Survey of heavy metal pollution and assessment of agricultural soil in Yangzhong district, Jiangsu Province, China

We investigated concentrations of Hg, Cd, Pb, Zn, Cu, As, Ni, and Cr in samples of soil, cereal, and vegetables from Yangzhong district, China. Compared to subsoils, the sampled topsoils are enriched in Hg, Cd, Cu, Pb, Zn, and As. High levels of Cd and Hg are observed in most agricultural soils. Concentrations of Cr and Ni show little spatial variation, and high Cu, Pb, and Zn contents correspond well to areas of urban development. High As contents are primarily recorded at the two ends of the sampled alluvion. The contents of Cd, Hg, and total organic carbon (TOC) increase gradually to maximum values in the upper parts of soil profiles, while Cr and Ni occur in low concentrations within sampled profiles. As, Pb, Cu, and Zn show patterns of slight enrichment within the surface layer. Compared to data obtained in 1990, Cd and Hg show increased concentrations in 2005; this is attributed to the long-term use of agrochemicals. Cr and Ni contents remained steady over this interval because they are derived from the weathering of parent material and subsequent pedogenesis. The measured As, Cu, Pb, and Zn contents show slight increases over time due to atmospheric deposition of material sourced from urban anthropogenic activity. Low concentrations of heavy metals are recorded in vegetables and cereals because the subalkaline environment of the soil limits their mobility. Although the heavy metal concentrations measured in this study do not pose a serious health risk, they do affect the quality of agricultural products.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Decomposition pathways and reaction intermediate formation of the purified, hydrolyzed azo reactive dye C.I. Reactive Red 120 during ozonation

In this study, an aqueous solution of purified, hydrolyzed C.I. Reactive Red 120 (RR 120, Color Index), was selected as a model to investigate the degradation pathways and to obtain additional information on the reaction intermediate formation. The dye was purified to avoid the influence of the impurities on the ozonation process and on the formation of oxidation by-products. To simulate the dye-bath effluents from dyeing processes with azo reactive dyes, a hydrolyzed form of the dye was chosen as a representative compound. High performance liquid chromatography/mass spectrometry and its tandem mass spectrometry was chosen to identify the decomposition pathways and reaction intermediate formation during the ozonation process. In addition total organic carbon and high performance ion chromatography analysis were employed to obtain further information on the reaction processes during ozonation. Purified, hydrolyzed RR 120 was decomposed under the direct nucleophilic attack by ozone resulting in oxidation and cleavage of azo group and aromatic ring, while the triazine group still remained in the solution even after prolonged oxidation time (120 min) due to its high resistance to ozonation. Phenol, 1,2-dihydroxysulfobezene, 1-hydroxysulfonbezene were detected as the degradation intermediates, which were further oxidized by O(3) and *OH to other open-ring products and then eventually led to simple oxalic and formic acid identified by HPIC.     

Modeling VOC-odor exposure risk in livestock buildings

This paper describes a novel idea of linking models of exposure, internal dosimetry, and health effects. Risk assessment approach that integrates predicted odor caused by volatile organic compounds (VOC-odor) of toluene/xylene concentrations in human tissues leads to predict exposure risks in livestock buildings. First, VOC transport model was developed to calculate airborne toluene/xylene concentrations. Based on a physiologically based pharmacokinetic (PBPK) model, concentrations within five compartments representing lung, liver, fat, slowly perfused tissues, and rapidly perfused tissues could be quantified. By using a pharmacodynamic (PD) Hill model, we can optimally fit data from rat and human experiments to reconstruct dose-response relationships for accounting human health effects from nose poke and eye irritation. Results demonstrated that peak tissue concentration occurring at 5-10h in that fat contains the highest concentration than other tissues at around 4ppm of toluene and 1.8ppm of xylene. The EC(10) values are 114 and 232ppm, whereas expected risks are estimated to be 0.71% and 0.26% of human exposure to toluene and xylene, respectively. Risk analyses indicate that inhalation exposure in livestock buildings poses no significant threat to human health under the present environmental conditions. This method provides a rigorous and effective approach to relate target tissue concentration to human nose poke or eye irritation. We suggest that our probabilistic framework and methods be taken seriously because they produce general conclusions that are more robust and could offer a risk-management framework for discussion of future establishment of limits for respiratory exposure to VOC-odor.     

The study on the dechlorination of OCDD with Pd/C catalyst in ethanol-water solution under mild conditions

Dechlorination of octachlorodibenzo-p-dioxin (OCDD) was carried out in ethanol-water (v/v=1:1) solution of NaOH in the presence of Pd/C catalysts with the use of H(2). The substrate was dechlorinated with Pd/C under mild conditions (atmospheric pressure and <100 degrees C) to give a chlorine-free product, dibenzo-p-dioxin (DD), in high yields. After reaction of 3h at 50 degrees C, 95.9% OCDD was degraded to low dechlorinated congeners and the yield of DD was 77.4%. We have also studied the dechlorination selectivity of chlorine atoms on the different substituted positions and postulated the dechlorination pathway of OCDD. For OCDD, the 2-position has higher reactivity than 1-position, but the difference is very small. From the distribution statistics of the intermediates during the reaction, we postulate that the steric effect plays an important role during the reaction and affect the dechlorination pathway of OCDD.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

The impact of sewage irrigation on the uptake of mercury in corn plants (Zea mays) from suburban Beijing

The impact of sewage irrigation on the uptake and translocation of mercury (Hg) in corn plants (Zea mays) was investigated. Corn plants were harvested the same day from two nearby fields in suburban Beijing, one irrigated historically with sewage effluent, and one irrigated solely with groundwater. Hg content was analyzed in the soil, roots and stems, while percent moisture and soil organic content were analyzed in the soil samples. The concentration of Hg in the soil and roots, and the soil organic content were not significantly different between the two fields, despite the historic practice of sewage irrigation. Hg content in roots was positively correlated with soil Hg concentration (r=0.95, n=6). The transfer coefficients between roots and stems were significantly higher in the control site (control: 2.06, sewage-irrigated: 0.44, p<0.05), indicating that the barrier effect of the roots was not consistent between the two fields.     

地下储库油气爆炸及抑爆机理与技术研究

针对地下储库受限空间的特点和油气爆炸抑制的需要.在前期所完成的系统油气爆炸试验和理论研究的基础上,采用超细冷气溶胶抑爆新技术,建立地下受限空间油气爆炸及其抑爆模拟试验系统,研制出新型超细冷气溶胶粉体抑爆剂,并对其进行可行性与有效性研究.对地下受限空间油气爆炸抑制的影响因素进行研究,分析了抑爆剂作用机理.结果表明:超细冷气溶胶是一种高效的抑制地下储库油气爆炸的抑爆剂;在相同试验条件下,迎着火焰传播方向喷射抑爆剂的抑爆效果优于垂直火焰传播方向喷射抑爆剂;喷射压力存在临界值,较小较大都不利于油气爆炸抑制,在本文试验条件下.最佳抑爆效果的喷射压力临界值约为0.8 Mpa;抑爆剂用量不能低于临界抑爆浓度,实验得到的抑爆刑临界浓度为0.232 ks/m3;布置方式对抑爆效果具有明显的影响.分散布置比集中布置具有更好的抑爆效果.本文的研究对后续抑爆装置的研制提供了重要的理论参考和关键设计参数.