The thermal transformation mechanism of chlorinated paraffins: An experimental and density functional theory study

The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.     

永定河(北京段)水资源、水环境的变迁及流域社会经济发展对其影响

考察了官厅水库和永定河（北京段）1954—2008年水资源及1980—2005年水环境的变迁,并通过Pearson相关分析探讨了流域社会经济发展对永定河（北京段）水资源和水环境的影响.研究结果表明,①官厅水库建成后近50年来水量和出库水量均大幅衰减,例如,官厅水库来水量从1959年的25.56亿m3锐减至2008年的0...     

Regulated emission characteristics of in-use LNG and diesel semi-trailer towing vehicles under real driving conditions using PEMS

On-road driving emissions of six liquefied natural gas(LNG) and diesel semi-trailer towing vehicles(STTVs) which met China Emission Standard IV and V were tested using Portable Emission Measurement System(PEMS) in northern China.Emission characteristics of these vehicles under real driving conditions were analyzed and proved that on-road emissions of heavy-duty vehicles(HDVs) were underestimated in the past.There were large differences among LNG and diesel vehicles, which also existed between China V vehicles and China IV vehicles.Emission factors showed the highest level under real driving conditions, which probably be caused by frequent acceleration, deceleration, and start-stop.NOx emission factors ranged from 2.855 to 20.939 g/km based on distance-traveled and 6.719–90.557 g/kg based on fuel consumption during whole tests, which were much higher than previous researches on chassis dynamometer.It was inferred from tests that the fuel consumption rate of the test vehicles had a strong correlation with NOx emission, and the exhaust temperature also affected the efficiency of Selected Catalytic Reduction(SCR) aftertreatment system, thus changing the NOx emission greatly.THC emission factors of LNG vehicles were 2.012–10.636 g/km, which were much higher than that of diesel vehicles(0.029–0.185 g/km).Unburned CH_4 may be an important reason for this phenomenon.Further on-road emission tests, especially CH_4 emission test should be carried out in subsequent research.In addition, the Particulate Number(PN) emission factors of diesel vehicles were at a very high level during whole tests, and Diesel Particulate Filter(DPF)should be installed to reduce PN emission.     

混凝法处理锰矿选矿废水的试验研究

选取聚合氯化铝（PAC）、聚合硫酸铁（PFS）、聚丙烯酰胺（PAM）和六水合氯化铁（FC）4种常用混凝剂,采用正交试验,以去浊率与去锰率作为综合评价指标,探讨了不同混凝剂处理锰矿选矿废水的效果及最佳混凝条件。结果表明：在以上混凝剂中,FC的混凝效果较差;PAM对锰矿选矿废水的处理效果最优,最佳的混凝条件为：处理500 ml的废水,投加1.5 ml的PAM,pH为7.0,搅拌后沉降20 min,废水经处理后去浊率与去锰率分别为96%、92%,其中废水的pH及投药量对混凝效果的影响较大。     

多氯联苯对我国土壤微生物的生态毒理效应

作为持久性有机污染物(POPs),多氯联苯(PCBs)一旦进入土壤将长期存留并对土栖生物产生潜在危害。土壤微生物是土壤生态系统重要组成部分,研究外源PCBs对土壤微生物的生态毒理效应,筛选出指示PCBs污染的敏感指标并获取可靠的生态毒理数据十分重要。研究以江西红壤和天津潮土为供试土壤,在室内25℃连续培养28 d的条件下进行了生态毒理实验,选择了微生物量碳、呼吸强度、代谢熵、硝化作用、脱氢酶活性、脲酶活性和微生物群落功能多样性为微生物指标。结果显示:1)在28 d培养时间内,多氯联苯(PCBs)的毒性作用随培养时间的延长而增强,且在红壤中的毒性作用强于在潮土中,表明PCBs对土壤微生物的毒性作用存在时间效应并受土壤性质的影响。2)各微生物指标的敏感性不同,微生物量碳、脲酶活性和微生物功能多样性对PCBs污染反应不够敏感,而土壤呼吸强度、代谢熵、硝化作用和脱氢酶活性对PCBs污染反应敏感。3)14 d时,红壤中PCBs对脱氢酶活性、呼吸强度和代谢熵的EC10值分别为1.20、3.18和1.09 mg·kg-1,而在潮土中分别为6.31、4.73和50 mg·kg-1;28 d时,红壤中PCBs对硝化作用、脱氢酶活性、呼吸强度和代谢熵的EC10值分别为2.32、0.77、0.51和0.71mg·kg-1,而在潮土中分别为5.91、1.65、3.00和50 mg·kg-1。综合考虑经济和实际需要等因素,建议将呼吸强度、硝化作用和脱氢酶活性作为PCBs污染土壤生态毒理评价中的首选敏感指标,并建议培养时间设置为28 d。     

