基于GIS和PMF模型的石嘴山市土壤多环芳烃空间分布及来源解析

随着城市化和工业化进程加速,城市土壤多环芳烃（PAHs）含量及污染状况受到广泛关注.以石嘴山市为例,分析8个城市功能区156个表层土壤（0~20 cm）样品PAHs含量的空间分布特征,运用单因子指数、内梅罗综合指数和终生癌症风险增量模型评价土壤PAHs污染状况,利用正定矩阵因子分解模型（PMF）对PAHs来源进行解析.结果表明,石嘴山市表层土壤PAHs总含量均值为489.82 ng·g^-1,除芘（Pyr）外的15种PAH单体变异系数均大于100%,属强变异;不同功能区土壤PAHs含量呈现出：交通区（1217.61 ng·g^-1） > 工业区（809.58 ng·g^-1） > 公园（273.66 ng·g^-1） > 文教区（268.18 ng·g^-1） > 商业区（240.05 ng·g^-1） > 农业区（226.81 ng·g^-1） > 医疗区（211.90 ng·g^-1） > 居民区（183.49 ng·g^-1）;内梅罗综合指数显示82.58%的样点不存在污染,轻微、轻度和中度污染占比分别为6.45%、4.52%和0.65%,5.8%的样点存在重度污染;健康风险评价结果表明,皮肤接触和误食是最主要的土壤PAHs暴露途径,其健康风险处于可接受水平;源解析表明石嘴山市土壤PAHs的主要来源为交通排放源、煤炭燃烧源、生物质/重油燃烧的混合源以及石油源,其贡献率分别为10.5%、36.6%、50.3%和2.6%,且高值大多分布在工业或煤炭生产区域.研究结果可为工业城市土壤污染研究提供参考,并对预防土壤污染、保障土壤环境质量及人体健康安全有积极作用.     

偏远高山湿地土壤中PAHs污染特征:以神农架大九湖为例

于2012年4月沿大九湖湿地平均分布10个采样点,各采集0~10、10~20以及20~30 cm浅层土壤,采用GC-MS对大九湖湿地浅层土壤中USEPA 16种优控多环芳烃（PAHs）进行分析,对其分布、组成、来源进行了详细的讨论,并对高山湿地PAHs污染标志物进行了浅析.结果表明,研究区0~10、10~20、20~30cm浅层土壤中∑₁₆PAHs含量分别为48.55~984.73、14.36~806.47、12.84~1191.53 ng·g^-1,均值分别为302.94、142.98、208.68 ng·g^-1;7种致癌单体多环芳烃含量范围分别为21.20~844.29、2.96~592.06、0.66~964.70 ng·g^-1,均值分别为197.25、93.16、147.16 ng·g^-1,分别占总PAHs的65.12%、65.13%、69.08%;泥炭区PAHs含量明显高于非泥炭区,且已达到重度污染程度;PAHs组成以4、5、6环为主;结合IcdP/（IcdP+BghiP）及Pyr/BaP比值分析,推测大九湖湿地浅层土壤中PAHs主要来源于化石燃料及木材的燃烧,近年来旅游车辆的进入对PAHs的贡献较大;对浅层土壤中各单体PAH与PAHs总含量进行回归分析表明、苯并（b）荧蒽、茚（1,2,3cd）并芘、苯并（a）蒽作为泥炭地PAHs标志性化合物,用来评价PAHs的污染程度.     

新疆典型地区植物和土壤多环芳烃污染特征、来源解析及健康风险评价

利用气相色谱-质谱法（GC-MS）测定新疆多段公路沿线和3个风景区植物和土壤中多环芳烃（PAHs）含量.结果表明,11个采样点的11个土壤样品Σ₁₆PAHs含量为18.82~2153.54 ng·g^-1,平均值为425.95 ng·g^-1,36个采样点的59个植物样品中Σ₁₆PAHs含量范围为9.93~748.30 ng·g^-1,平均值为154.11 ng·g^-1.植物样品中不同环数的PAHs平均含量高低次序为：低环（2~3环）>中环（4环）>高环（5~6环）,土壤样品不同环数的PAHs平均含量高低次序为：中环（4环）>高环（5~6环）>低环（2~3环）.特征比值法和主成分分析法分析得出,土壤中PAHs主要为燃烧和石油源,植物吸收的PAHs主要来源为木材燃烧和炼焦工业.健康风险评价结果表明,S323省道库尔勒段土壤PAHs对道路工作人员致癌风险值（CR）为1.26×10^-6,存在潜在健康风险.     

