Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in China and chemometric analysis of potential emission sources

Aimed to give a preliminary image of dioxin pollution in China, chemometric analysis was performed to determine background dioxin levels during the period 1994-2002 and potential emission sources. Using principal components analysis (PCA), the congener profiles of 71 sediment samples from rivers, lakes, and sea bays around China were compared with the congener profiles of various known or suspected industrial, residential, and municipal dioxin sources to determine whether the dioxin residues typically found in a broad range of potential environmental sources could explain the presence of these chemicals in China. It was found that the background dioxin levels of China were similar to those of lightly polluted samples from other countries during the period 1994-2002. Primary ferrous ore sintering and secondary lead and aluminum smelters were the major sources of dioxin emission in China. Chloranil and wastewater from chemical plants, sodium pentachlorophenate, and pulp bleaching were also important sources of dioxin emission. Open burning of e-waste as well as diesel-fueled and leaded gas-fueled vehicles were additional possible sources of dioxin. In contrast to other countries, in China, flue gases from incineration of municipal waste, hazardous waste, and medical waste might be minor sources of dioxin emission.     

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans from raw and solidified waste incineration residues

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues were examined via a nine-time multiple leaching test. The effect of injected activated carbon in the APC residues on the PCDD/F leachability was also evaluated. When humic acid solution was used as a leachant, the leaching concentrations of PCDD/Fs fluctuated between the first and the fifth leaching, followed by a gradual increase and then suddenly reached maximum values at the leaching sequences around seventh and eighth. This significant enhancement in PCDD/F leachability was mainly due to an increase in the release of highly chlorinated PCDD/Fs. Leaching of PCDD/Fs with n-hexane was, in contrast, primarily caused by the partitioning of hydrophobic PCDD/Fs between the APC residue surface and the liquid phase of n-hexane. Consequently, the largest leaching concentrations for n-hexane tests achieved at the first leaching, followed by a decrease and reached plateaus. Solidification/stabilization (S/S) decreased the PCDD/F leachability up to the fifth leaching by the use of humic acid solution. However, S/S increased the PCDD/F leaching concentrations and rates with n-hexane. The activated carbon in APC residues significantly inhibited the release of PCDD/F with n-hexane. The inhibiting effect provided by activated carbon was, however, less significant by the use of humic acid solution.     

Aging activity of DDE in dissimilar rice soils in a greenhouse experiment

A green-house study was conducted in late 2005 to investigate the aging behavior of p,p'-DDE in two types of soil, Hydragric Anthrosols (An) and Hydragric Acrisols (Ac), according to the World Reference Base (WRB) [FAO/ISRIC/ISSS. 1998. World reference base for soil resources. World soil resources reports, Rome. p. 87]. Paddy rice and dry rice were grown in submerged paddy soils and non-submerged upland soils, respectively. The concentration of extractable p,p'-DDE in fresh DDE-spiked soils was 746.2ngg(-1). During the first few weeks of the experiment, the extractability of p,p'-DDE became increasingly low as the aging period prolonged. However, certain amount of p,p'-DDE that had been captured by soil minerals and organic matter (OM) could be released and became extractable in the later period. The extractability of p,p'-DDE in submerged soils was significantly lower than that in non-submerged soil, because flooding could increase the binding of pollutants to soil particles. The plantation of both dry rice and paddy rice slowed down the aging process of p,p'-DDE. After one month's growth of rice, p,p'-DDE bound to soil particles was released and became extractable. The OM and silt content of An are higher than that of Ac, resulting in more bound residues and relative lower extractability of p,p'-DDE in An. In addition, the extractability of p,p'-DDE could be reduced by the addition of rice straw to soils.     

Radiation-induced degradation of methyl orange in aqueous solutions

Degradation of methyl orange under gamma-irradiation was investigated. The reactions followed pseudo first-order kinetics. Apparent degradation rate constant, estimated through linear regression analysis, increased with an increase of dose rate and a decrease of initial methyl orange concentration. Degradation of methyl orange was significantly accelerated under oxidative condition, but was slightly enhanced under reductive condition. However, the result of decoloration was better under reductive condition than oxidative one. An analysis on the intermediates using Fourier transform infrared and gas chromatography/mass spectrometry demonstrates that the radiolytic degradation of methyl orange was processed with different C-N cleavages under oxidative and reductive conditions.     

