某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况,对该矿区东河流域附近重金属污染源进行了调查,同时,对地下水和土壤样品进行了采样分析,结果表明：（1）该矿区东河流域附近的主要污染源有18个,其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源;（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995）,综合污染指数P综〉1,该矿区主要的重金属污染元素为Cd、As和Hg,且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系;（3）重金属元素在土壤中的纵向迁移不明显,该矿区附近20个采样点的地下水并未受到污染,综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Kinetics of peanut shell pyrolysis and hydrolysis in subcritical water

Biomass is recognized as an important solution to energy and the environmental problems related to fossil fuel usage. The rational utilization of biomass waste is important not only for the prevention of environmental issues, but also for the effective utilization of natural resources. Pyrolysis and hyrolysis in subcritical water are promising processes for biomass waste conversion. This paper deals with hydrolysis and pyrolysis of peanut shells. Hydrolysis and pyrolysis kinetics of peanut shell wastes were investigated for the in-depth exploration of process mechanisms and for the control of the reactions. Hydrolysis kinetics was conducted in a temperature range of 180–240 °C. A simplified kinetic model to describe the hydrolysis of peanut shells was proposed. Hydrolysis activation energy as well as the pre-exponential factor was determined according to the model. The target products of peanut shell hydrolysis, reducing sugars, can reach up to 40.5 % (maximum yield) at 220 °C and 180 s. Pyrolysis characteristics were investigated. The results showed that three stages appeared in this thermal degradation process. Kinetic parameters in terms of apparent pyrolysis activation energy and pre-exponential factor were obtained by the Coats–Redfern method.     

以焦炭为填料的生物滴滤塔处理含挥发性脂肪酸臭气

在以焦炭为填料的生物滴滤塔对挥发性脂肪酸臭气的处理研究中考察了空床停留时间、臭气浓度、体积负荷以及进气温度等参数对净化效果的影响。结果表明,空床停留时间较长时对臭气降解有利。在停留时间超过97 s时,能实现完全降解;此外,净化率随臭气浓度和体积负荷的不断增加呈先增加后降低的趋势。当臭气浓度为24.29 mg/m³即臭气的体积负荷为3 g/（m³·h）时,去除率约为96%;当臭气浓度增至1 345.74 mg/m³即体积负荷增至18 g/（m³·h）,去除率达100%;然而,当臭气浓度增至4 934.38 mg/m³即体积负荷增至66 g/（m³·h）时,去除率降至73.1%。另外,进气温度对净化率也有一定程度影响。当进气温度较低时,净化效率相对较高。     

盐析分相微萃取—高效液相色谱法测定水中含氯除草剂

采用盐析分相微萃取—高效液相色谱法同时测定水中3种含氯除草剂,建立并优化了反相离子对液相色谱条件,考察了萃取剂种类、盐析剂的种类和加入量及试样pH对萃取效果的影响。对氯苯氧乙酸、2,4-二氯苯氧乙酸和2,4-滴丁酯的质量浓度在0.1~100.0mg/L内与色谱峰面积呈良好的线性关系,相关系数不低于0.9992。平均回收率分别为96.29%、79.16%和70.21%,相对标准偏差小于5.3%。该方法操作简便、绿色环保,适合于水中含氯除草剂的测定。     

Chemical oxidation of sulfadiazine by the Fenton process: Kinetics,pathways, toxicity evaluation

This paper investigated sulfadiazine oxidation by the Fenton process under various reaction conditions. The reaction conditions tested in the experiments included the initial pH value of reaction solutions, and the dosages of ferrous ions and hydrogen peroxide. Under the reaction conditions with pH 3, 0.25 mM of ferrous ion and 2 mM of hydrogen peroxide, a removal efficiency of nearly 100% was achieved for sulfadiazine. A series of intermediate products including 4-OH-sulfadiazine/or 5-OH-sulfadiazine, 2-aminopyrimidine, sulfanilamide, formic acid, and oxalic acid were identified. Based on these products, the possible oxidation pathway of sulfadiazine by Fenton's reagent was proposed. The toxicity evaluation of reaction solutions showed increased antimicrobial effects following the Fenton oxidation process. The results from this study suggest that the Fenton oxidation process could remove sulfadiazine, but also increase solution toxicity due to the presence of more toxic products.     

Influence of Spartina alterniflora on the mobility of heavy metals in salt marsh sediments of the Yangtze River Estuary, China

Using bio-disturbed sulphide to trace the mobility and transformation of Cu, Pb, Ni and Zn in the sediments of the Spartina alterniflora-dominated salt marsh in the Yangtze River Estuary, measurements were made of the seasonal variations of acid-volatile sulphide (AVS) and of the simultaneously extracted metals (SEM) in the rhizosphere sediments. Microcosm incubation experiments recreating flooding conditions were conducted to evaluate the effect of AVS and other metal binding phases upon the dynamics of Cu, Pb, Ni and Zn in the salt marsh sediments. The results demonstrate that the ratio values of SEM/AVS have a significant seasonal variation in the rhizosphere sediments and that the anoxic conditions in the sediments were likely enhanced by S. alterniflora during the summer and autumn compared with the anoxic conditions resulting from the native species Phragmites australis and Scirpus mariqueter. The incubation experiments suggest that Fe(III) and Mn(IV/III) (hydr)oxides provide important binding sites for heavy metals under oxic conditions, and sulphide provides important binding sites for the Cu and Pb under anoxic conditions. Our observations indicate that the mobility of heavy metals in the salt marsh sediments is strongly influenced by biogeochemical redox processes and that the invasive S. alterniflora may increase the seasonal fluctuation in heavy metal bioavailability in the salt marsh ecosystem.     

