Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

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.     

Preliminary ecotoxicological characterization of a new energetic substance, CL-20

A new energetic substance hexanitrohexaazaisowurtzitane (or CL-20) was tested for its toxicities to various ecological receptors. CL-20 (epsilon-polymorph) was amended to soil or deionized water to construct concentration gradients. Results of Microtox (15-min contact) and 96-h algae growth inhibition tests indicate that CL-20 showed no adverse effects on the bioluminescence of marine bacteria Vibrio fischeri and the cell density of freshwater green algae Selenastrum capricornutum respectively, up to its water solubility (ca. 3.6 mg l(-1)). CL-20 and its possible biotransformation products did not inhibit seed germination and early seedling (16-19 d) growth of alfalfa (Medicago sativa) and perennial ryegrass (Lolium perenne) up to 10,000 mg kg(-1) in a Sassafras sandy loam soil (SSL). Indigenous soil microorganisms in SSL and a garden soil were exposed to CL-20 for one or two weeks before dehydrogenase activity (DHA) or potential nitrification activity (PNA) were assayed. Results indicate that up to 10,000 mg kg(-1) soil of CL-20 had no statistically significant effects on microbial communities measured as DHA or on the ammonium oxidizing bacteria determined as PNA in both soils. Data indicates that CL-20 was not acutely toxic to the species or microbial communities tested and that further studies are required to address the potential long-term environmental impact of CL-20 and its possible degradation products.     

Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Mercury biomethylation assessment in the estuary of Bilbao (North of Spain)

The relationship between the microbial methylation of mercury and the microbial activities in sediments and water collected from the estuary of Bilbao (North of Spain) was studied in three different sampling points and in two different seasons. Three different cultures were prepared with a sediment slurry to distinguish between biotic and abiotic methylation pathways and the variations of the methylmercury concentration and the variations of the population of total number of bacteria (TDC), anaerobic heterotrophic bacteria (AHB), sulphate-reducing bacteria (SRB) and Desulfovibrio were measured. From this work, it can be concluded that the variation of MeHg concentrations is a result of the methylation/demethylation processes in the sediments, and that the abiotic processes have a negligible contribution to those processes. According to the statistical analysis of the results (partial least squares analysis) a significant statistical correlation was established between methylmercury and the SRB counts.     

Anatomical element localization by EDXS in Grevillea exul var. exul under nickel stress

Grevillea exul var. exul, an endemic serpentinic Proteaceae of New Caledonia, was chosen to study the spatial distribution of Ni because this species supports strong content of metals, which can allow important absorptions thus detectable by microanalysis. Fine transversal sections of axenic G. exul var. exul plants grown during 15 days on nickel sulphate medium were examined by EDXS microanalysis. It showed that in Ni treated plants, Ni was concentrated mostly in the phloem compared to the xylem and the epidermis, either in roots or in the basal part of the stems and was mostly in the epidermis in the upper part of the stems and not detectable in the leaves. This metal took the place of P and K in the treated plants whereas the localization of these macroelements was quite uniform in control sections. We assume that a mechanism of phloem loading is implicated to restrict Ni accumulation in G. exul var. exul.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 x 10(-3) to 6.3 x 10(-3) min(-1).     

Agricultural reuse of reclaimed water and uptake of organic compounds: pilot study at Mutah University wastewater treatment plant, Jordan

The residues of polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated benzenes (CBs) and phenols were investigated for soil, wastewater, groundwater and plants. The uptake concentration of these compounds was comparatively determined using various plant types: Zea mays L., Helianthus annus L., Capsicum annum L., Abelmoschus esculentus L., Solanum melongena L. and Lycopersicon esculentum L. which were grown in a pilot site established at Mutah University wastewater treatment plant, Jordan. Soil, wastewater, groundwater and various plant parts (roots, leaves and fruits) samples were extracted in duplicate, cleaned up by open-column chromatography and analyzed by a multi-residue analytical methods using gas chromatography equipped with either mass selective detector (GC/MS), electron capture detector (GC/ECD), or flame ionization detector (FID). Environmentally relevant concentrations of targeted compounds were detected for wastewater much higher than for groundwater. The overall distribution profiles of PAHs and PCBs appeared similar for groundwater and wastewater indicating common potential pollution sources. The concentrations of PAHs, PCBs and phenols for different soils ranged from 169.34 to 673.20 microg kg(-1), 0.04 to 73.86 microg kg(-1) and 73.83 to 8724.42 microg kg(-1), respectively. However, much lower concentrations were detected for reference soil. CBs were detected in very low concentrations. Furthermore, it was found that different plants have different uptake and translocation behavior. As a consequence, there are some difficulties in evaluating the translocation of PAHs, CBs, PCBs and phenols from soil-roots-plant system. The uptake concentrations of various compounds from soil, in which plants grown, were dependent on plant variety and plant part, and they showed different uptake concentrations. Among the different plant parts, roots were found to be the most contaminated and fruits the least contaminated.     

Soil sensitivity to acidification in Asia: status and prospects

Exceedance of steady-state critical loads for soil acidification is consistently found in southern China and parts of SE Asia, but there is no evidence of impacts outside of China. This study describes a methodology for calculating the time to effects for soils sensitive to acidic deposition in Asia under potential future sulfur (S), nitrogen (N), and calcium (Ca) emission scenarios. The calculations are matched to data availability in Asia to produce regional-scale maps that provide estimates of the time (y) it will take for soil base saturation to reach a critical limit of 20% in response to acidic inputs. The results show that sensitive soil types in areas of South, Southeast, and East Asia, including parts of southern China, Burma, Hainan, Laos, Thailand, Vietnam, and the Western Ghats of India, may acidify to a significant degree on a 0-50 y timescale, depending on individual site management and abiotic and biotic characteristics. To make a clearer assessment of risk, site-specific data are required for soil chemistry and deposition (especially base cation deposition); S and N retention in soils and ecosystems; and biomass harvesting and weathering rates from sites across Asia representative of different soil and vegetation types and management regimes. National and regional assessments of soils using the simple methods described in this paper can provide an appreciation of the time dimension of soil acidification-related impacts and should be useful in planning further studies and, possibly, implementing measures to reduce risks of acidification.