In this study, the effectiveness of subcritical water extraction (SCWE) was assessed by extracting four pesticides, namely diazinon, parathion, phenthoat, and EPN, from contaminated soil. The extraction efficiencies of different temperatures (25, 75, 100, 125, and 150 C); times (10, 20, 30, and 40 min); pressures (1, 2, and 3 MPa); and water flow rates (0.5, 0.7, 1.0, and 1.5 mL/min) were investigated. The optimum temperature, time, pressure, and flow rate were found to be 150 C, 20 min, 2 MPa, and 0.5 mL/min, respectively, in lab-scale. At this operating condition, the residual concentration of pesticide was less than 0.5 mg/kg, corresponding to an extraction efficiency of 99.9 %. The aim of this study was to also evaluate the removal efficiency on 30- and 167-fold scale-up extraction at optimum extraction condition obtained from lab-scale studies. The scale-up method considering constant ratio of the volume of water to soil mass was a feasible procedure. The results of our study suggest that SCWE is a promising option for effective disposal of pesticide- contaminated soil. © 2013 Springer Science+Business Media Dordrecht.

The objectives of this study were to assess susceptibility to acidification and nitrogen (N) saturation caused by atmospheric deposition to northeastern US forests, evaluate the benefits and shortcomings of making critical load assessments using regional data, and assess the relationship between expected risk (exceedance) and forest health. We calculated the critical loads of nutrient N and of sulfur (S) + N using the steady-state mass balance method at >4,000 regional and national vegetation and soil monitoring network plots in the northeastern USA. Regional calculations of critical loads necessitate use of soil maps which provide a range for each soil characteristic resulting in a broad range of critical load of S + N and exceedance values. For the scenario most representative of regional conditions, over 80 % of the critical loads fell into the range of 850–2050 eq ha⁻¹ yr⁻¹; at 45 % of the plots, deposition exceeded the critical load. In contrast, the critical load for nutrient N, 200–300 eq ha⁻¹ yr⁻¹, was lower. Site measurements, especially to estimate soil weathering, would increase the certainty of the critical load. We observed significant negative correlations between critical load exceedance and growth (17 species) and crown density (4 species); we observed significant positive correlations of exceedance with declining vigor (four species), with crown dieback (six species) and crown transparency (seven species). Among the species which demonstrate the most significant detrimental responses to atmospheric deposition are balsam fir, red spruce, quaking aspen, and paper birch. These results indicate that significant detrimental responses to atmospheric deposition are being observed across the northeastern USA.

The speciation of mercury (Hg) is a major determinant of its methylation rate by sulfate-reducing bacteria (SRB), considered the primary methylators. Under anoxic conditions, sulfur (S) cycling may have a significant influence on Hg complexation and methylation, by influencing both SRB activity and the pool of available reduced S ligands, as the presence of zero-valent sulfur (S(0)) in sulfidic water results in the formation of polysulfides. While SRB frequently coexist with S-oxidizing bacteria in natural environments, the effect that these organisms may have on methylation by SRB is not understood. In this study, we investigate the role of S(0) in methylation by SRB monocultures and cocultures with phototrophic green or purple S-oxidizing bacteria. In the coculture experiments, the presence of S-oxidizers was found to increase Hg methylation rates, apparently by maintaining favorable chemical speciation in the environment. The measured Hg methylation rates were in accord with predictions based on geochemical modeling of speciation. In SRB monoculture experiments conducted in the presence and absence of S(0), the data showed that at limited total Hg, the presence of polysulfides resulted in decreased Hg methylation, presumably by causing a decrease in the most bioavailable Hg–sulfide complexes. These results indicate that models of Hg speciation and methylation in the environment should include a detailed investigation of S redox speciation.

Emissions of volatile organic compounds (VOCs) were studied from three heavily polluted rivers (Huijiang, Nancun, and Zengbian Rivers) in Guangzhou, South China. A total of 49 species of VOCs were identified. Nancun River had the highest concentration of total VOCs (TVOCs), which ranged from 1,467 to 5,522 μg m⁻³. Trichloroethene, benzene, toluene, ethylbenzene, m/p-xylene, o-xylene, styrene, and 1,3,5-trimethylbenzene were the main pollutants. The levels of VOCs evaporated from the three rivers exhibited different patterns. Correlations between the concentrations of major VOCs were established and found to be statistically significant, except for o-xylene. The ratios of toluene/benzene, ethylbenzene/benzene, and xylene/benzene were estimated and found to be higher than widely reported in the literature. TVOC fluxes in the three rivers were calculated to be the range from 24.8 to 765 μg m⁻² h⁻¹. This study provides a regional background for the emission inventories of VOCs from heavily polluted rivers in southern China and provides resource managers with important information to guide remediation and policy concerning VOC emissions to the environment.

