Activation of H2O2 by Amberlyst-15 resin supported with copper(II)-complexes towards oxidation of crystal violet

Copper(II) amine complexes supported on Amberlyst-15 cation resin were prepared and characterized by SEM, EDX and FTIR measurements. The kinetics of the heterogeneous oxidation of an organic dye, crystal violet, with H2O2 catalyzed by the supported catalysts was investigated in aqueous solution. The rate of reaction increases with increasing stability of the copper(II) amine complexes. The oxidation rate attained a first-order in the catalyst and the dye only at lower concentrations and second order in H2O2. A very fast formation of a peroxo-dye intermediate resulting from the interaction of H2O2 with the dye even in the presence of the catalyst was observed.     

Loading estimates of lead, copper, cadmium, and zinc in urban runoff from specific sources

Urban stormwater runoff is being recognized as a substantial source of pollutants to receiving waters. A number of investigators have found significant levels of metals in runoff from urban areas, especially in highway runoff. As an initiatory study, this work estimates lead, copper, cadmium, and zinc loadings from various sources in a developed area utilizing information available in the literature, in conjunction with controlled experimental and sampling investigations. Specific sources examined include building siding and roofs; automobile brakes, tires, and oil leakage; and wet and dry atmospheric deposition. Important sources identified are building siding for all four metals, vehicle brake emissions for copper and tire wear for zinc. Atmospheric deposition is an important source for cadmium, copper, and lead. Loadings and source distributions depend on building and automobile density assumptions and the type of materials present in the area examined. Identified important sources are targeted for future comprehensive mechanistic studies. Improved information on the metal release and distributions from the specific sources, along with detailed characterization of watershed areas will allow refinements in the predictions.     

Biochemical changes in needles of Pinus radiata D. Don trees in relationship to long-term ozone exposure indices

Ambient concentrations of ozone in Europe are high enough to cause negative effects on vegetation. Therefore, many efforts have been made to determine exposure indices and critical levels for protection of vegetation. In this context, the choice of a suitable attribute to determine the pollutant effect is of paramount importance. Until now, much of the work has been done with attributes such as biomass or growth. In the present work correlation factors have been established between biochemical parameters (peroxidase activity, ascorbate and sulfhydryl contents) of Pinus radiata trees and exposure indices of ozone. Our results show that peroxidase cannot be used as an indicator of effects of long-term exposure to ozone but still remains as an excellent indicator of short-term ozone fluctuations in the field. Ascorbate may act as an intermediate indicator responding to both short fluctuations and long-term exposures to ozone. Finally, sulfhydryl may be used as a long-term indicator in relation to the AOT (average over threshold) exposure index. Our results also point to the fact that Pinus radiata may be affected by ozone at AOT values lower than 10 ppm.h as already observed with other tree species.     

Patterns of metals and arsenic poisoning in Vibrio fischeri bacteria

The Microtox bioassay was used to establish dose-response curves for some toxic elements in aqueous solutions, namely, Zn(II), Pb(II), Cu(II), Hg(II), Ag(I), Co(II), Cd(II), Cr(VI), As(V) and As(III). Experiments were carried out at either pH 6.0 or pH 7.0 to indicate that pH may influence the measured toxicity of some elements due to pH-related changes of their chemical speciation. EC20 values, which represent a measurable threshold of toxicity, were determined for each element and were found to rank as Pb(II)>Ag(I)>Hg(II) approximately Cu(II)>Zn(II)>As(V)>Cd(II) approximately Co(II)>As(III)>Cr(VI). These values were compared to the limit concentrations allowed in industrial wastewater according to the official regulations in Catalonia (Spain). It appears that the Microtox test is sensitive enough for detecting some of the tested elements with respect to official regulations of Catalonia (Spain) dealing with pollution control, with the exception of cadmium, mercury, arsenate, arsenite and chromate.     

Sorption of pentachlorophenol on pine bark

The minimization of pentachlorophenol (PCP) transport in the environment driven by industrial wastewater discharges can be accomplished by sorption in natural, available and low cost by-products like pine bark. Taking into account that PCP is a chemical which behaviour is highly dominated by the surrounding features, this work intended to evaluate the sorption kinetics and equilibrium parameters according to the pH and temperature as well as the pine bark particle size. The PCP uptake by pine bark showed to be faster in the initial phase followed by a slower process, being 24 h the suitably time to reach the sorption equilibrium in the range of pH studied. The neutral PCP species showed to have higher binding capacity to pine bark than the anionic PCP, which was reflected in a decrease in the distribution coefficient (Kd) of the linear sorption isotherm with the increase of solution pH from 2 to 7. On the other hand, between 10 degrees C and 35 degrees C, the temperature does not seem to play a significant role in the PCP sorption by pine bark, while the sorbent size is a key parameter to enhance the overall process.     

