Bioaccumulation of heavy elements by Armadillidium vulgare (Crustacea,Isopoda) exposed to fallout of a municipal solid waste landfill

This paper reports the response of isopods exposed to fallout of a municipal solid waste landfill located in central Italy. Soil samples and specimens of Armadillidium vulgare were collected at different distances from the landfill and analyzed to determine the concentrations of heavy elements such as As, Cd, Co, Cr, Cu, Ni, Pb, Sb, V and Zn. The isopod analysis was performed on unpurged and purged specimens. Analytical data indicate that the soil contents of heavy elements were quite uniform and within the respective local geochemical background. Slight enrichments of Cu and Pb were found in some soils collected within the solid waste. Purged isopods showed an accumulation of As, Co, Cr, Ni, Sb and V whose body levels decreased as the distance from the landfill increased. Cd, Cu, Pb and Zn concentrations in purged specimens were rather uniform and no significant variation trend occurred. This result probably was due to the fact that the isopods are provided with physiological mechanisms of regulation for these heavy elements. Analytical data also indicate the ability of A. vulgare to adsorb differently the heavy elements according to the following order: As > Co > Ni > Pb > V. The contents of heavy elements in unpurged specimens were higher than in purged ones. This finding suggested that the defecation has marked effects on the tissue levels of heavy elements in isopods. This study indicates that the isopods provide useful information about environmental quality in areas characterized by low and discontinuous emission of heavy elements and their low accumulation in soil.     

Evidence of century-scale environmental changes: Trace element in tree-ring from Fuling Mausoleum Shenyang,China

In order to detect the response of trees to environmental pollution in Shenyang during the last century, tree rings of two 100+ year old Chinese pine (Pinus tabulaeformis Carr.) were analyzed for nine trace element concentrations (K, Ca, Mg, Mn, Cu, Zn, Al, Pb and Cd) and compared to local environmental change. The concentrations of Cu, Zn and Al had significant (p < 0.01) increasing trends after 1940s and correlated significantly (p < 0.01), with increasing production of nonferrous metal from local industrial processing. Concentrations of nutrient element (K, Ca and Mg) showed significant (p < 0.01) increasing trend from heartwood to sapwood with declines in the last three decades. Significant correlation between climatic factors and element concentration in tree rings were also found, in which the temperature (November to May) and relative humidity in April and May showed significant positive correlation with Ca, Zn and Cu (p < 0.05) as well as Al (p < 0.01) concentrations in tree rings. April rainfall showed significant positive correlation with K and Zn (p < 0.05) as well as Al (p < 0.01) concentration in tree rings. The results suggest that tree rings from Chinese pine in Shenyang are sensitive to environmental change and have the potential to be used as a biomonitor for the environmental pollution. The results also demonstrate the feasibility of applying dendrochemical techniques to areas with limited samples.     

Variations of chemical element composition of bee and beekeeping products in different taxons of the biosphere

Geographical variations in element composition of bee products are poorly investigated though a lot of attempts are made to utilize the data in ecological monitoring. So the comparison of chemical element composition of bee and beekeeping products in different taxons of the biosphere may become valuable to test the efficiency of such approach. For this purpose content of 25 elements in bee body, bee bread, propolis and honey from Ribnitsa district of Moldavia (unpolluted area, control), Henty province of Mongolia (selenium deficient area) and Voskresensk district of Moscow region (mineral fertilizers production) were determined by means of the ICP-MS. Among 3 investigated regions Mongolia was characterized by the lowest Se levels and the highest accumulation of Al, Ca, Cd, Cu, Co, K, Mn, Mg, Na, Ni, P, Zn and V in bee bodies. The highest levels of Pb, Cr, Fe, Si, Sr and B, Se, Li, Sn were typical for Voskresensk and Moldavia bees accordingly. The highest correlation coefficients were registered between element concentrations in bee body and bee bread (r = +0.97–0.99, P < 0.0001), less significant – in bee body and propolis (r = +0.5–0.7; P < 0.001) and no correlation was demonstrated between element composition of bee body and honey. Propolis was characterized by significantly higher capacity to accumulate Pb, Cr, Sn and Al than bee body. Compared to bee body honey accumulated the lowest level of Mn and the highest of Si in Se-deficient Mongolia but the opposite phenomenon was demonstrated in Moldavia with moderately increased Se content in the environment. The results suppose that the most promising object for ecological monitoring is bee body. Element composition of propolis seems to reflect prolonged accumulation of elements, especially Pb, Al, Sn and Cr, by plant resin rather than dynamic temporal elements loading. Accumulation levels of elements in bee bread may be used on a par with bee body mineral content only in cases with equal honey content in bee bread. Honey utilization in monitoring of geochemical elements loading should be used with caution due to peculiarities of pollen/nectar elements distribution.     