Hydrogels based on p(4-VP) of different dimensions were prepared and, after chemical modification, were used in the removal of one of the most potent toxic materials, cyanide. Macro and micron p(4-VP) hydrogel swelling behavior was evaluated in various aquatic environments. HCl, bromoethane, 1-bromobutane, 1-bromohexane, and 2-bromoethylamine were used as quaternizing agents to generate positive charges on both p(4-VP) macrogels and microgels. The modified p(4-VP) macrogels and microgels were used in cyanide ion removal for the first time from aqueous environments. The p(4-VP)-HCl at macro and micro sizes removed almost 49 and 61 mg cyanide ions per gram hydrogel in deionized water after modification, respectively. Moreover, the absorption capacity of the modified p(4-VP) hydrogel did not change significantly in tap, drinking, and creek waters. Parameters that affect the absorption process, such as cyanide concentration, contact time, hydrogel amount, and contaminated water source, were investigated. Additionally, magnetic field responsive macro and micro p(4-VP) hydrogel composites provided many advantages, such as easy handling after cyanide absorption, e.g., ready removal of cyanide-loaded p(4-VP) composites with an externally applied magnetic field. Langmuir and Freundlich adsorption isotherms were applied to the data obtained for cyanide uptake from aqueous environments.

The decolorization and degradation of anionic sulphonated azo dye (Reactive orange 16 (RO16)), which is suspected to be carcinogenic, were investigated using ozone. The decolorization process of the reactive dye was carried out by bubbling ozone at the bottom of a bubble column reactor containing the dye solution. The effect of pH, reaction time, dye concentration, ozone concentration, and decolorization time was studied. Also, degradation products and possible degradation mechanism were investigated. The results showed that ozonation was a highly effective way to remove color from wastewater. The color of a synthetic waste solution containing water-soluble reactive dye was reduced to 69.69 % under the basic condition (pH 12), with complete RO16 degradation occurring in 8 min. Ozone consumption continued for a further 16 min after which time most of the degradation reactions were complete. Kinetic studies showed that direct ozonation of the aqueous dyes represented a pseudo-first-order reaction with respect to the dye. The apparent rate constant increased with both the applied ozone dose and higher pH values and declined logarithmically with the initial dye concentration. Intermediates such as 6-acetylamino-3-aminonaphthalene-2-sulfonic acid, 2-(4-nitrosophenyl) sulfonylethyl hydrogen sulfate, and 6-acetamido-4-hydroxy-3-nitroso naphthalene-2-sulfonic acid were detected by gas chromatograph coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic, and oxalic acids were detected by ion chromatography.

Biodegradation of chlorpyrifos was studied in mineral medium and soil with a novel fungal strain JAS1 isolated from a paddy field soil. The molecular characterization based on 18S rRNA sequence homology confirmed its identity as Aspergillus terreus. The 300-mg L⁻¹ chlorpyrifos and its major metabolite 3,5,6-trichloro-2-pyridinol (TCP) were completely degraded within 24 h of incubation in the mineral medium. In soil enriched with chlorpyrifos and nutrients (carbon, nitrogen, and phosphorous), A. terreus JAS1 was able to degrade chlorpyrifos and its metabolite TCP (300 mg kg⁻¹ soil) in 24 and 48 h, respectively. The soil was spiked with chlorpyrifos (300 mg kg⁻¹ soil) devoid of nutrients and the fungal strain was capable of degrading both chlorpyrifos and TCP in 24 and 48 h, respectively. The course of the degradation process was studied using high-performance liquid chromatography and Fourier transform infrared analyses. These results showed that the chlorpyrifos-degrading fungal strain had the potential to degrade the pesticide-contaminated agricultural soils even without addition of nutrients.