Sorption of pentachlorophenol on surficial sediments: the roles of metal oxides and organic materials with co-existed copper present

The sorption characteristics of pentachlorophenol (PCP) in the surficial sediments were investigated using a selective extraction procedure. The results show that the Gamma(max) of PCP sorption decreased from 1.60mumolg(-1) to 0.69mumolg(-1) by approximately 60% after selective removal of organic materials from the sediments. The sorption of PCP in the sediments after selective removal of Mn oxides increased nearly up to 600% (from 1.60mumolg(-1) to 11.11mumolg(-1)) and, to a less degree, the PCP sorption in the sediments after simultaneous removal of Fe/Mn oxides (Gamma(max)=3.53mumolg(-1)). The analysis of the data using an additional model indicates that the contribution of Mn oxides to PCP sorption was negative, and Fe oxides and organic materials both have greater potential for sorption of PCP with less contribution from residues including Mn and Fe oxides in the residual fractions determined by a sequential extraction procedure and clay and silicate minerals. The differences in the decreased degrees of PCP sorption with increasing of Cu suggest that competition between Cu and PCP for sorption sites mainly takes place on Fe oxides.     

Antioxidative response to Cd in a newly discovered cadmium hyperaccumulator, Arabis paniculata F

A hydroponic experiment was carried out to study the effect of cadmium (Cd) on growth, Cd accumulation, lipid peroxidation, reactive oxygen species (ROS) content and antioxidative enzymes in leaves and roots of Arabis paniculata F., a new Cd hyperaccumuator found in China. The results showed that 22-89 microM Cd in solution enhanced the growth of A. paniculata after three weeks, with 21-27% biomass increase compared to the control. Cd concentrations in shoots and roots increased with increasing Cd supply levels, and reached a maximum of 1662 and 8670 mg kg(-1) Cd dry weight at 178 microM Cd treatment, respectively. In roots, 22-89 microM Cd reduced the content of malondialdehyde (MDA), superoxide (O(2)(-1)) and H(2)O(2) as well as the activities of superoxide dismutase (SOD), guaiacol peroxidase (GPX), ascorbate peroxidase (APX) and glutathione reductase (GR). In leaves, the contents of MDA, O(2)(-1) and H(2)O(2) remained unaffected by 22-89 microM Cd, while 178 microM Cd treatment significantly increased the MDA content, 69.5% higher than that of the control; generally, the activities of SOD, catalase (CAT), GPX and APX showed an increasing pattern with increasing Cd supply levels. Our present work concluded that A. paniculata has a great capability of Cd tolerance and accumulation. Moderate Cd treatment (22-89 microM Cd) alleviated the oxidative stress in roots, while higher level of Cd addition (178 microM) could cause an increasing generation of ROS, which was effectively scavenged by the antioxidative system.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

扁平圆环局限空间蒸气云爆炸数值模拟及其在事故调查中的应用

传统方法不能深入描述扁平圆环局限空间蒸气云爆炸过程,笔者利用AutoReaGas软件对这一特殊形状和边界条件的蒸气云爆炸过程进行了数值模拟.其结果表明:对于单一点火源,扁平圆环局限空间蒸气云爆炸冲击波传播方向有2个,相向传播的2个冲击波最后会发生叠加效应而使冲击波超压增大;数值模拟结果和事故现场结果对照相吻合,能为事故调查确定最初起爆点位置等提供依据.     

基于混沌、灰色理论模型,预测煤矿生产中安全状况的对比分析

建立煤矿安全生产状况预测的非线性回归模型、混沌动力学模型、灰色模型和灰色残差模型,用4种模型对我国百万吨煤矿死亡率进行预测分析,其结果表明:混沌动力学预测模型和非线性回归模型使用参数较少、计算简单,易于推广,但预测精度尚不高,误差较大;使用灰色残差模型进行预测,虽然计算复杂,但预测精度较高,验证2007年度百万吨死亡率相对误差仅为0.96%,煤炭生产的安全性指标百万吨死亡率宜采用残差模型进行预测。笔者认为,灰色残差模型在对煤矿安全生产的宏观管理领域有广泛的应用前景。     

HAN阻隔防爆模型研究

通过合理简化,利用多方气体状态方程,分别建立油品储运容器内可燃混合气体定容爆炸模型和装设阻隔防爆材料的油品储运容器内可燃混合气体爆炸模型,获得了阻隔防爆性能测试装置的燃爆容器抗爆设计限值,以及其在HAN阻隔防爆测试中燃爆容器试爆压力量级的控制下限值,同时,还给出HAN工程应用中容器留空率的计算方法,具有实际指导意义。