三峡库区涪陵和忠县两地居民发汞含量水平及影响因素分析

为评价三峡库区居民汞暴露风险,在三峡库区腹心地带的涪陵和忠县两地采集了238份当地居民头发样本,分析了总汞(THg)和甲基汞(Me Hg)含量.结果表明,两地居民头发THg、Me Hg平均含量分别为(0.50±0.54)μg·g~(-1)、(0.35±0.25)μg·g~(-1).其中,涪陵居民头发THg、Me Hg平均含量分别为(0.71±0.87)μg·g~(-1)、(0.53±0.46)μg·g~(-1),均高于忠县居民头发THg[(0.41±0.36)μg·g~(-1)]、Me Hg[(0.28±0.26)μg·g~(-1)]平均含量水平,但两地头发总汞平均含量均低于美国EPA安全参考剂量(1μg·g~(-1)).不同年龄段的居民发汞含量存在显著性差异(P0.05),其中40~50岁年龄段居民发汞含量最高;不同性别间发汞含量差异不显著(P0.05),但女性发汞含量略高于男性.居民发汞含量与食鱼频率呈正相关,渔民发汞含量显著高于非渔民发汞含量(P0.01),且渔民头发样本总汞含量均值(1.44±0.79)μg·g~(-1)超过了EPA安全参考剂量.两地吸烟者头发总汞含量[(0.55±0.24)μg·g~(-1)、(0.58±0.54)μg·g~(-1)]均显著高于非吸烟者头发总汞含量[(0.51±0.30)μg·g~(-1)、(0.36±0.26)μg·g~(-1)].三峡库区居民汞暴露风险总体较低,但渔民存在一定的汞暴露风险.     

上海市居民人发重金属含量及其空间分布特征研究

采集上海市15个区(不包括崇明县),年龄在0~80岁之间的84例居民人发样品作为研究对象,着重分析上海市居民头发中镉(Cd)、铜(Cu)、铅(Pb)和锌(Zn)4种重金属元素含量,探究其与年龄的关系及空间分布特征.结果显示,上海市居民头发中Cd、Cu、Pb和Zn 4种重金属平均含量均在正常范围内,Cd含量为(0.11±0.19)μg·g~(-1),Cu为(11.42±8.75)μg·g~(-1),Pb为(1.64±2.12)μg·g~(-1),Zn为(121.20±106.59)μg·g~(-1),与国内外其他地区相比,上海市居民这4种重金属的污染水平较低.单因素方差分析(one-way ANOVA)表明,Pb和Cd含量的高值集中于0~10岁儿童,且与其他年龄段有显著差异,说明儿童较容易受到Pb和Cd的污染;利用样本数据进行反距离加权插值(IDW),得到上海市居民头发中4种重金属含量的空间分布规律,其中发Pb和发Cd含量呈现出由市区向郊区递减的变化特征.     

桂林市交警尿汞含量及分布研究

对桂林市3个城区交警按年龄、工龄、工种和性别比例采集尿样44件,测定和研究尿样汞浓度分布状况,并采集普通人群发样128件加以对照。结果表明,车流量越大,从事交警的工龄越长,交警尿样中汞浓度越高。从事外勤工作交警尿样汞平均浓度高于内勤工作交警。桂林市交警尿样汞平均浓度为(2.372±0.657)μg/L,是普通人群(0.348±0.193)μg/L的6.82倍。对交警与普通人群以及外勤交警与内勤交警尿样的汞浓度分别进行独立样本t检验,差异性均显著。男性交警尿样汞平均浓度为(2.429±0.628)μg/L,略高于女交警(2.114±0.722)μg/L。对不同性别交警尿汞浓度进行独立样本t检验,差异性不显著。无铅汽油的使用降低了大气中铅的污染,但汞的污染依然存在,应当引起高度重视。     