A study was undertaken to assess the extent of mercury contamination in the water and sediment in a seasonal wetland, as well as to determine the relationship between environmental parameters and the distribution of the mercury contamination. Water and sediment samples were collected and analysed for methylmercury, inorganic mercury and other physical and chemical variables. One-way analysis of variance and homogeneity of variance were performed, and linear regression analysis was used to determine correlations between mercury and other environmental variables. The highest mercury concentrations were recorded at the sites located closest to the industrial complex. Methylmercury concentrations in the water and sediment were mostly higher during the low flow season, while inorganic mercury concentrations in the water and sediment were higher during the high flow and low flow seasons, respectively. Chromium, manganese, organic carbon and fine sediment particles were found to have significantly positive correlations with mercury concentrations in water and sediment. It was also found that the mercury concentrations decreased within a relatively short distance from the sites closer to the industrial complex to the sites further downstream.

In this paper, the possible effect of surface ozone on soybean, wheat, rice, and maize crops in East Asia in 2000, 2005, and 2020 is estimated. Spatial distribution and temporal variation of surface ozone concentrations are simulated using the Models-3 Community Multiscale Air Quality Modeling System coupled with the Regional Emission Inventory in Asia (CMAQ/REAS). The effect of surface ozone on main crops in East Asia is evaluated based on accumulated exposure over a threshold of 40 ppb (AOT40 index) during a period of 3 months of the growing season. We demonstrate some of the implications for policy-making in air quality management for East Asia by highlighting the effect of elevated surface ozone concentrations on harvest losses and the corresponding value of the main crops. These concentrations are calculated based on three scenarios of emission reduction policies in 2020: policy success case (PSC), reference case (REF), and policy failure case (PFC). Assuming no future changes in land use or cropping patterns from 2000 to 2020, we find that the highest relative yield (RY) losses are in wheat and soybean in East Asia. The RY losses for wheat are estimated to range between 17 and 35 % in 2000, 21 and 49 % in 2005, 18 and 36 % in 2020 (PSC), 20 and 46 % in 2020 (REF), and 22 and 62 % in 2020 (PFC); the corresponding values for rice are 6 and 12 %, 6 and 17 %, 6 and 15 %, 6 and 17 %, and 7 and 20 %; for soybean, they are 12 and 16 %, 19 and 25 %, 18 and 33 %, 21 and 40 %, and 25 and 49 %; and for maize, they are 3 and 4 %, 5.7 and 6 %, 6 and 9 %, 9 and 11 %, and 12 and 14 %. Quantitatively, the estimated losses in production of wheat in East Asia in 2000, 2005, and 2020 (PSC, REF, and PFC scenarios) are 32.4, 44.3, 42.2, 54.0, and 72.3 t, respectively; for rice, 34.9, 39.4, 42.4, 46.5, and 54.6 mmt; for soybean, 1.9, 3.3, 3.6, 4.9, and 7.0 mmt; and for maize, 3.6, 8.1, 11.4, 15.4, and 21.5 mmt. The estimated values of crop losses in East Asia in 2000, 2005, and 2020 (PSC, REF, and PFC scenarios) are as follows: 13.8, 17.4, 18.2, 21.3, and 26.7 billion Int. $. Therefore, adaptation measures in the PSC scenario in contrast to the PFC scenario could save around 8.5 billion Int. $ across East Asian countries in 2020.

The growth of white-rot fungus Pleurotus eryngii F032 in a suitable medium can degrade an azo dye Reactive Black 5 (RB5), because of its ability to produce ligninolytic enzymes such as lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase that able to degrade and transform the complex structure of the dye into a less toxic compound. The effect of environmental factors such as initial concentration of Reactive Black 5, pH, temperature of growth medium, surfactant (Tween 80), and agitation were also investigated. The productions of ligninolytic enzymes were enhanced by increasing the white-rot fungi growth in optimum conditions. The decolorization of Reactive Black 5 were analyzed by using UV–vis spectrophotometer at the maximum absorbance of 596 nm. The white-rot fungus, P. eryngii F032 culture exhibited 93.56 % decolorization of 10 mg/L RB5 within 72 h of incubation in dark condition with agitation. The optimum pH and temperature for the decolorizing activity was recorded at pH 3 and 40 °C, respectively. The addition of surfactant (Tween 80) increased the decolorization to 93.57 % and agitation of growth medium at 120 rpm enhanced the distribution of nutrients to the fungus thus optimized the enzymatic reaction that resulted maximum decolorization of RB5 which was 93.57 %. The molecular docking studies were performed using Chimera visualization software as to analyze the decolorization mechanism of RB5 at molecular level.