total of 71 collected samples were analysed for SiO2, TiO2, Al203, Fe2O3, CaO, MgO, Na2O, K2O, P2O5, Sr, U and Pb by XRF and their mineral constituents were determined by the use of XRD techniques. In addition, the natural radioactivity of the phosphatic samples due to their uranium, thorium and potassium contents was measured by gamma-spectrometry. The uranium content in the phosphate rocks with P2O5 > 15% (average of 106.6 ppm) is higher than in rocks with P2O5 < 15% (average of 35.5 ppm). Uranium distribution is essentially controlled by the variations of P2O5 and CaO, whereas it is not related to changes in SiO2, TiO2, Al2O3, Fe2O3, MgO, Na2O and K2O concentrations.-Factor analysis and the Pearson correlation coefficient revealed that uranium belaves geochemically in different ways in the phosphatic sediments and phosphorites in the Red Sea, Nile Valley and Western Desert. In the Red Sea and Western Desert phosphorites, uranium occurs mainly in oxidized U6+ state where it seems to be fixed by the phosphate ion, forming secondary uranium phosphate minerals such as phosphuranylite. In the Nile Valley phosphorites, ionic substitution of Ca2+ by U4 is the main controlling factor in the concentration of uranium in phosphate rocks. Moreover, fixation of U6- by phosphate ion and adsorption of uranium on phosphate minerals play subordinate roles.     

Intercomparison of INAA and ICP-MS results for thorium determination in Pakistani diet

A pilot study on ingestion and organ content of trace elements of importance in radiological protection was to be carried out in Pakistan. Baseline analytical data on daily dietary intake of thorium was to be measured using Instrumental Neutron Activation Analysis (INAA) technique. To determine the accuracy and reliability of our technique, some samples were measured in Pakistan using INAA and in Japan using Inductively Coupled Plasma-Mass Spectrometry. For intercomparison of results overall mean Z-scores were calculated. The results showed validity of our technique. Mean value of 232Th concentration in Pakistani diet samples using INAA technique is 0.0062 +/- 0.0028 microg/g and with ICP-MS technique is 0.0069 +/- 0.0032 microg/g.     

Acidification in developing countries: ecosystem sensitivity and the critical load approach on a global scale

Acidification represents a growing threat to certain developing country ecosystems in tropical and subtropical climates. A methodology investigating the extent of acidification risks from sulfur emissions on a global scale is presented. Atmospheric transfer models have been used to calculate transfer and deposition of sulfur (using emissions for 1990 and a projection for 2050) and alkaline soil dust. A method to derive the relative sensitivity of terrestrial ecosystems is explained and preliminary critical load values are assigned. A range of values for critical loads and base cation deposition have been used to investigate uncertainty in maps depicting the excess of deposition above critical loads. These show an increasing risk of acidification in 2050 in extended regions of southern and eastern Asia, as well as parts of southern Africa, in comparison to 1990. Certain areas, especially in Asia, are shown at risk even when high values of critical load and base cation deposition are used.     

Effects of contamination level of dioxins and related chemicals on thyroid hormone and immune response systems in patients with "Yusho"

Effects of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) on thyroid hormone and immune response systems were examined in 16 Yusho patients at about 30 years after the outbreak of the Yusho accident. Their toxic equivalent (TEQ) levels in the blood were 27.8-1048.5 pg/g fat with the median level of 222.4 pg/g fat, which was about seven times higher than that of healthy Japanese people. Even at such high blood TEQ concentrations, they seemed not to affect the serum levels of thyroid hormones, thyroid stimulating hormone (TSH), immunoglobulins (A, G and M), autoantibodies (antinuclear antibody, rheumatoid and lupus erythematosus (LE) factors), and lymphocyte subsets in the blood. However, positive rates of rheumatoid factor were considered to increase in higher blood TEQ groups. This investigation was done using rather small number of Yusho patients, so further large-scale investigations are needed to get more conclusive findings concerning their effects on thyroid hormone and immune response systems.     

Electrochemical oxidation of bisphenol A. Application to the removal of bisphenol A using a carbon fiber electrode

Leachate samples with a high strength of ammonium-nitrogen (NH4+-N) were collected from a local landfill site in Hong Kong. Two experiments were carried out to study (1) the inhibition of microbial activity of activated sludge by NH4+-N and (2) the chemical precipitation of NH4+-N from leachate as a preliminary treatment prior to the activated sludge process. The experimental results demonstrated that the efficiency of COD removal decreased from 97.7% to 78.1%, and the dehydrogenase activity of activated sludge decreased from 9.29 to 4.93 microg TF/mg MLSS, respectively, when the NH4+-N concentration increased from 53 to 800 mg/l. The experiment also demonstrated that the NH4+-N in the leachate can be quickly precipitated as MgNH4PO4 x 6H2O after addition of MgCl2 x 6H2O + Na2HPO4 x 12H2O. The NH4+-N concentration was reduced from 5618 to 112 mg/l within 15 min when a molar ratio of Mg2+:NH+:PO4(3-) = 1:1:1 was used. The optimum pH to reach the minimum solubility of MgNH4PO4 x 6H2O was found to be in the range of 8.5-9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl2 x 6H2O + Na2HPO4 x 12H2O, which may affect microbial activity in the following biological treatment processes. Using two other combinations of chemicals [MgO + 85%H3PO4 and Ca(H2PO4)2 x H2O + MgSO4 x 7H2O] could minimise salinity generation after precipitation, while they were less efficient for NH4+-N removal.     

Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process

Simultaneous effect of inorganic anions, such as chloride and bicarbonate ions, on the scavenging of hydroxyl radicals (HO*) in the H2O2/UV process is the focus of this paper. The model compound of n-chlorobutane (BuCl) was used as the probe of HO*. By changing the pH conditions (2-9) and the concentrations of NaCl (0.25-2500 mM) and NaHCO3 (25 mM), the variation of HO* concentrations and the rate of H2O2 decomposition were compared. In general, the BuCl and H2O2 follow closely the first-order reaction within the first 10 and 40 min, respectively. In the presence of chloride alone at the pH range of 2-6, the HO* concentration in the reaction mixture increases with the increase of pH, and the HO* concentration at pH = 6 is 100 times of that at pH = 2. Including bicarbonate species in the solution, the peak HO* concentration was found at a certain pH, which shifts from 4, 5, to 5-7, as the molar ratios of chloride/bicarbonate species increase from 1 to 100. In addition, without bicarbonate species HO* concentration decreases significantly with increasing chloride concentration but remained rather unchanged beyond 1250 mM. In contrast, the HO* scavenging in the presence of bicarbonate species became relatively significant only when the chloride concentration reached beyond 250 mM. Throughout all experiments of different water quality conditions, the H2O2 decomposition rate remains rather unchanged.     

Comparison among air pollutants, meteorological conditions and some chemical parameters in the transplanted lichen Usnea amblyoclada

The response of Usnea amblyoclada (Müll. Arg.) Zahlbr. to real concentrations of atmospheric pollutants measured by two automatic monitoring stations, was studied in Córdoba City, Argentina. The influence of different weather conditions on the biomonitor's response was also assessed. The concentration of chlorophyll a, chlorophyll b, hydroperoxy-conjugated dienes, and malondialdehyde were quantified in lichen thalli collected from a clean area and in transplanted thalli after 1 month of exposure in an urban area, from April to October, 1996. The dry weight/fresh weight, chlorophyll b/chlorophyll a and phaeophytin a/chlorophyll a ratios were also calculated. Data sets were evaluated by two-way analysis of variance and correlation analysis. It was observed that hydroperoxy-conjugated dienes, malondialdehyde, chlorophylls, and pigment degradation increase during winter-time, when higher levels of suspended particles, non-methane hydrocarbons, hydrogen sulfide and ozone were also measured. These findings would be connected mainly with meteorological conditions, as most pollutants did not exceed prescribed threshold levels.     

Monitoring laboratory-scale bioventing using synchronous scan fluorescence spectroscopy: analysis of the vapor phase

Bioventing is an improved method of soil remediation that is being used with increasing frequency. In this paper, we refine techniques to measure the progress of petroleum hydrocarbon decomposition by monitoring vapor phase composition with synchronous scan fluorescence spectroscopy (SSFS). Analysis of the vapor phase has advantages compared to standard extraction techniques that require extensive sample handling and clean up. For comparison, hydrocarbon contamination in the soil was measured by analysis of Soxhlet extractions with gas chromatography-mass spectrometry (GC-MS). Comparison of the GC-MS and SSFS data showed that changes in hydrocarbon composition measured in the vapor phase provide an accurate measure of decomposition reactions taking place in the soil.     

Critical remarks on the use of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) for monitoring of airborne pollution

Duplicate samples of the two terrestrial moss species Hylocomium splendens and Pleurozium schreberi, which are widely used to monitor airborne heavy metal pollution, have been collected from eight catchments spread over a 1,500,000 km2 area in northern Europe. These were analysed for a total of 38 elements by inductively coupled plasma-mass spectrometry, inductively coupled plasma-atomic emission spectrometry and cold vapour-atomic absorption spectometry techniques. Results show that the moss species can be combined without interspecies calibration for regional mapping purposes. For the majority of elements the observed within-catchment variation is large--big composite samples over a large area should thus be collected when moss is to be used for monitoring purposes. For the majority of elements the input of dust governs moss chemistry. For a reliable 'contamination' signal over a sizeable area a major source is needed. Some elements show a dependence on climate/vegetation zone. In coastal areas the input of marine aerosols will alter the chemical signal obtained from moss samples.