南丹矿业活动影响区人群头发中重金属含量特征

为探讨矿业活动对"有色金属之乡"南丹矿区周边常住居民健康的影响,采集矿业活动影响区车河镇、大厂镇、长老乡及对照区六寨镇中典型村庄居民发样200个,用原子荧光形态分析仪(AFS-9700)、石墨炉原子吸收分光光谱仪(AA 700)和电感耦合等离子发射光谱仪(Optima 7000)测试其重金属含量.结果表明,受影响区人群发样中As、Sb、Cd和Pb的平均含量分别为1.260、2.161、2.466和20.92μg·g-1,分别是对照区的4.0、20、2.1和1.9倍,且车河、大厂人群发样中Sb含量超出推荐正常范围;受影响区人群发样中Zn含量与居民年龄呈负相关(P0.05,n=151),Cd和Pb含量与居民年龄呈弱负相关(P0.1,n=151);通过独立样本t检验,受影响区男性居民发样中Cd含量显著高于女性(P0.05),而女性居民发样中Cu和Zn含量显著高于男性(P0.05).调查区域人群发样中As与Sb、Cd与Pb、As与Cd呈显著相关性(P0.01).可见,南丹矿业活动对周边常住人群人发重金属积累效应明显.     

大连市居民头发典型重金属富集特征研究

测定了大连市居民102份头发样品中Pb、Cd、Hg、As等重金属含量,评估了其暴露风险,并对头发中重金属的含量与年龄、性别的关系进行了分析.结果表明,大连市居民头发中Pb、Cd、Hg、As含量均低于中国居民头发中重金属的建议正常值上限,4种重金属暴露风险较低.男性头发中Cd、Pb和As的平均含量明显高于女性(p0.05),其中As平均含量差异达到极显著水平(p0.01).PCA分析显示样本分布集中在第一排序轴和第二排序轴中间,表明性别并不是影响头发中重金属含量的主要因素.19～35岁年龄组居民头发中Cd和Pb含量最高,且均与56～75岁年龄组呈现显著差异(p0.05);As和Hg在56～75岁年龄组居民头发中含量最高,与其它组比较均达到了显著水平(p0.05).PCA和Pearson分析表明4种重金属间相关性较好,大连市居民对4种重金属暴露途径基本相同.     

锡矿山矿区和贵阳市人发中锑、砷和汞的污染特征

采用氢化物发生-原子荧光光谱法(HG-AFS),对经过硝酸-高氯酸消解后的锡矿山矿区和贵阳市人体头发样品中重金属锑(Sb)、砷(As)、汞(Hg)含量进行分析.结果表明,锡矿山矿区人体头发中Sb、As、Hg平均含量分别为15.9、 4.21、 1.79 μg/g,贵阳市人体头发中Sb、As、Hg平均含量分别为0.532、 0.280、 0.338 μg/g.锡矿山矿区人体头发中Sb、As、Hg含量明显高于贵阳市人体头发中相应元素的含量.通过独立样本的t检验发现,Sb、As在锡矿山矿区和贵阳市两地男性人体发样中和女性人体发样中含量不具显著差异(p>0.05);Hg在锡矿山矿区男性和女性人体头发中含量差异不显著(p>0.05),而在贵阳市则男性人体头发样品中Hg含量显著高于女性(p<0.05).人发中重金属As与Sb、As与Hg含量之间有较明显的相关性,Sb与Hg含量之间不具有显著相关性(p≤0.01).研究结果说明,锑矿开采和冶炼区域重金属Sb、As、Hg对人体健康的危害明显比非锑矿开采区域相应的重金属对人体健康的危害严重.     

西南有色金属矿区周边居民头发中重金属含量特征

为了研究金属矿石开采、冶炼等工业活动对周边居民身体健康的影响,该研究采用氢化物发生-原子荧光光谱法(HG-AFS)和石墨炉原子吸收光谱法(GF-AAS)测定我国西南有色金属矿区周边2个村庄(A村、B村)居民头发中As、Pb、Cr、Cu 4种重金属含量(93例)。结果表明,矿区周边A村居民头发中As、Pb、Cr和Cu平均含量分别为0.75、8.77、0.40和6.98μg/g,B村平均含量分别为0.25、4.20、0.39和7.91μg/g;A村居民头发中As、Pb含量明显高于B村(P0.01)。相关分析表明,A村居民头发中As和Pb、Cr和Cu均有较明显相关性,即人发中As和Pb的累积可能来自于同一污染源,而B村居民头发中各元素均不存在显著相关性。主成分分析结果表明,A村居民头发中As和Pb主要来源于周边铅锌矿采选和冶炼等。不同年龄段人发中重金属含量分析表明,2个村居民头发中As、Pb含量均随着年龄增长呈上升趋势,而Cr和Cu含量随着年龄增长没有明显变化。不同性别的人发中重金属含量分析表明,A村和B村居民头发中As和Pb含量男性均显著高于女性(P0.01),而Cr和Cu含量没有显著性差异。     