Isostructural M(RL)2(hfac)2 complexes with RL = 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine

5-(4-(N-tert-Butyl-N-aminoxylphenyl))pyrimidine (RL, 4PPN) forms crystallographically isostructural and isomorphic pseudo-octahedral M(RL)₂(hfac)₂ complexes with M(hfac)₂, M = Zn, Cu, Ni, Co, and Mn. Multiple close contacts occur between sites of significant spin density of the organic radical units. Magnetic behavior of the Zn, Cu, Ni, Co complexes appears to involve multiple exchange pathways, with multiple close crystallographic contacts between sites that EPR (of 4PPN) indicates to have observable spin density. Powder EPR spectra at room temperature and low temperature are reported for each complex. Near room temperature, the magnetic moments of the complexes are roughly equal to those expected by a sum of non-interacting moments (two radicals plus ion). As temperature decreases, AFM exchange interactions become evident in all of the complexes. The closest fits to the magnetic data were found for a 1-D Heisenberg AFM chain model in the Zn(II) complex (J/k = (?)7 K), and for three-spin RL—M—RL exchange in the other complexes (J/k = (?)26 K, (?)3 K, (?)6 K, for Cu(II), Ni(II), and Co(II) complexes, respectively).     

Effect of CoCl2 treatment on major and trace elements metabolism and protein concentration in mice

Cobalt (Co) is a transition metal and an essential trace element, required for vitamin B₁₂ biosynthesis, enzyme activation and other biological processes, but toxic in high concentrations. There is lack of data for the effect of long-term Co(II) treatment on the concentrations of other trace elements. We estimate the influence of cobalt chloride (CoCl₂) on the relative content of different metals in mouse plasma using two-jet arc plasmatron atomic emission and on the total protein content. On average, the content of different elements in the plasma of 2-month-old balb/c mice (control group) decreased in the order: Ca > Mg > Si > Fe > Zn > Cu ≥ Al ≥ B. The treatment of mice for 60 days with CoCl₂ (daily dose 125 mg/kg) did not appreciably change the relative content of Ca, Cu, and Zn, while a 2.4-fold statistically significant decrease in the content of B and significant increase in the content of Mg (1.4-fold), Al and Fe (2.0-fold) and Si (3.2-fold) was found. A detectable amount of Mo was observed only for two control mice, while the plasma of 9 out of 16 mice of the treated group contained this metal. The administration of Co made its concentration detectable in the plasma of all mice of the treated group, but the relative content varied significantly. The treatment led to a 2.2-fold decrease in the concentration of the total plasma protein. Chronic exposure to CoCl₂ affects homeostasis as well as the concentrations and metabolism of other essential elements, probably due to competition of Co ions for similar binding sites within cells, altered signal transduction and protein biosynthesis. Long-term treatment also leads to significant weight changes and reduces the total protein concentration.The data may be useful for an understanding of Co toxicity, its effect on the concentration of other metal ions and different physiological processes.     

