丁二烯过氧化物的生成、危害及安全性研究

综述了国内外丁二烯过氧化物研究进展，主要包括丁二烯过氧化物的危害性、成因、危险评价和热稳定性，并对今后的研究方向进行了展望。     

珠江上游少数民族县域经济活动的累积环境效应研究--以贵州三都水族自治县为例

为了探索珠江上游少数民族区域经济活动的累积环境效应与生态安全，我们选择三都水族自治县作为定位研究基地．对建国以来区域内经济活动变迁进行历史、现状研究和综合评估，揭示历史时期发展政策、发展模式、重大经济活动等人为扰动因素在区域生态环境系统退化过程中的作用．评估少数民族经济活动的累积环境效应与生态安全。     

A review of polybrominated diphenyl ethers and alternative brominated flame retardants in wildlife from China: Levels, trends, and bioaccumulation characteristics

Accelerated industrialization and urbanization, and unregulated disposal of waste of electric and electronic equipment (e-waste) in China have caused environmental pollution of brominated flame retardants (BFRs). This review summarized the levels, trends, and bioaccumulation characteristics of polybrominated diphenyl ethers (PBDEs) and other potential alternative BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-dibromophenoxy) ethane (BTBPE) and decabromodiphenylethane (DBDPE) in wildlife from China. PBDE levels in wildlife from China were generally higher than those from other parts in Asia, and were comparable to those from Europe but were lower than those from North America. However, wildlife from the e-waste recycling sites in South China and East China contained much higher PBDEs compared to other reports around the world, suggesting the heavy contamination of PBDEs in these regions. The alternative BFRs were also detected in wildlife, revealing that the animals are exposed to these chemicals, in addition to PBDEs. Temporal trends indicated by levels in marine mammals from South China suggested that PBDE levels increased from the beginning of 1990s to 2000s, but decreased from the middle of 2000s, followed by relatively steady levels. In contrast, HBCDs were found to be continuously increasing from 1997 to 2007, indicating the increasing usage of HBCDs in China in recent years. Compared to PBDE profiles found in other parts, aquatic species and birds from China contained relatively higher contributions of BDE-28 and 209, respectively, suggesting the possible different usage pattern of PBDEs. Future works including keeping monitoring at a reasonable scale and frequency to make sure levels near urban centers indicative of population do not increase are needed. Additionally, focus effort on e-waste recycling regions to look for impacts and to determine if regulation/controls are resulting in lower environmental contamination, and incorporation of sentinel species in monitoring efforts are recommended.     

Operating condition influences on PCDD/Fs emissions from sinter pot tests with hot flue gas recycling

This study was designed to clarify the influence of operating conditions on the formation and emissions of polychlorinated-pdibenzodioxins and dibenzofurans (PCDD/Fs) from a sintering process with hot flue gas recycling. A pilot scale sinter pot with simulated flue gas recycling was developed, and four key operational parameters, including temperature, oxygen content of the simulated waste flue gas, the coke rate of the sintering mixture, and the quicklime quality, were selected for exploring PCDD/Fs formation. The results showed that the temperature of the recycled flue gas had a major affect on PCDD/Fs formation, and a high temperature could significantly increase their formation during sintering. A clear linear correlation between the temperature of recycling flue gas and PCDD/Fs emission (r = 0.93) was found. PCDD/Fs could be reduced to a certain extent by decreasing the level of oxygen in the recycled flue gas, while sintering quality was unchanged. The coke rate had no significant influence on the formation of PCDD/Fs, but the quality of quicklime used in the sintering mixture could affect not only the amount of PCDD/Fs emissions but also the sintering productivity. Compared with a benchmark sinter pot test, PCDD/Fs emissions markedly decreased with improvements to quicklime quality. However, the reduction in PCDD/Fs emissions realized by using high-quality quicklime was limited by the temperature of the inlet gas. The highest reduction achieved was 51% compared with conventional quicklime when the temperature of the inlet gas was 150°C.     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Occurrence of selected aliphatic amines in source water of major cities in China

The formation of toxic nitrogenous disinfection byproducts (N-DBPs), such as nitrosamines, halonitromethanes and haloacetonitriles, from reactions between chlorine/chloramine and dissolved organic nitrogen in drinking water has caused great concern with regarding public health. This study revealed the occurrence of 17 aliphatic amines, some of which have been confirmed to be the precursors of N-DBPs, in source water across China. A sensitive method based on benzenesulfonyl chloride derivatization and liquid-liquid extraction followed by GC-MS analysis was established for the simultaneous analysis of the selected amines in aqueous samples. In total, 37 source water samples from the capital cities of 20 provinces were collected for the survey. Among the 17 amines, 14 were detected with an average frequency of detection of 36%. The most relevant amines in terms of frequency and maximum concentrations detected were dimethylamine (100%, 24.82 μg/L), methylamine (78%, 0.92 μg/L), N-methylethylamine (70%, 8.84 μg/L), propylamine (59%, 10.69 μg/L), diethylamine (54%, 3.76 μg/L), N-methylbutylamine (35%, 3.07 μg/L), N-ethylpropylamine (35%, 0.52 μg/L), and piperidine (32%, 2.35 μg/L). This is the first large scale survey of the aliphatic amines occurrence in source water in the world. The wide presence of nitrosamine precursors like dimethylamine, N-methylethylamine and diethylamine, and the precursors of haloacetonitriles and halonitromethanes like methylamine and propylamine suggests that better source water management is required to ensure the safety of drinking water.     