东北小兴凯湖沉积物POPs污染特征及生态风险评价

采用GC-MS分析了小兴凯湖表层沉积物多环芳烃（PAHs）、有机氯农药（OCPs）和邻-苯二甲酸酯（PAEs）的污染特征,探讨了污染物的主要来源及生物毒性风险.结果表明：①小兴凯湖沉积物中PAHs含量范围在82.1~534.6 ng·g^-1之间,西北湖区含量较高.沉积物中OCPs和PAEs含量范围分别在4.8~50.4 ng·g^-1和33.3~401.6 ng·g^-1之间,东南湖区含量较高;②沉积物中PAHs以3~5环化合物为主（占85%以上）,主要为燃烧源,其中煤和薪柴燃烧贡献47%,汽油和柴油燃烧贡献39%,石油产品泄漏贡献14%.OCPs以六氯环己烷（HCH）为主（占78%）,主要来源于新的林丹的使用和少量工业HCHs的输入.PAEs以邻-苯二甲酸二正丁酯（DBP）和邻-苯二甲酸二（2-乙基己）酯（DEHP）为主（占94%）,生活垃圾和工农业生产为其主要来源;③小兴凯湖沉积物中PAHs、OCPs和PAEs在东北地区处于低水平污染,相比于国内其他地区的湖泊河流,总体处于低污染水平,目前无生态风险,但部分点位OCPs具有中度生态风险.     

南水北调中线源头淹没区土壤中多环芳烃的赋存分布特征

研究了南水北调中线源头淹没区农田土壤中多环芳烃(PAHs)的分布特征与来源.采集了丹江口水库淅川淹没区(高程170 m以下)8个乡镇的18个农田土壤.以索氏提取法对样品处理后,采用GC/MS对土壤中美国EPA优先控制的16种PAHs进行了检测分析.结果表明,淹没区农田土壤中共有10种PAHs组分检测出,总残留量范围为5.29~173.11 ng·g^-1,平均值为41.89 ng·g^-1,具有致癌作用的组分苯并 蒽(Baa)、 (Chr)和苯并(b)荧蒽(Bbf)含量约占PAHs总残留量的2.4%.个别采样点的PAHs残留量高于荷兰政府规定的无污染土壤的PAHs值(干重:20~50 ng·g^-1),表明淹没区部分农田土壤已受到轻微的PAHs污染.通过使用PAHs环数相对丰度法和Phe/Ant、Fla/Pyr、Ant/(Ant+Phe)和Fla/(Fla+Pyr)等分子标志物指示法来解析PAHs来源,结果显示,淅川淹没区土壤中PAHs的来源主要是煤等化石燃料和草木等植物性燃料的燃烧,少量来源于汽车尾气的排放以及石油产品的泄漏.淹没区农田土壤中PAHs污染存在一定的生态风险,值得进一步关注.     

北江中上游地表水和沉积物中PAHs和PCBs污染特征和风险评估

采用气相色谱-质谱法（GC-MS）测定了北江中上游流域地表水和沉积物样品中多环芳烃（PAHs）和多氯联苯（PCBs）类污染物的含量,分析了PAHs和PCBs的污染水平和空间分布,并评估了污染物的健康风险和生态风险.结果表明,16种PAHs单体在所有水样和沉积物样品中均被检出,检出范围分别为41.82~443.04 ng·L^-1和59.58~635.73 ng·g^-1,北江中上游PAHs的污染水平为中、轻度.水中PAHs以二环芳烃和三环芳烃为主,沉积物中以三环芳烃和四环芳烃为主.在水样中检出了17种PCBs,浓度范围0.81~287.50 ng·L^-1,以六氯联苯和七氯联苯为主;沉积物中检出了8种PCBs,含量范围0.13~3.96 ng·g^-1,以五氯联苯和七氯联苯为主.整个调查区域内地表水中PAHs和PCBs的终生致癌风险指数小于10^-4,处于中、低水平;非致癌风险指数均小于1,不存在非致癌风险.采用风险商值（RQ）法对地表水中污染物进行生态风险评价,研究区域内地表水中PAHs和PCBs生态风险总体处于中低风险水平,个别点位存在重度风险的污染物单体,值得引起重视.采用沉积物质量基准法（SQGs）对沉积物中污染物进行生态风险评估,沉积物中PAHs和PCBs均处于较低的生态风险水平.     

江汉平原典型土壤环境中有机磷农药的分布特征及影响因素

为了研究江汉平原土壤中有机磷农药（OPPs）的分布特征,项目组于2015年9月在地下水监测场所在区域,采集了78个剖面土和7个表层土土样,通过气相色谱-氮磷检测器（GC-NPD）分析OPPs的含量,研究江汉平原土壤中OPPs的分布特征.结果表明,研究区土壤普遍存在OPPs,其中地表土中OPPs的含量范围为89.80~193.85 ng·g^-1,平均值为140.05 ng·g^-1;剖面土中OPPs的整体含量范围为19.81~138.28 ng·g^-1,平均值为40.99 ng·g^-1.地表土和剖面土中OPPs主要检出成分均为甲胺磷、氧化乐果、二嗪农和喹硫磷等,并且根据美国土壤农药残留限量标准,研究区土壤中10种OPPs的残留量已对农产品的安全构成威胁.研究区剖面土中∑OPPs分布为：水平方向,沿河农田剖面土 > 沿河非农田剖面土 > 中部农田剖面土,即：GS1-1 > GS4 > GS2 > GS3;垂直方向,大部分剖面土随着深度的增加整体上呈先减小后增大的趋势;研究区土壤中OPPs的分布受多种因素的影响：农业生产过程中施用OPPs的量、土壤对OPPs的吸附、解吸附作用、地下水的垂直运动、研究区的地形环境、土壤有机质的含量等.     

燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃的赋存特征和毒性风险

研究了燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃（HPAHs）的赋存特征、生成机制和毒性效应.结果表明,燃煤电厂和垃圾电厂飞灰中氯代PAHs （Cl-PAHs）的含量为1.06~1.67 ng·g^-1和2.76 ng·g^-1,溴代PAHs （Br-PAHs）的含量为26.4~44.2 ng·g^-1和6.31 ng·g^-1;垃圾电厂飞灰中Cl-PAHs的含量明显高于燃煤电厂,主要是因为生活垃圾中含有大量的聚氯乙烯为代表的塑料.来自煤粉炉的飞灰中Br-PAHs和Cl-PAHs的含量明显低于循环流化床燃煤飞灰,主要是因为煤粉炉具有更高的燃烧温度和燃烧效率.燃煤电厂飞灰中主要为7-BrBaA和9-ClPhe;垃圾电厂除尘器飞灰中Br-PAHs主要为9-BrPhe和2-ClAnt.7-BrBaA和9,10-Br₂Ant在燃煤电厂除尘器飞灰的含量远高于其在底灰和脱硫石膏的含量,但摩尔质量相对较小的2-BrFle在飞灰、底灰和脱硫石膏中的含量相近.垃圾电厂除尘器飞灰经过半干法脱酸后Br-PAHs的含量减少50%以上,但是经过螯合剂稳固化作用之后飞灰中Br-PAHs的含量明显升高.Pearson相关分析结果表明,燃煤电厂不同燃烧产物的HPAHs生成机制相同,而垃圾焚烧电厂不同产物中HPAHs具有不同的生成机制,飞灰螯合化过程导致HPAHs的二次生成.垃圾电厂除尘器飞灰中HPAHs的TEQs值（10.0×10^-3 ng·g^-1）与燃煤电厂相近（8.87×10^-3~15.0×10^-3 ng·g^-1）.对于垃圾电厂不同燃烧产物,脱酸工艺能够显著去除7-BrBaA从而降低飞灰的TEQ值,而飞灰螯合化后TEQ值达到螯合前的5.4倍.燃煤电厂的飞灰因年产量较大,且总HPAHs的TEQs值相对较高,对其处理和资源化利用应考虑HPAHs带来的生态风险.     

辽河口湿地土壤多环芳烃的分布及来源研究

于2008年10月、2009年5月和8月采集辽河口湿地31个表层土壤样品,利用GC-FID技术定量分析其16种优控多环芳烃（PAH）含量.结果表明,PAHs总量分布范围为293.4～1936.9 ng·g^-1,平均值为851.5 ng·g^-1,其中油井区苇田PAHs含量最高（1717.5 ng·g^-1）,滩涂区最低（614.6 ng·g^-1）.2008年10月PAHs总量和中高环组分比重均高于2009年5月和8月.应用不同环数的相对丰度和比值法进行来源解析,结果表明,燃烧是2008年10月的主要来源,石油污染和燃烧源的混合来源为2009年5月和8月的主要来源.主成分分析和多元线性回归法显示交通污染和燃煤混合来源为2008年10月PAHs的主要来源,贡献率为45.5%;石油和交通混合污染是2009年5月和8月PAHs的主要来源,贡献率分别为75.2%和42.2%.     

珠江三角洲典型区域农业土壤中多环芳烃的含量分布特征及其污染来源

2002-10～2005-11采集珠江三角洲典型区域（东莞市、惠州市、中山市、珠海市和佛山市顺德区）的农业土壤表层样品260个,运用气相色谱-质谱方法对美国EPA优控的16种多环芳烃（PAHs）进行分析测定.结果显示,研究区农业土壤中16种PAHs含量范围在3.3～4 079.0 ng·g^-1,平均含量244.2 ng·g^-1,以3环和4环的PAHs为主;中心城区土壤中PAHs含量高于远郊区,菜地>水稻田>香蕉地>旱坡地果园地>甘蔗地.依据荧蒽/芘及2+3环与4环以上PAHs化合物分布特点,表明该区域农业土壤中PAHs主要来源于化石燃料的不完全燃烧.通过与国内外土壤中PAHs含量的对比,研究区的农业土壤受到一定程度的PAHs污染,含量处于中等水平.     

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.