Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Copper and zinc speciation in the solution of a soil-sludge mixture

Only a small fraction of the transition metals content in sludge-amended soils is soluble, and yet this fraction is a major contributor to the mobility and bioavailability of the metals. The chemical species of zinc (Zn) and copper (Cu) in the soluble fractions of soil-sludge mixtures were characterized with respect to their charge, molecular weight, and stoichiometry using ion exchange resin and gel chromatography procedures. The change in the metals' species with time after sludge application was followed for 100 d. Copper in the water extracts of the sludge-sand mixtures was found almost exclusively in low molecular weight (below 1000 Da) complexes. Higher molecular weight (around 2500 Da) dissolved organic carbon (DOC) was present in the extracts as well, but this DOC fraction exhibited little complexation. Copper was present in the extracts mainly as negatively charged species throughout the incubation period, and zinc tended to form zwitter ions. As incubation progressed, the relative content of positively charged Zn in solution increased. Complexation capacity of DOC in sludge water extract, extrapolated to infinite dilution, was 8.75 mM Ca g(-1) DOC. When the complexation capacity of the extract is near saturation, a mean Cu-DOC complex can be defined. It consists of 1.9 Cu atoms attached to DOC species containing 5.6 C atoms. Thus, the organic Cu complexes consist primarily of about two Cu ions attached to DOC species containing only five or six C atoms. Amino acids and small peptides or polycarboxylic acids, such as citric acid, thus may be important complexing agents of the metal.     

Vegetation stress detection through chlorophyll a + b estimation and fluorescence effects on hyperspectral imagery

Physical principles applied to remote sensing data are key to successfully quantifying vegetation physiological condition from the study of the light interaction with the canopy under observation. We used the fluorescence-reflectance-transmittance (FRT) and PROSPECT leaf models to simulate reflectance as a function of leaf biochemical and fluorescence variables. A series of laboratory measurements of spectral reflectance at leaf and canopy levels and a modeling study were conducted, demonstrating that effects of chlorophyll fluorescence (CF) can be detected by remote sensing. The coupled FRT and PROSPECT model enabled CF and chlorophyll a + b (Ca + b) content to be estimated by inversion. Laboratory measurements of leaf reflectance (r) and transmittance (t) from leaves with constant Ca + b allowed the study of CF effects on specific fluorescence-sensitive indices calculated in the Photosystem I (PS-I) and Photosystem II (PS-II) optical region, such as the curvature index [CUR; (R675.R690)/R2(683)]. Dark-adapted and steady-state fluorescence measurements, such as the ratio of variable to maximal fluorescence (Fv/Fm), steady state maximal fluorescence (F'm), steady state fluorescence (Ft), and the effective quantum yield (delta F/F'm) are accurately estimated by inverting the FRT-PROSPECT model. A double peak in the derivative reflectance (DR) was related to increased CF and Ca + b concentration. These results were consistent with imagery collected with a compact airborne spectrographic imager (CASI) sensor from sites of sugar maple (Acer saccharum Marshall) of high and low stress conditions, showing a double peak on canopy derivative reflectance in the red-edge spectral region. We developed a derivative chlorophyll index (DCI; calculated as D705/D722), a function of the combined effects of CF and Ca + b content, and used it to detect vegetation stress.     

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.     

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.