Effect of isoflavones on reproductive performance, testosterone levels, lipid peroxidation, and seminal plasma biochemistry of male rabbits

The objective of this study was to determine the effect of either 2.5 mg/kg Body Weight or 5 mg/kg Body Weight (BW) doses of isoflavones on semen quality, testosterone levels, lipid peroxidation and semen biochemistry of male New Zealand White rabbits. Animals were given both 2.5 mg/kg BW and 5 mg/kg BW doses of isoflavones. The tested doses were given to rabbits orally every other day for 13 weeks. Treatment with isoflavones caused an increase (p < 0.05) in libido (by decreasing the reaction time), sperm concentration, sperm motility (%), total motile sperm per ejaculate (TMS), packed sperm volume (PSV), total functional sperm fraction (TFSF), total sperm output, initial fructose concentration and normal sperm, while dead sperm was reduced compared to control animals. On the other hand, ejaculate volume, initial hydrogen ion concentration (pH) and plasma testosterone levels did not change in treated animals with both doses of isoflavones as compared to control. Concentrations of thiobarbituric acid-reactive substances (TBARS), total lipids, and low density lipoprotein were significantly (p < 0.05) reduced in seminal plasma of rabbits treated with either 2.5 mg/kg BW or 5 mg/kg BW doses of isoflavones. While, the activities of glutathione S-transferase (GST), lactate dehydrogenase (LDH), aspartate aminotransferase (AST), alanine aminotransferase (ALT), acid phosphatase (AcP), and alkaline phosphatase (AlP) were significantly (p < 0.05) increased in seminal plasma of treated animals. Also, total cholesterol, percentage cholesterol (out of total lipids), and high density lipoprotein were significantly (p < 0.05) increased, while triglyceride did not change in seminal plasma of treated animals. Supplementation at either level of isoflavones did not cause changes in live body weight (LBW), dry matter intake (DMI), and relative weights of testes and epididymis. The present results showed that either 2.5 mg/kg BW or 5 mg/kg BW doses of isoflavones caused an improvement of some semen characteristics and did not have negative effects on male fertility.     

Heavy metal pollution and forest health in the Ukrainian Carpathians

The Ukrainian Carpathians are characterized by high air pollution caused by emissions from numerous industries. We have been monitoring the state of forests in this region since 1989. The highest levels of tree defoliation (>30%) are found close to industrial emission sources and in the upper mountain forests of the Ivano-Frankivsk and Chernivtsi regions. This is caused by a combination of strong anthropogenic influences (pollution, illegal uses, recreation) as well as poor site and climatic conditions. In the Ivano-Frankivsk region, Cd and Mo accumulate in forest soils; Cr, Mo and Zn soil concentrations are higher than their limit levels; and Pb concentrations exceed toxic levels close to industrial areas (10% of the region territory). Local background levels of heavy metals are greatly exceeded in snow close to industrial regions. Analysis of correlation matrices shows that the chemical elements Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V and Zn occur at pollution levels in natural ecosystems in the Ukrainian Carpathians. Maximum concentrations of toxic elements occur in the oak forest zone; the most industrially developed area of the region. Toxic heavy metals in the Ukrainian Carpathians forests enter with precipitation and dustfall, then become fixed in soil and accumulate in leaves, needles of vascular plants and mosses. Concentrations of these metals decrease with altitude: highest in the oak forests, less in beech, and lowest in the spruce forest zones. However, some chemical elements have the highest concentrations in spruce forests; V in needles, As in snow, and Ba and Al in soils.     

Role of alpha-tocopherol and beta-carotene in ameliorating the fenvalerate-induced changes in oxidative stress, hemato-biochemical parameters, and semen quality of male rats

Role of alpha-tocopherol (vitamin E), beta-carotene and/or their combination as antioxidants against the toxicity of fenvalerate on blood hematology, free radicals, biochemical parameters, and semen quality were studied in male rats. Fenvalerate (20 mg/kg BW), vitamin E (100 mg/kg BW), beta-carotene (10 mg/kg BW), and vitamin E plus beta-carotene (100 + 10 mg/kg BW, respectively) were given alone or in combination with fenvalerate. The tested doses were given to rats every other day for 30 days. Results obtained showed that fenvalerate significantly (P < 0.05) induced free radicals in plasma and brain and insignificantly in liver and testes. While, vitamin E, beta-carotene alone and/or in combination decreased the levels of free radicals in plasma, liver, testes, and brain. The activities of glutathione S-transferase (liver), alkaline phosphatase (plasma and liver), aspartate aminotransferase (plasma, liver, and testes) and alanine aminotransferase (plasma and liver) were significantly (P < 0.05) increased due to fenvalerate administration. The activity of acetylcholinesterase was significantly (P < 0.05) decreased in brain and plasma, while plasma glucose, urea, creatinine, and bilirubin concentrations were significantly (P < 0.05) increased in rats treated with fenvalerate. Also, results showed a significant (P < 0.05) alterations in plasma proteins, hematological parameters, body weight, and relative weights of organs. Sperm concentration and motility (%) were significantly (P < 0.05) decreased, while dead and abnormal sperm increased in rats exposed to fenvalerate. Vitamin E, beta-carotene alone and/or in combination did not cause any changes in the investigated parameters, but improved semen quality and minimized the toxic effect of fenvalerate. The obtained results demonstrated the beneficial influences of vitamin E, beta-carotene alone and/or in combination in reducing the harmful effects of fenvalerate.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Correlation of gas chromatographic properties of chlorobenzenes and polychlorinated biphenyls with the occurrence of reductive dechlorination by untamed microorganisms

To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.