北京大气沉降样品中的PCBs

采集了4个北京大气沉降样品,包括3个总沉降与1个湿沉降样品.利用高分辨率气质联用仪(HRGC-HRMS),参照国际标准方法分析测定了其中的多氯联苯(PCBs)含量.总沉降样品的PCBs含量水平为4.47～7.08ng·g-1(平均为5.52ng·g-1)和TEQ为0.55～5.43 pg·g-1(平均为2.27 pg·g-1).湿沉降样品含量水平为15.02 ng·g-1,其TEQ为2.87 pg·g-1.首钢样品的TEQ远高于其它3个样品.根据我国大气降尘数据,粗略估计北京PCBs大气沉降通量平均值为67.9 ng·m-2·m-1和TEQ平均通量为27.9 pg·m-2·m-1.首钢样品中,IUPAC编号为77的类二(噁)英PCBs含量异常高,但TEQ仍以编号为126的PCBs所占比例最高.随着取代氯原子数的增加,同族体的含量逐渐降低.     

废弃电容器封存点及旧工业场地多氯联苯的污染特征

研究了四川资阳机车厂废弃电力电容器封存点与旧工业场地土壤与降尘中28种多氯联苯（PCBs）的污染水平与组成特征.电容器封存山洞未封闭洞口处土壤中PCBs含量最高,28种PCBs的总含量（ΣPCBs）达227 502 ng.g-1,铸铁车间窗台降尘中也有高残留的PCBs,ΣPCBs在10μg.g-1以上,封存点和铸铁车间样品中PCBs单体含量之间均存在显著的正相关关系（P〈0.01）.高污染样品中PCBs的同族体分布均以四氯代PCBs为最高,其次为三氯代PCBs和五氯代PCBs.与封存点土壤相比,铸铁车间样品中高氯代PCBs的贡献更大.12种类二英PCBs的毒性当量（TEQ）介于75.43～24 027 pg.g-1之间,远大于电子垃圾拆解区土壤,但普遍都以PCB126的毒性当量贡献占绝对优势.     

典型电力电容器污染土壤中多氯联苯水平及特性

以3个PCBs污染物封存点周边土壤为对象,详尽研究了典型电力电容器污染土壤中209种PCBs同系物含量水平、分布特性及毒性当量,了解污染土壤中PCBs的污染水平和环境风险,为PCBs污染土壤的场地修复提供支撑.对来自于3个污染场地的12个污染土样分析表明,Soil A总PCBs含量为1 705.0μg·g-1±424.3μg·g-1(n=4),高于Soil B(233.0μg·g-1±80.0μg·g-1,n=4)和Soil C(225.7μg·g-1±90.2μg·g-1,n=4),显示3种土壤均受到PCBs严重污染.不同氯代数的PCBs分子中,三氯联苯及四氯联苯含量最高.Soil A、Soil B及Soil C中PCBs的氯元素质量分数分别为43.7%±1.0%、45.5%±0.5%和44.9%±0.3%,这一比例接近Aroclor1242以及国产1号PCB绝缘油.指示性PCBs与总PCBs含量之间存在明显相关关系,线性拟合方程R2=0.998.应用指示性PCBs可有效估算总PCBs含量,简化样品分析过程.类二英多氯联苯以PCB77、PCB105及PCB118为主,三者之和占dl-PCBs的89.5%±4.0%.污染土样的毒性当量(以WHO-TEQ计)介于3.56~63.55 ng·g-1之间,显示该区域具有较高的环境风险.PCB28/31、PCB33/20、PCB66/80、PCB70、PCB32及PCB18等是含量最高的PCB单体.与国内外其他研究相比,该封存点土壤受到了高浓度PCBs污染,具有较高的环境风险.     

官厅水库周边土壤中有机氯农药残留的统计分布特征

采用气相色谱(GC ECD)分析方法测定了官厅水库周边地区土壤样品中HCH、DDT、七氯、艾氏剂等多种有机氯农药的含量,采用数理统计方法研究了不同土地利用类型、不同采样方位与土壤中有机氯农药含量的关系.结果表明,官厅水库周边地区土壤中总HCH含量为0～19 63ng g-1(中位数0 50ng·g-1),总DDT含量为0～176 01ng·g-1(中位数4 42ng·g-1).其它几种有机氯农药的含量未检出.不同的土地利用类型土壤中HCH和DDT的含量均有显著性差异,不同的官厅水库方位对土壤中HCH和DDT的含量不造成显著影响.     