马拉硫磷及其水解产物对圆瘤浮萍的生长抑制及氧化损伤作用

为了探讨马拉硫磷和主要水解产物对圆瘤浮萍的生长抑制作用及可能的氧化损伤机制,采用静态培养法,研究不同浓度的马拉硫磷及其水解产物二甲基二硫代磷酸酯(DMDTP)、二甲基硫代磷酸酯(DMTP)、二甲基磷酸酯(DMP)对圆瘤浮萍生长、叶绿素含量、叶绿体活性、超氧化物歧化酶(SOD)、过氧化物酶(POD)和过氧化氢酶(CAT)活性及丙二醛(MDA)含量的影响。结果表明,暴露7 d后,浓度为100 mg a.i.·L-1处理下的浮萍叶状体生长量与空白对照组无显著性差异;DMDTP、DMTP和DMP对圆瘤浮萍叶状体生长量的半数抑制浓度(7 d-IC50)分别为52.9、45.5和98.0 mg a.i.·L-1。随着试验液中DMDTP、DMTP和DMP浓度的升高,圆瘤浮萍叶绿素含量均明显降低,叶绿体活性则分别表现为诱导-抑制、抑制和抑制效应。在DMDTP、DMTP和DMP胁迫下,脂质过氧化产物丙二醛(MDA)含量明显增加;圆瘤浮萍体内的抗氧化酶系统均受到影响。总体表现为随着DMDTP浓度的增加,SOD活性先降低后升高;DMTP和DMP胁迫下,SOD活性呈现先降后升再降的趋势;POD和CAT活性则随3种水解产物浓度的增加呈现先升后降趋势;这表明抗氧化酶系统对外部胁迫的应答很复杂。马拉硫磷对圆瘤浮萍的毒性较小,其水解产物DMDTP、DMTP和DMP均对圆瘤浮萍的生长产生一定的毒性作用。在实际生产中,应多加关注马拉硫磷水解产物对环境生物的风险评估。     

In vitro biotransformation of PBDEs by root crude enzyme extracts: Potential role of nitrate reductase (NaR) and glutathione S-transferase (GST) in their debromination

In order to investigate the enzyme transformation of PBDEs and to track the key enzymes involved in PBDE degradation in plants, in vivo exposure of plants of ryegrass, pumpkin and maize and in vitro exposure of their root crude enzyme extracts to PBDEs were conducted. Degradation of PBDEs in the root crude enzyme solutions fit well with the first order kinetics (R² = 0.52–0.97, P < 0.05), and higher PBDEs degraded faster than the lower ones. PBDEs could be transformed to lower brominated PBDEs and hydroxylated-PBDEs by the root crude enzyme extracts with debromination as the main pathway which contributed over 90% of PBDE depletion. In vitro and in vivo exposure to PBDEs produced similar responses in root enzyme activities of which the nitroreductase (NaR) and glutathione-transferase (GST) activities decreased significantly, while the peroxidase, catalase and cytochrome P-450 activities had no significant changes. Furthermore, higher enzyme concentrations of NaR and GST led to higher PBDE debromination rates, and the time-dependent activities of NaR and GST in the root crude enzyme extracts were similar to the trends of PBDE depletion. All these results suggest that NaR and GST were the key enzymes responsible for PBDE degradation. This conclusion was further confirmed by the in vitro debromination of PBDEs with the commercial pure NaR and GST.     

Estimation and characterization of PCDD/Fs and dioxin-like PCBs from Chinese iron foundries

The iron foundry industry is considered to be a potential source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study investigated the emission factors and total emission amounts of PCDD/Fs and dioxin-like polychlorinated biphenyls (DL-PCBs) from iron foundries in China. The concentrations and the World Health Organization toxicity equivalents (WHO-TEQs) are presented and the congener profiles are discussed in this paper.In the present work, 26 fly ash samples were collected and tested to quantify the PCDD/Fs and DL-PCBs generated by 14 plants of different scales, and five stack gas samples were collected from two (named as EFG and LFG) of those plants. The emission levels of PCDD/Fs and DL-PCBs indicated that hot-air cupolas had lower emissions than cold-air cupolas. When iron ore lump and sinter were used as raw material, the emission factors were about 250 ng TEQ t⁻¹ of product. However, if the raw material was scrap, the emission factors varied owing to the different contents of organic materials in the raw materials. It was found that the mean WHO-TEQ values of PCDD/Fs and DL-PCBs were 144 and 34.2 pg Nm⁻³ in stack gas and 20.0 and 1.58 pg g⁻¹ in fly ash. In multiple tests, it was estimated that the mean emission factors of PCDD/Fs and DL-PCBs were 365 and 10.9 ng WHO-TEQ t⁻¹ released to residue and 2719 and 555 ng TEQ t⁻¹ released to air. The total emission amounts of PCDD/Fs and DL-PCBs from Chinese iron foundries with cupola furnaces released to residue and air were 16.8 and 146 g WHO-TEQ in 2008, respectively.     

高负荷人工土层地下渗滤系统处理生活污水中试工程的研究

对传统的地下渗滤系统进行改进,采用多层过渡结构的人工土层来增大对颗粒有机物的接触氧化表面积,同时设置曝气装置保证好氧过程的氧气供应,可以大大提高污水地下处理系统的水力负荷.以中国南方典型的红壤土、河沙和砾石为填充材料,处理广州地化所小区的生活污水,水力负荷达40 cm/d,远大于类似系统.试验结果表明,改进后的系统能创造良好的好氧/厌氧环境,对污染物去除效果良好,COD、BOD5、TN、NH 4-N、TP和SS去除率分别达到了76.7%～89.1%、83.3%～92.5%、50.3%～66.1%、65.2%～79.6%、75.4%～90.1%和77.0%～91.3%,出水主要污染物达到了《污水综合排放标准》(GB 8978-1996)一级排放标准或二级排放标准.     

风雨联合作用下风向对大跨度悬挑屋盖的压力分布影响研究

强降雨通常伴有强风作用,风向成为影响结构表面压力分布的重要因素之一。目前大跨度挑檐屋盖设计基本只考虑垂直于结构表面的单独雨荷载作用,对风雨联合作用下建筑表面压力分布研究甚少。研究风雨联合作用下,不同风向对大跨度悬挑屋盖表面的压力分布影响特性。基于数值模拟平台,采用欧拉-欧拉方法,模拟得到了不同风向工况下大跨度悬挑屋盖结构表面平均压力分布规律,并研究得到了一次自然降雨过程中最不利抗风雨位置,对相应大跨度悬挑结构设计提出了有益参考。