Potential of Typha angustifolia for phytoremediation of heavy metals from aqueous solution of phenol and melanoidin

Typha angustifolia was evaluated for various heavy metals (Cu, Pb, Ni, Fe, Mn, and Zn) bioremediation potential from aqueous solution containing variable concentrations of phenol (100–800 mg l^?1) and melanoidin (2500–8500 Co–Pt) at 20, 40, and 60 days. The concentration of phenol (200–400 mg l^?1) along with melanoidin 2500 Co–Pt showed optimum for phytoremediation of tested heavy metals, while, higher concentrations of melanoidin (5600–8500 Co–Pt) showed toxic effect on T. angustifolia along with phenol. Phenol and melanoidin showed adverse effect on T. angustifolia of up to 20 days incubation, but this leads to induction of peroxidase and ascorbic acid activity to cope with adverse conditions. Subsequently, as pollutants were decreased along with plant growth, peroxidase and ascorbic acid also declined. However, with reduction of peroxidase, catalase level was increased. The Cu, Zn, and Ni were accumulated at maximum in all tested conditions. The TEM observations of T. angustifolia showed clotted deposition of metals and shrinkage of cell in root, breakdown of spongy and palisade parenchyma of leaves at higher concentration of phenol (100 mg l^?1) and melanoidin (5500 Co–Pt). Thus, this study concluded that T. angustifolia could be a potential phytoremediator for heavy metals from metal, melanoidin, and phenol containing industrial wastewater at optimized condition.     

Synthesis,structures and magnetic properties of pentanuclear and trinuclear heterometallic complexes with bended and linear cyano-bridges (tren = tris(2-aminoethyl)amine)

The reaction of [Cu(tren)(OH₂)](ClO₄)₂ with KCN gave a mononuclear complex [Cu(tren)(CN)](ClO₄) (1) (tren = tris(2-aminoethyl)amine). Using 1 as a building block, one pentanuclear compound, [{Cu(tren)(NC)}₄Ni](ClO₄)₆ (2) and two trinuclear complexes, [{Cu(tren)NC}₂Co(tren)](ClO₄)₅ · 2H₂O (3), [{Cu(tren)CN}₂NiL](ClO₄)₄ (4) (L = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) were prepared and characterized by single crystal X-ray analysis. In 1, Cu(II) atom adopts a distorted trigonal bipyramidal (TBP) geometry. In 2, the Ni(II) atom occupies the center of the pentanuclear compound with a square-planar coordination geometry. In 3, the six-coordinated Co(III) atom presents a distorted octahedral geometry with four nitrogen atoms from tren and two carbon atoms of bridged cyano groups in cis-positions. In 4, the nickel atom is located in an inversion center and coordinated with two [(tren)CuCN]⁺ moieties through cyano-bridging ligands. Magnetic susceptibility measurements of 2–4 show that the magnetic interactions between the heterometallic ions are antiferromagnetical coupling through the cyano bridges with g = 2.25, J = −0.142 cm⁻¹ and J′ = −0.167 cm⁻¹ for 2, g = 2.06, J = −0.094 cm⁻¹ for 3, and g = 2.20, J = −33.133 cm⁻¹ for 4. The correlations between the structures and the J values are discussed.     

Bioaccumulation and translocation of heavy metals by Plantago major L. grown in contaminated soils under the effect of traffic pollution

The present study was performed at a heavy-traffic affected soil to examine the efficacy of bioaccumulation and translocation potentials of heavy metals by the naturally growing weed Plantago major. Heavy metals were analyzed in soil as well as in plant below- and above-ground parts along different distances from a heavy-traffic highway. All the investigated soil heavy metals, except Cd, varied significantly, while pH and E.C had no significant difference, with increasing distance from the highway. Likewise, there was a significant decrease of heavy metals in plant below- and aboveground parts. In addition, no significant difference between most soil and root heavy metals at 20 and 100 m as well as those at 500 and 750 m distance from the highway. The bioaccumulation factor (BF) of all heavy metals, except Cd and Sr, were less than unity at most distances. However, Cd showed relative BF decline with the distance in contrast to Sr, which increases as distance from the highway increases. On the other hand, the translocation factors (TF) of Cd, Co, Cu, Pb and Zn were higher at the distances far from the highway, while that of Fe, Cr and Sr were higher near the highway. Furthermore, the enrichment factor (EF) showed small variations, among the investigated heavy metals, with varying distances from the pollution source. It was found that soil Fe, Al, Cr, Ni, Sr, V and Zn had significant positive correlation with all investigated heavy metals in P. major roots. The higher TFs of Cd, Fe and Pb in P. major shoots makes it suitable for phytoextraction from soil, while the lower ratios of Al, Mn, V, Co, Ni, Cr, Zn, Cu and Sr make it suitable for their phytostabilization. Therefore, this plant can be used as a bioindicator and biomonitor for traffic related heavy metals.     