某危险废物填埋场地下水污染预测及控制模拟

以某危险废物填埋场为研究对象,在收集其水文地质资料基础上,运用Visual Modflow建立填埋场地下水水流和溶质运移耦合模型,对填埋场防渗层发生渗漏后,渗滤液中Cr6+在地下水中的运移过程以及地面硬化、防渗墙和排水沟3种污染控制措施对污染羽阻隔效果进行模拟预测.结果表明,Cr6+随地下水流方向运移形成污染羽,10 a后污染羽到达水塘边界,运移距离约为1 450 m,但随后10～20 a之间污染羽扩散范围没有明显扩大;地表硬化后,20 a内污染羽未扩散至水塘边界;防渗墙设置到上层含水层底部时,监测井Cr6+浓度高于未设置防渗墙时浓度,设置到下层含水层底部时,Cr6+浓度与设置于上层含水层时监测结果相反;排水沟日排水量达到2 642 m3时能有效控制污染羽扩散,20 a后污染羽尚未污染监测井;地表硬化与排水沟组合控制污染物扩散,效果最佳,同时排水沟日排水量可减少为1 878 m3.因此,当填埋场发生渗漏时,建议采用设置排水沟与周边地表硬化组合的地下水污染控制措施.     

全国大气扩散输送模态与区划研究

基于NCEP再分析气象资料,使用HYSPLIT模式对我国大陆区域进行了一整年的连续轨迹计算.轨迹以1°×1°的网格化经纬度分辨率进行计算.考虑气候、地理及经济因素,将全国计算区域分为10个大区,分别统计各大区出发的轨迹在全国的分布频率.根据全年和各季的轨迹统计结果,分析我国不同区域的大气输送扩散特征以及区域间大气环境的相互影响潜势.结果表明,全国10个大区的大气扩散输送模态可分为特性不同的7大类,其中以西北方向的3个大区为一类,西南高原的2个大区为另一类,其它各区自成一类.10个大区大气扩散物质的累积效应差异显著且季节变化特征各异.全国以西南区(XN)东部大气累积效应最强,东北区(DB)累积效应最弱.     

基于遥感资料的中国东部地区植被VOCs排放强度研究

本研究充分基于遥感资料获取中国东部地区叶面积指数和叶生物量的最新信息,并广泛调研了植被VOCs排放因子的最新研究进展,以2008—2010年的植被和气象的平均状态为背景,基于MEGAN排放模型,研究了中国东部地区植被VOCs(BVOCs)排放的时空分布特征.结果表明,我国东部地区BVOCs年排放总量为11.3×106t(以C计,下同),其中异戊二烯(ISOP)、单萜烯(MON)和其它VOC(OVOC)质量分数(下同),分别为44.9%、31.5%、23.6%.BVOCs排放呈现明显的季节变化特征,春、夏、秋、冬4个季节分别占全年的11.2%、71.8%、14.1%和3.0%.空间分布上,排放高值区主要分布于大小兴安岭、长白山脉、秦岭大巴山脉、东南丘陵、海南等植被茂密的区域,年均排放强度一般在1500～6000kg·km-·2a-1之间,福建、广东、江西、浙江、湖南、湖北等省份BVOCs的排放总量与平均排放强度均较高.本研究所得到的高时空分辨率的BVOCs排放清单,可以为区域环境与气候的数值模拟研究提供基础.     

缺氧条件下土壤砷的形态转化与环境行为研究

采集张士污灌区0～100 cm深的土壤并在实验室里负载低浓度的砷,采用不加硫和加硫对比研究了厌氧条件下土著微生物对土壤中砷的形态转化、环境行为影响及其机制.结果表明,在不外加硫酸盐条件下厌氧培养8 d后,微生物还原作用造成砷的大量还原和释放,释放的砷70%以上是以As(Ⅲ)形式存在,尤其20～40 cm深度土壤砷的释放量明显高于其它层土壤,As(Ⅲ)和As(T)分别达到892.8μg.L-1和1 240.6μg.L-1.与非生物对照相比每层土中盐酸可提取的砷总量都大大降低,且盐酸提取的As(T)几乎全部转化为As(Ⅲ).伴随砷的释放,铁发生还原和释放,溶解态的亚铁基本都在40 mg.L-1以上,不同土层固相中亚铁离子的量都在9.0～13.4 g.kg-1范围内,固相盐酸可提取态总铁中亚铁离子所占的比例基本都在50%以上,说明微生物还原作用造成固相中铁氧化物发生还原性溶解和矿物结构转化.当体系中添加10 mmol.L-1的硫酸盐时,每层土的生物培养体系中铁的释放几乎完全被抑制,砷和铁浓度也减少了50%.与不加硫生物培养体系相比,固相中盐酸可提取的砷量减少了50%,一部分砷被转化为稳定的硫化物As2S3而固定.可见在硫酸盐不足条件下微生物还原作用可造成砷被还原、活化和释放,而补充土壤中硫酸盐的量可促使微生物还原/活化的砷转化成更加稳定的形态,稳定的硫化物矿物As2S3是土壤微生物固定砷的重要途径.