广州市不同人群硒摄入量研究

通过酸消解、原子荧光-氢化物发生法测定了广州市市售109种常见食物中硒的含量,结合膳食结构计算了广州市不同人群的每日硒摄入量.结果表明,广州市不同食品硒含量有较大差异,均值为4.97～457.3 μg·kg-1,其中动物性食品硒含量明显高于植物性食品硒含量,硒含量较高的食品有动物内脏、鱼虾类、蛋及蛋制品、猪肉等,均大于150 μg·kg-1.广州市不同人群膳食硒摄入量有明显差别,不同收入人群的摄入量为高收入人群(102.6 μg·d-1)＞中收入人群(83.8 μg·d-1)＞低收入人群(66.6 μg·d-1);老人硒摄入量为73.3 μg·d-1,儿童为44.3 μg·d-1,大学生为86.8 μg·d-1,工人为69.7 μg·d-1;标准人摄入量为98.5 μg·d-1.动物性食品是广州居民硒摄入量的主要来源;其次是大米;蔬菜、水果和豆类及制品等植物性食品贡献很小.广州市不同人群每日硒摄入量处于良好水平.     

广东省食品中的氯丙醇酯水平及其人体暴露评估

氯丙醇酯是氯丙醇与脂肪酸反应的一类污染物,该文旨在通过评估食品中的此类污染物对不同人群进行暴露风险评估.在广东省的3个地区采集了包括油条、方便面饼和麻花在内的食品样品,用GC-MS测定了4种氯丙醇酯类化合物,其中主要为2-MCPD酯和3-MCPD酯.氯丙醇酯浓度最高的为麻花,其次为方便面饼和油条.样品中3-MCPD酯和2-MCPD酯的浓度范围分别为n.d.~0.49 mg·kg~(-1)和n.d.~0.64 mg·kg~(-1).不同样品中2-MCPD酯的浓度均大于3-MCPD酯.对各个年龄的人群暴露评估的结果表明,3~9岁儿童的3-MCPD酯的暴露大于耐受量(TDI)0.8μg·kg-1·d-1,青年与成年组均小于每日最大耐受量(PMTDI)2μg·kg-1·d-1.本研究中的食品样本,对于儿童的暴露均存在健康风险,所以应该减少对油炸食品的摄入量以降低氯丙醇酯对儿童造成的健康风险.     

不同评估方法得出的五氯酚的PNEC值的比较研究

预测的无效应浓度(PNEC)是进行风险污染物水生态安全管理的重要依据,一直是水环境风险管理者研究的热点.为了比较不同评估方法对PNEC计算结果的影响,以五氯酚(PCP)的PNEC值评估为例,使用点评估、统计评估和区间评估进行PCP的PNEC值研究,并对这几种方法进行比较,同时对控制PNEC值大小的主要影响因素进行了分析.结果表明,由点评估通过急慢性毒性数据和评估因子获得的PCP的PNEC值分别为0.420μg·L-1和0.500μg·L-1,相差不大;由统计评估的probit和logit单位法获得的PCP的PNEC值分别为10.1μg·L-1和8.10μg·L-1;由区间评估获得的PNEC-L95%和PNEC-L50%的值分别为6.00μg·L-1和11.8μg·L-1,可见由统计评估和区间评估获得的PNEC值比较接近,而点评估获得的PNEC值比其它两种方法低一到两个数量级;并且毒性数据类型和统计模型对毒性数据量丰富的PCP的PNEC值的得出影响不大.因此统计评估和区间评估可以被选为数据量较丰富的化合物如PCP的PNEC值的计算方法,其结果比点评估计算出的PNEC值更具有可信度.     

邻苯二甲酸二丁酯的人群综合暴露评估

为了解我国人群邻苯二甲酸二丁酯(DBP)的健康风险负荷,在国内外文献分析和现场监测数据的基础上,对我国DBP的人群暴露状况进行评估.结果表明,DBP广泛存在于环境和人体生物样品中,估计每日总摄入量为14.8μg/(kg·d),食物是其主要的摄入途径,占总摄入量的90.2%,其次为饮用水,占8.6%;说明我国人群DBP的污染已达一定负荷.     

长期施用粪肥蔬菜基地蔬菜中典型抗生素的污染特征

利用高效液相色谱-串联质谱(HPLC-MS/MS)技术,分析了珠三角地区某长期施用粪肥蔬菜基地蔬菜中16种典型抗生素的含量,并初步评价其健康风险.结果表明,绝大部分抗生素不同程度被检出,检出率为11%～100%,大多数含量<5μg·kg-1(干重),最高为23.88μg·kg-1,平均为0.91μg·kg-1,以恩诺沙星、环丙沙星、磺胺二甲基嘧啶和磺胺嘧啶为主.各蔬菜样品中至少检出1种抗生素,最多达10种.蔬菜不同器官中喹诺酮类抗生素含量为地下部>地上部.人体通过食用研究区蔬菜摄入抗生素的量低于日允许摄入量(ADI),表明其健康风险较小,但多种抗生素的联合毒性及其耐药性问题不容忽视.     