Relationship of lead and essential elements in whole blood from school-age children in Nanning,China

ObjectivesThe aim of this study was to investigate blood lead level and its relationship to essential elements (zinc, copper, iron, calcium and magnesium) in school-age children from Nanning, China.MethodsA total of 2457 children aged from 6 to 14 years were enrolled in Nanning, China. The levels of lead (Pb), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca) and magnesium (Mg) were determined by an atomic absorption spectrometer.ResultsThe mean blood lead level (BLL) was 57.21 ± 35.00 μg/L. 188 (7.65%) asymptomatic children had toxic lead level higher than 100 μg/L. The school-age boys had similar lead level among different age groups, while the elder girls had less BLL. The blood Zn and Fe were found to be increased in the boys with elevated BLL, but similar trends were not observed in the girls. Positive correlations between Pb and Fe or Mg (r = 0.112, 0.062, respectively, p < 0.01) and a negative correlation between Pb and Ca (r = −0.047, p < 0.05) were further established in the studied children.ConclusionsLead exposure in school-age children was still prevalent in Nanning. The boys and girls differed in blood levels of lead and other metallic elements. Lead exposure may induce metabolic disorder of other metallic elements in body.     

Monitoring of trace metals in tissues of Wallago attu (lanchi) from the Indus River as an indicator of environmental pollution

We aimed to assess the bioaccumulation of selected four trace metals (Cd, Ni, Zn and Co) in four tissues (muscles, skin, gills and liver) of a freshwater fish Wallago attu (lanchi) from three different sites (upstream, middle stream and downstream) of the Indus River in Mianwali district of Pakistan. Heavy metal contents in water samples and from different selected tissues of fish were examined by using flame atomic absorption spectrometry. The data were statistically compared to study the effects of the site and fish organs and their interaction on the bioaccumulation pattern of these metals at P < 0.05. In W. attu the level of cadmium ranged from 0.004 to 0.24; nickel 0.003–0.708; cobalt 0.002–0.768 and zinc 47.4–1147.5 μg/g wet weight. The magnitude of metal bioaccumulation in different organs of fish species had the following order gills > liver > skin > muscle. The order of bioaccumulation of these metals was Ni < Zn < Co < Cd. Heavy metal concentrations were increased during the dry season as compared to the wet season. The results of this study indicate that freshwater fish produced and marketed in Mianwali have concentrations below the standards of FEPA/WHO for these toxic metals.     

Calorimetric and spectroscopic investigations of the binding of metallated porphyrins to G-quadruplex DNA

BackgroundThe human telomere contains tandem repeat of (TTAGG) capable of forming a higher order DNA structure known as G-quadruplex. Porphyrin molecules such as TMPyP4 bind and stabilize G-quadruplex structure.MethodsIsothermal titration calorimetry (ITC), circular dichroism (CD), and mass spectroscopy (ESI/MS), were used to investigate the interactions between TMPyP4 and the Co(III), Ni(II), Cu(II), and Zn(II) complexes of TMPyP4 (e.g. Co(III)-TMPyP4) and a model human telomere G-quadruplex (hTel22) at or near physiologic ionic strength ([Na⁺] or [K⁺] ≈ 0.15 M).ResultsThe apo-TMPyP4, Ni(II)-TMPyP4, and Cu(II)-TMPyP4 all formed complexes having a saturation stoichiometry of 4:1, moles of ligand per mole of DNA. Binding of apo-TMPyP4, Ni(II)-TMPyP4, and Cu(II)-TMPyP4 is described by a “four-independent-sites model”. The two highest-affinity sites exhibit a K in the range of 10⁸ to 10¹⁰ M^− 1 with the two lower-affinity sites exhibiting a K in the range of 10⁴ to 10⁵ M^− 1. Binding of Co(III)-TMPyP4, and Zn(II)-TMPyP4, is best described by a “two-independent-sites model” in which only the end-stacking binding mode is observed with a K in the range of 10⁴ to 10⁵ M^− 1.ConclusionsIn the case of apo-TMPyP4, Ni(II)-TMPyP4, and Cu(II)-TMPyP4, the thermodynamic signatures for the two binding modes are consistent with an “end stacking” mechanism for the higher affinity binding mode and an “intercalation” mechanism for the lower affinity binding mode. In the case of Co(III)-TMPyP4 and Zn(II)-TMPyP4, both the lower affinity for the “end-stacking” mode and the loss of the intercalative mode for forming the 2:1 complexes with hTel22 are attributed to the preferred metal coordination geometry and the presence of axial ligands.General significanceThe preferred coordination geometry around the metal center strongly influences the energetics of the interactions between the metallated-TMPyP4 and the model human telomeric G-quadruplex. This article is part of a Special Issue entitled Microcalorimetry in the BioSciences — Principles and Applications, edited by Fadi Bou-Abdallah.     