前郭灌区居民发汞含量及影响因素研究

从第二松花江(二松)下游的前郭灌区内采集了120名居民的头发样品(发样),测定了发样中的总汞(发汞)含量,分析了人体汞累积的影响因素,评价了当地居民的汞暴露风险水平.结果表明,居民发汞含量为0.15～1.01mg/kg,平均含量为0.56mg/kg.其中,男性发汞平均含量为0.55mg/kg,略低于女性发汞平均含量(0.60mg/kg).随年龄的增长,居民发汞含量呈现先增长后降低的趋势.其中,低于20岁人群的发汞含量最低,平均值为0.47mg/kg;40～50岁人群发汞含量最高,平均值为0.73mg/kg;发汞含量与个体性别、身高、体重等生理特征及吸烟、饮酒、食鱼量等生活习惯的相关关系不显著.120份发样中,仅有1例发汞含量超过了美国环保局制定的参考剂量(RFD)限值(1.00mg/kg).本研究表明,目前二松下游居民的汞暴露风险水平已经很低,长期提取二松江水灌溉对当地居民健康未构成威胁.据此推断,以二松为主要水源的哈达山水库建成后,通过灌溉对当地居民健康造成的影响也较低.     

哈尔滨市融雪径流中重金属污染空间分布及源解析

根据2018年哈尔滨市融雪径流中重金属(Fe、Pb、Cr、Cd、Hg和Zn)监测数据,结合气象数据,运用暴雨洪水管理模型(SWMM)构建了城市融雪过程水文及水质模型.对各排水口及汇水区融雪径流产出量、单位面积重金属负荷量进行了计算,并在此基础上分析了融雪径流中重金属污染的空间分布特征及主要来源.结果表明:在采集的融雪径流样品中,Fe浓度最大,平均值为4.95 mg·L~(-1);Hg浓度最小,平均值为0.542μg·L~(-1);Pb浓度变化范围最大,在32.14～254.36μg·L~(-1)之间;Hg浓度变化范围最小,为0.038～0.841μg·L~(-1).在空间分布上, Fe、Pb、Cr、Cd和Zn 5种重金属浓度的高值区均分布在人口密集的居民区、商业区及主要交通道路周围.排水口重金属污染产出量与径流量成正比,总产出量FePbCrCdHgZn. Zn产出量由高到低的排放口依次为马家沟、阿什河、松北区排放口、何家沟、道里区排放口和道外区排放口,其它5种重金属产污量总体呈现阿什河马家沟何家沟松北区排放口道里区排放口道外区排放口的趋势.Fe的单位面积负荷总量最大,为2405.94μg·m~(-2);Pb和Cr次之,为36.36μg·m~(-2)和14μg·m~(-2).主成分分析结果表明哈尔滨市春季融雪径流中重金属的主要来源依次为工业源、生活与机动车源和燃煤源,贡献率分别为43.237%、23.598%和12.012%.     

某金属冶炼厂周围居民人发的6种元素含量特征

为研究金属冶炼对人体健康的危害水平,利用原子吸收分光光度计和AFS-930型原子荧光光度计对浙江富阳郊区某金属冶炼厂周围部分人发的6种元素Cu、2n、Pb、Cd、As、Se含量进行了测定.结果表明,研究区居民人发样品中具有较高含量,其中Cu、Zn、Pb和Cd最高含量分别达312、513、700和7.41 μg·g-1, As和Se最高量达10.08和0.85 μg·g-1.人发中Cu、Zn、Pb、Cd、As含量呈明显相关关系,这在一定程度上反映了人发中元素污染程度的相似来源可能是小高炉冶炼.不同年龄的人发元素含量分析表明,40岁以上人发中Cu、Pb、Cd、As平均含量高于40岁以下约2倍;不同性别的人发元素含量分析表明, Cu、Zn、Cd、Se没有多大差别, Pb和As表现为男性略高于女性,但是经统计检验各元素在年龄和性别差异上均不显著.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.