珠三角电子垃圾和城市地区家庭灰尘中多氯联苯的来源及暴露风险

本研究对珠三角电子垃圾和城市地区家庭灰尘中多氯联苯(PCBs)进行了分析.结果表明,清远电子垃圾区灰尘中PCBs的含量为12.4～87765 ng·g-1,平均10167 ng·g-1.室内和庭院灰尘中PCBs的含量无显著差别.电子垃圾区灰尘中PCBs组成模式(以3、5、6、4氯代PCBs为主),与我国工业品中PCBs的组成并不相似,并且室内外灰尘中的组成没有明显的差别.采用化学质量平衡受体模型进行源解析显示,电子垃圾区灰尘中PCBs主要来自Aroclor 1262(36.7%)、Aroclor 1254(26.7%)、Aroclor 1242(21.4%)和Aroclor 1248(18.5%).电子垃圾区婴幼儿、儿童/青少年、成人通过灰尘对PCBs的平均日暴露量分别为42、17和2.9 ng·(kg·d)-1.风险评估显示,婴幼儿、儿童和青少年通过灰尘暴露PCBs的总非癌症危害商数(HQ)均高于1,可对身体健康产生危害,人群终生平均致癌风险为4.5×10-5,处于美国EPA可接受的致癌风险范围.广州地区家庭灰尘中PCBs的平均含量仅为48.7 ng·g-1,这与PCBs并未在我国大范围使用一致.广州地区人群通过家庭灰尘暴露PCBs的风险很低.     

贵州红枫湖地区水稻土多氯联苯和有机氯农药的残留

调查了红枫湖周边水稻土的7种多氯联苯（PCBs）和13种有机氯农药（OCPs）的含量分布.结果显示,DDTs及其代谢产物、HCHs的异构体、异狄氏剂、七氯等有机氯农药及PCB 28和PCB 52在所有样品中均被检出.与国内外污染区相比,PCBs含量较低.研究区土壤中污染物的组成结果类似,PCBs以3～5氯取代的同属物为主,农药以DDTs为主.剖面土壤中∑PCBs含量范围为8.9～55.9 ng/g,主要以3～5氯取代的PCBs为主,平均占PCBs总量的89%.∑DDTs含量为 4.7～42.6ng/g,以p,p′-DDE,p,p′-DDT为主.DDT/（DDD+DDE）的比率表明红枫湖地区水稻田中DDTs的降解速率不同,暗示其环境条件的差异.α-HCH/γ-HCH为0.28～0.90,表明红枫湖地区水稻田中HCHs在环境中残留时间很长,经历了光解和生物作用等变化.PCBs对TEQ的贡献较低,为0.06～0.51 pg/g.     

南海北部沿岸牡蛎体内PCBs的时空分布特征及评价

于2008~2012年间在南海北部沿岸海域的23个重要港湾采集近江牡蛎(Crassostrea rivularis Gould )样品,用气相色谱法测定其中多氯联苯(PCBs)的残留量,并对其残留水平、时空分布趋势、组成特征以及食用安全性进行探讨与评价.结果表明:南海北部沿岸牡蛎体内的PCBs的含量范围在8.11~29.10ng/g之间(湿重,下同),平均值是(16.57±4.40)ng/g,出现频率呈正态分布.在时间上,广东、广西和海南沿岸PCBs含量随时间呈下降的总体趋势;空间分布上,珠江口岸段PCBs含量明显高于粤东、粤西、广西和海南4个岸段.PCBs同系物中以五氯联苯在总PCBs含量最高,占47.9%,其次是三氯和四氯联苯,二者之和占总PCBs的30.6%; 同系物以PCBl05、PCB118和PCB101+113为优势组分,3者之和占总量的百分比为24.0%.南海北部沿岸牡蛎体内的PCBs残留量远低于国内外相关食品安全限量标准,估算的沿海居民食用牡蛎的PCBs 暴露量为5.52ng/(kg·d),仅占世界卫生组织(WHO)设定的每日耐受量值的27.6%.PCBs的二 毒性当量(TEQ)平均值为39.4pg/g.     