Apolipoprotein A-I inhibits chemotaxis,adhesion, activation of THP-1 cells and improves the plasma HDL inflammatory index

The anti-inflammatory effects of high density lipoprotein (HDL) are well described, however, such effects of Apolipoprotein A-I (ApoA-I) are less studied. Building on our previous study, we further explored the mechanism of anti-inflammatory effects of ApoA-I, and focused especially on the interaction between monocyte and endothelial cells and plasma HDL inflammatory index in LPS-challenged rabbits. Our results show that ApoA-I significantly decreased LPS-induced MCP-1 release from THP-1 cells and ox-LDL-induced THP-1 migration ratio (P < 0.01, respectively). ApoA-I significantly decreased sL-selectin, sICAM-1 and sVCAM-1 release (P < 0.01, P < 0.01, P < 0.05, respectively) from LPS-stimulated THP-1 cells. Furthermore, ApoA-I significantly inhibited LPS-induced CD11b and VCAM-1 expression on THP-1 cells (P < 0.01, P < 0.05, respectively). ApoA-I diminished LPS-induced mCD14 expression (P < 0.01) and NFκB nuclear translocation in THP-1 cells. After single dose treatment of ApoA-I, the value of plasma HDL inflammatory index in LPS-challenged rabbits was improved significantly (P < 0.05). These results suggest that ApoA-I can inhibit chemotaxis, adhesion and activation of human monocytes and improve plasma HDL inflammatory index with presenting beneficial anti-inflammatory effects.     

Trace amounts of nickel in belowground rhizomes of Vaccinium myrtillus L. decrease anthocyanin concentrations in aerial shoots without water stress

Nickel (Ni) may impair plant water balance through detrimental effects on the belowground level. Bilberry (Vaccinium myrtillus L.) plants were grown in a mesic heath forest-type soil and subjected to Ni sulphate (NiSO₄·6H₂O) concentrations of 0, 10, 50, 100 and 500 mg m⁻² during an entire growing season in northern Finland (65°N). Biomass of belowground rhizomes, and tissue water content (TWC) and anthocyanin concentrations of aerial shoots were determined from mature plants in order to study rhizospheric Ni stress, and its possible long-distance effects on aerial shoots. As the major proportion of biomass of bilberry is invested in belowground parts, it was hypothesised that Ni-induced rhizospheric disturbance causes water stress in aerial shoots and increases their anthocyanin concentrations for osmotic regulation. Uptake of Ni from the soil to the rhizome and aerial shoots was measured with X-ray fluorescence spectrometry. Ni concentrations in the soil and rhizome exhibited a dose–response relationship, but the concentrations in the rhizome were about 10-fold lower (<3 mg Ni kg⁻¹) than those in the soil (<30 mg Ni kg⁻¹). Translocation of Ni from the rhizome to aerial shoots did not occur, as Ni concentrations in shoots remained at 1 mg Ni kg⁻¹. Although Ni concentrations in the rhizome were below the threshold values of Ni toxicity (i.e. 10–50 mg Ni kg⁻¹), Ni decreased the rhizome biomass. Anthocyanins decreased in aerial shoots along with the Ni accumulation in the rhizome, while TWC was unaffected. The result suggests that anthocyanins are not involved in osmotic regulation under Ni stress, since anthocyanins in aerial shoots responded to the Ni concentrations in the rhizome despite the lack of water stress.     