人体硼暴露生物标志物的筛选研究

为了寻找一种合适的硼暴露生物标志物,为环境风险评价提供依据,分析了硼暴露下人体尿液、血液和精液中的硼浓度及其与人体日硼摄入量的相互关系.结果发现,硼暴露组工人、社区对照人群和背景对照人群的日硼摄入量分别为31.3、4.25和1.40mg·d-1,下班时的尿硼肌酐校正浓度分别为14 7、4.49和1.58 mg·g-1,血清硼浓度分别为252、114和39.1ng·mL-1,精液硼浓度分别为592、281和146ng·mL-1.受试者的班后尿硼浓度、血清硼浓度和精液硼浓度均与日硼摄入量存在着显著的对数线性关系,回归方程的确定系数分别为0.856、0.702和0.610.尿硼浓度与日硼摄入量的关系最好,可以更好地反映人体硼暴露的情况.尿硼、血清硼和精硼浓度两两之间也存在着显著的对数线性关系,其中尿硼-血清硼的关系最好,Spearman相关系数为0.801,可以用尿硼浓度来反映血清硼与精硼的水平.根据生物标志物的筛选条件,尿硼浓度可以较好地反映硼的内外暴露情况,筛选出班后尿硼作为硼暴露的生物标志物.     

评污染物质对健康的影响

一、多氯联苯(PCBs)和多氯三联苯(PCTs) PCBs和PCTs是以混合状态生产和使用的。世界各地在环境的空气、水、土壤、残渣以及人体和动物体的细胞中都已发现了PCBs。据估计,从空气和食用水中人平均日摄入量小于1μg。在工业化的国家,平均每天从食物中摄入5μg～100μg(近似1μg/kg体重) PCBs聚集于动物细胞中,也同样聚集在人体细胞中。对人体的多脂细胞组织取样测定,大部分含量相当于1mg/kg,是日摄入量的一千倍。这是由于PCBs在脂肪层中长期滞留造成的。对国民调查的结果表明;在不受职业性暴露的人体中,血中PCBs的含量为3—12μg/l;而在受职业性暴露的人体血中竟高达1900μg/l,多脂细胞中高达700mg/kg。     

五氯酚对稀有鮈鲫卵黄蛋白原及p53的诱导效应

采用中国特有鱼种稀有鮈鲫为实验动物,研究五氯酚（PCP）对其肝脏卵黄蛋白原（VTG）、VTG基因及抑癌基因p53的诱导效应,评价PCP的内分泌干扰作用,并从蛋白和基因表达水平上筛选PCP检测的敏感生物标志物.1.5、15、40、80、120、150、160μg.L-1PCP暴露稀有鮈鲫,同时设置空白、溶剂对照和17α-雌二醇（EE2）阳性对照,运用SDS-PAGE,ELISA法检测经PCP暴露后稀有鮈鲫肝脏VTG蛋白的表达差异;克隆稀有鮈鲫新的VTG和p53基因序列片段,运用实时荧光定量PCR方法检测PCP暴露对基因表达的影响.结果表明,40、80、120、160μg.L-1PCP均能诱导雌雄稀有鮈鲫肝脏VTG蛋白的表达,具有显著的浓度-效应关系;1.5、15、150μg.L-1PCP暴露后,雄性稀有鮈鲫肝脏VTG和p53基因表达均明显升高,具有显著的浓度-效应和时间-效应关系.证明PCP具有雌激素效应,稀有鮈鲫肝脏的VTG蛋白、VTG及p53基因可作为PCP检测的敏感分子生物标志物.     

华北地区城镇多环芳烃干沉降特征

分别于冬季和夏季采集了北京、天津和秦皇岛3个城市,遵化、沧县、涞源和张北4个县城以及两处人为活动较少的背景地区降尘样品,分析了降尘量及降尘中多环芳烃含量,据此计算了各样点多环芳烃干沉降通量.结果表明,所研究城市夏季和冬季多环芳烃平均沉降通量分别为(6.3±7.4)μg·m-2·d-1和(16.4±14.9)μg·m-2.d-1,县城为(2.2 4±0.9)μg·m-2 d-1和(16.3±3.8)μg·m-2·d-1,对照点明显低于城镇,两季多环芳烃沉降通量分别为(1.0±0.3)μg·m-2 d-1和(1.6 4±0.7)μg·m-2,d-1.两季节获得的所有样点多环芳烃干沉降通量与降尘量显著相关,若分季节统计,相关性更加明显,且冬季降尘中多环芳烃含量显著高于夏季.由此可见,对多数样点而言,导致其多环芳烃干沉降通量差别的首要因素是降尘量,其次为季节差异.仅个别数据(夏季秦皇岛)表现出不同.降尘中多环芳烃成分谱具有明显的季节差异,城市与县城冬季降尘中菲的相对含量显著高于夏季.不同类型样点间差别较小,表现出区域性趋同现象,同种类型样点之间的多环芳烃成分谱则非常一致.     

黄浦江铅的人体健康水质基准研究

铅是我国水环境质量监控的重点污染物之一.我国成人和儿童铅中毒事件时有发生,制定铅的人体健康水质基准在我国有着特殊意义.本文以黄浦江流域为研究对象,采集并分析流域水样和不同营养级的鱼样本中铅含量,结合文献调研,确定了人体暴露参数、生物蓄积系数等相关本土参数,推导出该流域铅的基于人体健康风险水质基准值为13.45μg·L~(-1).虽然该值略高于我国和大部分发达国家的现行饮用水标准(10μg·L~(-1)),但明显低于我国地表三类水环境标准(50μg·L~(-1)),提示黄浦江流域水体铅污染需要进一步加强防控.另外,通过引入铅的敏感人群儿童对基准推导进行了优化,并应用IEUBK模型(The Integrated Exposure Uptake Biokinetic Model,综合暴露吸收生物动力学模型)对儿童血铅含量进行预测分析.研究发现引入了铅的敏感人群儿童后,推导得出基于人体健康的水质基准值为1.718μg·L~(-1),提示黄浦江流域的儿童在日常饮用水的选择上,应选择铅浓度比饮水标准更低的饮用水.本研究提出本土铅的基于人体健康风险水质基准值,对我国基准技术指南案例研究以及铅相关水质标准修订等具有重要的科学意义和参考价值.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.