Joint action and lethal levels of toluene, ethylbenzene, and xylene on midge (Chironomus plumosus) larvae

Aquatic ecosystems are vulnerable to the exposure with petrochemicals such as toluene, ethylbenzene, and xylene (o-, m-, and p-xylene) (TEX) and their adverse effects. Considering the widespread use, occurrence, and high toxicity of TEX, the aim of this work was to investigate the differential toxicity of TEX against midge (Chironomus plumosus) larvae and reveal the joint action of binary and ternary mixtures of TEX using the predictive concentration addition model. More importantly, this research can afford the basic toxicity data and scientific reference for the establishment of water quality criteria or benchmark, water pollution control, and aquatic risk assessment. Single and joint toxic effects of TEX on C. plumosus larvae were investigated using a semi-static bioassay, and the type of joint effects of TEX was ascertained. In the single toxicant experiments, the toxicity of the three pollutants could be sequenced as ethylbenzene > xylene > toluene. Specifically, LC_50s of T, E, and X after a 48-h exposure were 64.9, 37.8, and 42.0 mg/L, respectively. In the binary mixture experiments, the interaction between toluene and ethylbenzene, ethylbenzene and xylene, and toluene and xylene was largely in conformity with partial additive or additive effect as determined by isobologram representation and toxic unit models. In the ternary mixture experiments, the interaction was basically dependent on the use of additive index and mixture toxicity index methods. However, the antagonistic and synergistic actions were not significant. Thus, the tertiary mixture interaction could be regarded as additive action. The concentration addition model could successfully predict the joint action of TEX mixtures on C. plumosus larvae. Particularly, the additive action of TEX on C. plumosus larvae can be further recommended to evaluate water quality criteria of TEX.     

Simultaneous adsorption and degradation of Zn2+ and Cu2+ from wastewaters using nanoscale zero-valent iron impregnated with clays

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu²⁺ and Zn²⁺ from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu²⁺ and Zn²⁺ from a aqueous solution containing a 100 mg/l of Cu²⁺ and Zn²⁺, where 92.9 % Cu²⁺ and 58.3 % Zn²⁺ were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu²⁺ and Zn²⁺. A kinetics study indicated that removing Cu²⁺ and Zn²⁺ with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu²⁺and Zn²⁺ on bentonite and the degradation of Cu²⁺and Zn²⁺ by nZVI on the bentonite. However, Cu²⁺ removal by B-nZVI was reduced rather than adsorption, while Zn²⁺ removal was main adsorption. Finally, Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.     

Distribution and temporal trend of polybrominated diphenyl ethers in one Shanghai municipal landfill, China

The scarcity of information on polybrominated diphenyl ethers’ (PBDEs) flow in landfill restricts the life cycle analysis of PBDEs. In this study, eight PBDE congeners (BDEs 28, 47, 99, 100, 153, 154, 183, and 209) in topsoil, vegetation leaves, leachate, and municipal aged refuse collected from Shanghai Laogang Municipal Landfill (SLML) were investigated. The present study revealed elevated PBDE concentrations in topsoil and proved PBDE leakage from SLML and vegetation uptake. BDE-209 was the predominant congener, and this could be due to massive usage of deca-BDE mixture in Shanghai. ΣPBDE concentrations in leachates treated by reed wetland and A²/O process fell in the low end of the worldwide range. ΣPBDE concentrations in aged refuse samples rose from under 50 ng/g dw in 1989 to the range of 5,150–5,718 ng/g dw in 2002. PBDE concentrations increase in aged refuse samples throughout the 1990s into the 2000s paralleled municipal solid waste output from 1991 to 2002 in Shanghai. Exponential increase in BDE-209 concentration in aged refuse suggested the increasing market demands for deca-BDE mixture after 1990 in China. Notably, the inventory of PBDEs in SLML was 28.7 MT, and the doubling time of BDE-209 in aged refuse was calculated to be 1.6 year. SLML can be considered as a source of PBDE and one main recipient of PBDE as well, receiving inputs predominantly from the PBDE-containing waste. Priority should be given to formulate regulation on PBDEs and sorting work before landfill disposal.     

H(+)/phenanthrene symporter and aquaglyceroporin are implicated in phenanthrene uptake by wheat (Triticum aestivum L.) roots

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic pollutants that are toxic to human and nonhuman organisms. Dietary intake of PAHs is a dominant route of exposure for the general population because food crops are a major source of dietary PAHs. The mechanism for crop root uptake of PAHs remains unclear. Here we reveal that wheat root uptake of PAHs involves active and passive processes. The passive uptake is mercury and glycerol dependent. Mercury and glycerol inhibit uptake, indicating that aquaglyceroporins sensitive to mercury contribute to passive uptake. Active uptake is mediated by a phenanthrene/H symporter. The electrical response of wheat roots triggered by phenanthrene consists of two sequential phases: depolarization followed by repolarization. The depolarization is phenanthrene concentration dependent, with saturation kinetics that have an apparent of K(m) 10.8 μmol L(-1). As uptake proceeds, external solution pH increase is noticed. Lower pH favors the uptake. Vanadate and 2,4-dinitrophenol suppress the electrical response to phenanthrene and phenanthrene uptake, suggesting that plasma membrane H(+)-ATPase is involved in the establishment of an electrochemical proton gradient acting as a driving force for active uptake. Therefore, it is suggested that aquaglyceroporin and phenanthrene/H symporter are implicated in phenanthrene uptake. Our results provide insight into PAH uptake mechanism in wheat roots that is relevant to strategies for reducing PAH accumulation in wheat for food safety, improving phytoremediation of PAH-contaminated soils or water by agronomic practices and genetic modification to target remedial plants for higher PAH uptake capacity.