Sensitivity of ruminal bacteria isolates of sheep,cattle and buffalo to some heavy metals

This study was conducted to investigate the toxicity of 12 heavy metals (i.e., HM), namely Hg, Cd, Co, Ni, Cr, Cu, Ag, Mo, Zn, Pb, Li and Na on bacterial isolates from the rumen of sheep, cattle and buffaloes. Rumen samples were collected immediately after slaughter during the dry season. Ruminal bacterial isolates, 59, were obtained from two sheep, five cows and nine buffaloes. Sensitivity of ruminal bacterial isolates to each HM was determined by the clearance zone (CZ) using the Kirby-Bauer disc diffusion susceptibility test. Bacterial populations isolated from the rumens of sheep and buffalo had a lower resistance (P<0.001) to HM toxicity than did cattle. Regardless of ruminant species, bacterial isolates revealed a higher tolerance (P<0.001) to Li and Na, whereas Hg and Cd were the most toxic HM for all isolates. We conclude that inhibition of these HM to the isolated microbial population of sheep, cattle and buffalo is ranked: Hg (most toxic) > Cd > Co ～ Ag ～ Cu ～ Cr ～ Ni > Mo ～ Zn ～ Pb > Li ～ Na. Further research is required to explain the mechanism of toxicity of these HM, and also to explore the variation among ruminant species.     

Effect of dietary cobalt supplementation on plasma and rumen metabolites in Mehraban lambs

Two experiments were conducted to study the effects of different levels of dietary cobalt on performance, plasma and rumen metabolites and nutrient digestibility in Mehraban male lambs. Experiment 1: 28, 8–9-month-old lambs were randomly divided into four groups. Animals were fed a basal diet containing 0.088 mg Co/kg DM and were supplied with 0 (control), 0.25, 0.50, or 1.00 mg Co/kg DM as reagent grade CoSO₄·7H₂O. The experiment lasted for 70 days. Experiment 2: four lambs from each group in Experiment 1 were randomly allocated to the individual metabolic crates to measure the effects of dietary Co on nutrient digestibility. Final body weight, average daily gain and gain efficiency were higher (p < 0.05) in the group supplemented with 0.50 mg Co/kg DM compared to other groups. Plasma glucose and vitamin B₁₂ concentrations increased (p < 0.05) at all levels of Co supplementation on day 68 of the experiment and for vitamin B₁₂ were higher (p < 0.05) at 0.50 and 1.00 mg Co/kg DM compared to 0.25 mg Co/kg DM. There was no significant difference among treatments for TVFA and ruminal fluid pH. Digestibility of dry matter, organic matter, crude protein and neutral detergent fiber increased (p < 0.05) by Co supplementation, but did not differ among Co supplied treatments. The obtained results showed that lambs fed the control diet containing 0.088 mg Co/kg DM had a reduced appetite and gained less than the supplemented animals, suggesting that the level of 0.088 mg Co/kg DM was inadequate for normal growth of Mehraban male lambs, and a total level of 0.58 mg Co/kg DM might be optimum level for enhancing performance.     

Copper/zinc and copper/selenium ratios,and oxidative stress as biochemical markers in recurrent aphthous stomatitis

