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.     

Biodegradation of trifluralin in Harran soil

Degradation of trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0-10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain. were incubated in biometer flasks for 350 days at 25 degrees C. Ring-UL-14C-trifluralin was applied at the rate of 2 microg g(-1) with 78.7 kBq radioactivity per 100 g soil flask. Evolved (14)CO2 was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound 14C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3/' of the applied radiocarbon was evolved as (14)CO2 from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound 14C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

Conditioning of aluminium-based water treatment sludge with Fenton's reagent: effectiveness and optimising study to improve dewaterability

Alternative conditioning of aluminium-based drinking water treatment sludge using Fenton reagent (Fe2+/H2O2) was examined in this study. Focuses were placed on effectiveness and factors to affect such novel application of Fenton process. Experiments have demonstrated that considerable improvement of alum sludge dewaterability evaluated by capillary suction time (CST) can be obtained at the relative low concentrations of Fenton reagent. A Box-Behnken experimental design based on the response surface methodology was applied to evaluate the optimum of the influencing variables, i.e. iron concentration, hydrogen peroxide concentration and pH. The optimal values for Fe2+, H2O2, and pH are 21 mg g(-1)DS(-1)(dry solids), 105 mg g(-1)DS(-1) and 6, respectively, at which the CST reduction efficiency of 48+/-3% can be achieved, this agreed with that predicted by an established polynomial model in this study.     

Modulation of steroidogenesis by coastal waters and sewage effluents of Hong Kong, China, using the H295R assay

BACKGROUND, AIM, AND SCOPE: The presence of a variety of pollutants in the aquatic environment that can potentially interfere with the production of sex steroid hormones in wildlife and humans has been of increasing concern. The aim of the present study was to investigate the effects of extracts from Hong Kong marine waters, and influents and effluents from wastewater treatment plants on steroidogenesis using the H295R cell bioassay. After exposing H295R cells to extracts of water, the expression of four steroidogenic genes and the production of three steroid hormones were measured. MATERIALS AND METHODS: Water samples were collected during the summer of 2005 from 24 coastal marine areas and from the influents and effluents of two major waste water treatment plants (WWTPs) in Hong Kong, China. Samples were extracted by solid phase extraction (SPE). H295R cells were exposed for 48 h to dilutions of these extracts. Modulations of the expression of the steroidogenic genes CYP19, CYP17, 3betaHSD2, and CYP11beta2 were determined by measuring mRNA concentrations by real-time polymerase chain reaction (Q-RT-PCR). Production of the hormones progesterone (P), estradiol (E2), and testosterone (T) was quantified using enzyme linked immunosorbent assays (ELISA). RESULTS: Extracts from samples collected in two fish culture areas inhibited growth and proliferation of H295R cells at concentrations greater or equal to 10(5) L equivalents. The cells were exposed to the equivalent concentration of active substances in 10,000 L of water. Thus, to observe the same level of effect as observed in vitro on aquatic organisms would require a bioaccumulation factor of this same magnitude. None of the other 22 marine samples affected growth of the cells at any dilution tested. Twelve of the marine water samples completely inhibited the expression of CYP19 without affecting E2 production; inhibition of CYP17 expression was observed only in one of the samples while expression of CYP11beta2 was induced as much as five- and ninefold after exposure of cells to extracts from two locations. The expression of the progesterone gene 3betaHSD2 was not affected by any of the samples; only one sample induced approximately fourfold the production of E2. Although more than twofold inductions were observed for P and T production, none of these values were statistically significant to conclude effects on the production of these two hormones. While influents from WWTPs did not affect gene expression, an approximately 30% inhibition in the production of E2 and a 40% increase in P occurred for the exposure with influents from the Sha Tin and Stonecutters WWTPs, respectively. Effluents from WWTPs did not affect the production of any of the studied hormones, but a decrement in the expression of the aldosterone gene CYP11beta2 was observed for the Sha Tin WWTP exposure. No direct correlation could be established between gene expression and hormone production. DISCUSSION: Observed cytotoxicity in the two samples from fish culture areas suggest the presence of toxic compounds; chemical analysis is required for their full identification. Although effluents from WWTPs did not affect hormone production, other types of endocrine activity such as receptor-mediated effects cannot be ruled out. Interactions due to the complexity of the samples and alternative steroidogenic pathways might explain the lack of correlation between gene expression and hormone production results. CONCLUSIONS: Changes observed in gene expression and hormone production suggest the presence in Hong Kong coastal waters of pollutants with endocrine disruption potential and others of significant toxic effects. The aromatase and aldosterone genes seem to be the most affected by the exposures, while E2 and P are the hormones with more significant changes observed. Results also suggest effectiveness in the removing of compounds with endocrine activity by the WWTPs studied, as effluent samples did not significantly affect hormone production. The H295R cell showed to be a valuable toll in the battery required for the analysis of endocrine disrupting activities of complex environmental samples. RECOMMENDATIONS AND PERSPECTIVES: Due to the intrinsic complexity of environmental samples, a combination of analytical tools is required to realistically assess environmental conditions, especially in aquatic systems. In the evaluation of endocrine disrupting activities, the H295R cell bioassay should be used in combination with other genomic, biological, chemical, and hydrological tests to establish viable modes for endocrine disruption and identify compounds responsible for the observed effects.     

Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

苯胺-邻氨基酚共聚物对水中Hg(Ⅱ)吸附性能的研究

利用化学氧化法合成了苯胺-邻氨基苯酚的共聚物,并通过静态实验研究了材料对水中汞离子的吸附性能。研究结果表明,该共聚物对废水中汞离子有优异的去除效果,其吸附容量可达212.13 mg/g;吸附等温线符合Langmu ir单层吸附模型,动力学过程符合准二级动力学模型;溶液pH值对吸附影响不是很大,pH 5~10范围都有较好的吸附效果;氯离子易与汞离子形成水溶性更强的络合物,对共聚物的吸附有很大的抑制作用。     

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO₃ process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO₃ process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO₃ and UV/TiO₂ was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.     

Numerical simulation of an array of fences in Saemangeum reclaimed land

This paper discusses about the quantitative effect of windbreak fences on wind velocity in the reclaimed land at Saemangeum in South Korea. Windbreak fences were constructed in the reclaimed land to reduce the wind velocity to prevent the generation and diffusion of dust. However, up to this time, no in-depth studies were conducted to quantitatively measure the effect of the windbreak fences on wind velocity thus an optimum windbreak structure is not yet determined. Using CFD simulations, the effects of fence porosity, fence height, and the distance between the adjacent fences were investigated. A wind tunnel experiment was initially conducted and data gathered were used to develop the CFD models. From the experiments and CFD simulations, the overall percentage difference of the measured velocities was 7.20% which is generally acceptable to establishing the reliability of the CFD models. The reduction effect on wind velocity was measured in between the adjacent fences up to a height of 0.6 m from the ground surface. In terms of porosity ( = 0, 0.2, 0.4, 0.6), 0.2 was found to be the optimum value. Conversely, the effect of fence height (0.6, 0.8 and 1.0 m) showed no significant difference; therefore, 0.6 m height is recommended. In addition, the reduction effect of distance between the adjacent fences (2, 4 and 6 m) on wind velocity having a 0.2 porosity has decreased to about 75% regardless of the distance. In the case of the reclaimed land in Saemangeum, a decrease of 75% can prevent the generation and diffusion of dusts. However, the source of dusts is very large. Therefore, constructing an array of windbreak with 6 m distance between them is deemed necessary.     

Persistence of repeated triadimefon application and its impact on soil microbial functional diversity

The effects of repeated applications of the fungicide triadimefon in agricultural soil on the microbial functional diversity of the soil and on the persistence of the fungicide in the soil were investigated under laboratory conditions. The degradation half-lives of triadimefon at the recommended dosage, simulated by a first-order kinetic model, were 23.90, 22.95, and 21.52 days for the first, second, and third applications, respectively. Throughout this study, no significant inhibition of the Shannon-Wiener index (H') was observed. However, the Simpson index (1/D) and the McIntosh index (U) were obviously reduced (p ≤ 0.05) during the initial 3 days after the first triadimefon application and thereafter, gradually recovered to or exceeded the level of the control soil. A similar trend in variation but with a faster recovery in the 1/D and U was observed after the second and third triadimefon applications, respectively. Taken together, the above results indicate that the repeated application of triadimefon enhanced the degradation rate of the fungicide and the recovery rate of the soil microbial functional diversity. It is concluded that repeated triadimefon applications in soil have a transient or temporary inhibitory effect on soil microbial communities.