典型钢铁厂周边土壤中多氯联苯分布特征研究

钢铁厂中各工业热过程车间都会产生污染物并对周边环境造成危害,本文以迁安市钢铁厂周边土壤为研究对象,对该市内及钢铁厂周边土壤样品进行采集,采用同位素稀释高分辨气相色谱-高分辨质谱方法(HRGC/HRMS)测定了多氯联苯(PCBs)的含量,研究了PCBs的同类物分布特征.结果发现,市内及钢铁厂周边土壤样品中dl-PCBs的总含量为4.77~462.04 pg·g~(-1),WHO-TEQ(Toxic Equivalent Quantity)即毒性当量值为0.03~1.34 pg·g~(-1).由此可以看出,该市及钢铁厂周边环境土壤受到了PCBs等有毒污染物的影响.大部分土壤样品的同类物分布特征相似;PCB~(-1)18对土壤dl-PCBs含量贡献率最大,贡献率为34%.PCB~(-1)01对土壤指示性PCBs含量贡献率最大,贡献率为42.5%.同时,通过对样品中同类物分布可以看出,低氯代的同类物(Tr CBs~Hx CBs)的含量要远高于高氯代同类物(Hp CBs~De CBs).     

安徽省部分城市土壤中全氟化合物空间分布及来源解析

为探究安徽省城市土壤中全氟化合物(perfluorinated compounds,PFCs)的污染特征、空间分布及潜在的来源.2013年采集安徽省7个城市共11个土壤样品,利用超高效液相色谱-串联质谱联用分析了15种PFCs的含量,并运用主成分分析-线性回归法解析其可能来源.结果表明,被调查的11个城市土壤样品中的ΣPFCs的含量(以干重计,下同)范围为1.15~5.89 ng·g-1,平均含量2.69 ng·g-1.含量最高的单体PFCs是全氟辛烷磺酸(perfluorooctane sulfonate,PFOS),含量范围为n.d.~3.56 ng·g-1,均值含量为0.96 ng·g-1,其次是全氟辛烷羧酸(perfluorooctane acid,PFOA),含量范围为n.d.~2.89ng·g-1,均值含量为0.64 ng·g-1;ΣPFCs含量最高地区是滁州地区(5.89 ng·g-1),以PFOS和PFOA为主,其次为宣城市泾县(4.04 ng·g-1),而其中PFOS含量高达3.56 ng·g-1,占ΣPFCs的88.1%,这可能与该地发达的造纸行业有关;与我国其他地区土壤中PFCs含量相比,安徽省被调查地区的城市土壤中PFCs的含量居于中等水平;安徽省部分城市土壤中60%的PFCs可以有4个因子进行解释,代表性PFCs有PFOA、全氟丁烷磺酸(perfluorobutane sulfonate,PFBS)、全氟十二烷羧酸(perfluorododecanoic acid,PFDo A)、全氟丁烷羧酸(perfluorobutane acid,PFBA)和PFOS.     

珠江三角洲地区大气和土壤中多氯联苯分布特征研究

为了考察珠江三角洲地区大气和土壤中多氯联苯(PCBs)残留现状,于2012年在珠江三角洲地区采集了空气和土壤样品,并利用GC-MS进行PCBs分析测定。结果表明,大气中Σ24PCBs的总浓度为240~2 258 pg/m3,平均为1 243 pg/m3,且PCBs主要存在于气相中,占24种PCBs总浓度的90%以上,单体分布主要以三氯~五氯联苯为主。自2001年以来珠江三角洲地区大气中PCBs浓度有小幅波动,说明部分地区有PCBs源释放的可能。土壤中24种PCBs的总浓度为ND~20.68 ng/g,平均为3.77 ng/g。三氯联苯是土壤中PCBs的主要同类物,平均占土壤中24种PCBs总浓度的45%,其次是四氯联苯,平均占19%。部分地点低氯代PCBs比例下降,高氯代比例升高。     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.