ProjectRecurrent aphthous stomatitis (RAS) is a common oral mucosal disorder characterized by recurrent, painful oral aphthae, and oxidative stress presumably contributes to its pathogenesis. The aim of this study is to scrutinize the relationship between oxidative stress and serum trace elements (copper, Cu; zinc, Zn; selenium, Se), and to evaluate the ratios of Cu/Zn and Cu/Se in this disorder.ProcedurePatients with RAS (n = 33) and age- and sex-matched healthy control subjects (n = 30) were enrolled in this study. Malondialdehyde (MDA) concentrations in plasma and the activities of superoxide dismutase (SOD1; CuZnSOD), glutathione peroxidase (GPx) and catalase (CAT) in erythrocyte were determined as spectrophotometric. Also, the levels of Se, Zn and Cu in serum were determined on flame and furnace atomic absorption spectrophotometer using Zeeman background correction.Results and conclusionsOxidative stress was confirmed by the significant elevation in plasma MDA, and by the significant decrease in CAT, SOD1, and GPx (p < 0.05). When compared to controls, Zn and Se levels were significantly lower in patients, whereas Cu levels was higher in RAS patients than those in controls (p < 0.05). In addition, the correlation results of this study were firstly shown that there were significant and positive correlations between Se–CAT, Se–GPx, and Cu–MDA parameters, but negative correlations between Se–Cu, Se–MDA, Cu–CAT, Cu–SOD1 and Cu–GPx parameters in RAS patients. Furthermore, the ratios of Cu/Zn and Cu/Se were significantly higher in the patients than the control subjects (p < 0.05). Our results indicated that lipid peroxidation associated with the imbalance of the trace elements seems to play a crucial role in the pathogenesis of RAS. Furthermore, the serum Cu/Zn and Cu/Se ratios may be used as biochemical markers in these patients.     

Diverse magnetic and electrical properties of molecular solids containing the thiazyl radical BDTA

We have examined the crystal structures and the electrical and magnetic properties of the molecular compounds of a thiazyl radical, 1,3,2-benzodithiazolyl (abbreviated as BDTA). BDTA was found to be a useful building block for molecular conductors and magnets because it can operate as a counter cation, a donor or a ligand, depending on its charge. (i) A charge-transfer complex, [BDTA][TCNQ], crystallizes into a uniform segregated stacking structure with a short contact between the donor and acceptor columns. In spite of the partial charge transfer between the two components, this complex exhibits semiconductive behaviour, probably due to a large electron correlation on BDTA. (ii) The crystal structure of [BDTA][Ni(mnt)₂] (mnt = maleonitriledithiolate) consists of alternating stacking columns of S = 0 [BDTA]⁺ and S = 1/2 [Ni(mnt)₂]^?, in which a ferromagnetic coupling operates between the [Ni(mnt)₂]^? anions through the [BDTA] ⁺ cation. (iii) [BDTA]₂[Cu(mnt)₂] consists of an alternating stack of a head-to-head [BDTA]⁺ dimer and a planar [Cu(mnt)₂]^2? dianion. Short intermolecular S?S contacts between the stacks give rise to an ideal 1D Heisenberg antiferromagnetic chain of [Cu(mnt)₂]^2? with a coupling constant of J/k_B = 16–17 K. (iv) The crystal structure of [BDTA]₂[Co(mnt)₂] is similar to that of [BDTA]₂[Cu(mnt)₂] at 253 K, but this salt undergoes a phase transition at 190 K, below which a partial electron transfer occurs from [Co(mnt)₂]^2? to one of the [BDTA]⁺ cations along with formation of a coordination bond. (v) [BDTA][Ni(dmit)₂]₂ (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) exhibits room-temperature conductivity of 0.1 S cm^?1 and semiconductive behaviour over the range 80–200 K, which can be interpreted in terms of multi-conducting bands.     

Effect of the presence of lead on the biosorption of copper,cadmium and nickel by anaerobic biomass

Heavy metals are toxic pollutants released into the environment as a result of industrial, mining and agricultural activities. The biosorption of Pb, Cu, Cd, and Ni from single and binary metal systems were studied in equilibrium systems and in a flow-through column packed with a calcium-saturated anaerobic sludge biosorbent, respectively. The single-metal sorption uptake capacity of the biomass for Pb was slightly inhibited by the presence of Cu and Cd cations (by 6%) and by the presence of nickel (by 11%). The affinity order of anaerobic biomass for the four metals was established as: Pb > Cu > Ni > Cd. Factors such as hydration effects, hydrolysis effects and covalent binding of the metal ions may contribute to this result. By studying the breakthrough curves obtained from a fixed bed column fed with an equimolar mixture of Pb, Cd, Cu, and Ni, it was determined that lead was the last metal to break through the column at the 150 bed volume mark compared to 4, 15, 30 bed volume marks for Ni, Cd, and Cu, respectively.     

Associations of soil iron with citrus tree decline and variability of sand,soil water,pH, magnesium and Diaprepes abbreviatus root weevil: Two-site study

The hypothesis of associations of environmental soil heterogeneity with citrus tree decline and Diaprepes abbreviatus (L.) root weevil variability was tested in two flatwoods fields of ‘Hamlin’ orange trees (Citrus sinensis (L.) Osb.). Studies were conducted on a loamy, poorly drained Mollisol in Osceola County, central Florida in 2002, and on a sandy, poorly drained Spodosol in DeSoto County, south-west Florida during 2001–2003. Adult weevils were monitored using 50 Tedders traps arranged in a 34 m × 25 m grid at the Osceola site, and using 100 identical traps in a 30 m × 15 m grid at the DeSoto site. Soil water content (SWC), texture, pH, Ca, Mg, Fe, Cu and other nutrients were measured at each trap. Soil was strongly acidic (pH 4.9 ± 0.4) at the Osceola site but near neutral (pH 6.6 ± 0.4) at the DeSoto site. The Mehlich-I extractable soil Mg and Ca were correlated to soil pH and SWC in both soils, and extractable Fe was related to pH, SWC and Mg in the Spodosol (0.30 < R² < 0.65, P < 0.01). The weevil density was high in areas low in soil Mg and Ca in the acidic Mollisol, but high in areas with high soil pH, and Mg and low sand content in the near neutral Spodosol (P < 0.05). Tree decline was associated with soil Fe concentrations >40 mg kg⁻¹ in the Mollisol (P < 0.01). Weevil density was low at a soil pH between 5.7 and 6.2. The range of spatial dependence of weevil population, soil pH, SWC, Fe, Mg and sand varied between 60 and 100 m in the Mollisol and the Spodosol. Soil-weevil-tree simple and multivariate linear models were established to put into practices for predicting and controlling the weevil population and tree decline in the future. Differences in site characteristics suggested the need for site-specific weevil and citrus tree management.     

The concentrations of major and trace elements in rat kidney: Aging effects and mutual relationships

The concentrations of 26 major to trace elements in rat kidneys aging from 5 to 113 weeks old were determined. The rats investigated were the same rats used previously reported to have 29 elements in bones (femurs). The samples were decomposed by high purity nitric acid and hydrogen peroxide. Eight elements (Na, Mg, Si, P, K, Ca, Fe and Zn) were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES) and 18 elements (Mn, Co, Ni, Cu, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Cs, Ba, Tl, Pb, Bi and U) were determined using inductively coupled plasma mass spectrometry (ICP-MS). The aging effects on the concentrations of these elements and mutual elemental relationships were investigated. Analysis of variance (ANOVA) for age variations indicated that the concentrations of P, K, Mn and Mo were almost constant across the age of rats (p > 0.3). The concentration of many elements such as Na, Mg, Ca, Fe, Co, Cu, Zn, As, Se, Cd, Sn, Sb, Tl, Pb and Bi, showed significant increasing trends (p < 0.01) with different patterns. Rubidium, Cs, Pb and Bi showed significant age variations but not monotonic trends. Silicon, Ni, Sr, Ba and U showed large concentration scatterings without any significant trends (p > 0.01). The metabolism of these elements may not be well established in the kidney. Many toxic elements such as As, Cd, Sn, Pb and Bi showed a narrow concentration range among age-matched rats. The kidney may have established metabolic mechanisms to confine or accumulate these toxic elements even though their concentrations are very low (e.g., 10 ng g^?1 of Cd). These elements also closely coupled with Fe. A cluster analysis was performed using an elemental correlation matrix and indicated that these elements, including Fe, formed a cluster. However, another cluster analysis using “an aging effect eliminated” elemental correlation showed different clustering in which the Fe, Cd cluster disappeared.