围产期二英暴露对学龄前儿童类固醇激素的影响

为揭示围产期二噁英(PCDD/DFs)暴露对学龄前儿童类固醇激素水平的影响.采用液相色谱-质谱联用法(LC-MS/MS)及高分辨气相色谱法/高分辨质谱联用法(HRGC/HRMS)分析二噁英污染地区5岁儿童(n=37)及非污染地区5岁儿童(n=44)血清中8种类固醇激素水平及母乳中17种二噁英同系物浓度.结果显示污染地区男孩血清中睾酮、双氢睾酮、脱氢表雄酮的水平明显低于非污染地区(p0.05).污染地区女孩血清中睾酮、双氢睾酮、脱氢表雄酮、17α-羟孕酮、孕酮的水平明显低于非污染地区(p0.05).上述类固醇激素与部分二噁英同系物浓度存在显著性负相关.以上结果表明围产期二■英暴露导致学龄前儿童类固醇激素水平降低.     

二噁英暴露对成年男性血清类固醇激素的影响

为了解二噁英（PCDD/DFs）对成年男性类固醇激素水平的影响,采用高分辨气相色谱法/高分辨质谱联用法（HRGC/HRMS）及液相色谱-质谱联用法（LC-MS/MS）分析二噁英污染地区成年男性（n=50）及非污染地区成年男性（n=48）血清中9种类固醇激素水平和17种二噁英同类物浓度.结果显示成年男性血清中双氢睾酮、睾酮、雌二醇的水平与部分二噁英同类物浓度存在显著性相关.污染地区成年男性双氢睾酮、睾酮、雌二醇的水平与年龄呈显著性正相关.以上结果表明二噁英暴露导致成年男性类固醇激素中的性激素变化异常.     

中国南海流沙湾中雄激素、糖皮质激素和孕激素的污染特征及其生态风险评价

近年来,类固醇激素在淡水水体中不断被检出,但是其在海水中的污染特征研究相对较少.本文对中国南海流沙湾进行样品采集,通过高效液相色谱与质谱联用技术(UPLC-MS/MS),研究了33种类固醇激素的污染特征及空间分布.结果表明,在海水和沉积物中均检出7种类固醇激素,含量范围为0. 003(甲羟孕酮,MP)～9. 023(去氢孕酮,DGT) ng·L~(-1)和0. 017(1,4-雄烯二酮,ADD)～9. 281(雄烯二酮,AED) ng·g~(-1).在海水中,类固醇激素浓度高低顺序为合成类高于天然类,丰水期高于枯水期,养殖区高于非养殖区.在沉积物中,类固醇激素在时空分布上无明显差异.海洋环境中类固醇激素的主要来源为水产养殖人为饲料添加和废水排放.生态风险评价结果表明,AED处于低风险,其他类固醇激素处于无风险.相关性分析表明,海洋环境中类固醇激素的含量分布规律与盐度、水温、颗粒物(SS)和化学需氧量(COD)有关.本研究有助于认识流沙湾地区类固醇激素的污染特征,并为其生态风险评价和管控提供科学依据.     

电子废弃物拆解区二噁英污染特征及暴露风险评估

应用高分辨气相色谱/高分辨质谱(HRGC-HRMS)联用技术对电子废弃物拆解不同生产工艺排放废气、周边环境空气、土壤及地下水中二噁英(PCDD/Fs)浓度水平和排放特征进行了监测分析,并采用VLIER-HUMAAN模型评估其对人体的暴露风险.结果表明,该电子废弃物拆解废气PCDD/Fs毒性当量浓度为0.0033～9.1...     

北京冬季大气中多溴联苯醚的污染水平和分布特征

2010年11月至2011年2月利用聚氨酯泡沫(PUF)大气被动采样技术采集了北京市海淀、朝阳、丰台、石景山、昌平、大兴、通州等区域的大气样品,采用高分辨气相色谱/高分辨质谱联用法(HRGC/HRMS)分析了其中13种多溴联苯醚(PBDEs)同族体的污染浓度和分布特征.结果表明,北京大气中PBDEs总含量(Σ13PBDEs)为0.97~41.1pg/m3,平均值为7.85pg/m3.在区域分布规律方面呈现东南地区的采样点污染物浓度明显高于西北地区,工业地区和人口密集的商业地区明显高于郊区和背景对照区的分布特征.     

深圳市废弃物焚烧炉飞灰中二噁英含量水平和特征分析

采用同位素稀释的高分辨气相色谱/高分辨磁式质谱联用仪(HRGC/HRMS)对深圳市8所垃圾焚烧厂飞灰中二噁英进行准确定量检测,分析比较不同炉型、不同种类废弃物焚烧厂飞灰中的二噁英浓度水平和分布情况.结果发现8所废弃物焚烧炉飞灰中二噁英浓度差异较大,5所往复炉排生活垃圾焚烧炉样品中二噁英的质量浓度和TEQ浓度平均值都小于热解型医疗垃圾焚烧炉.两所不同的工业危险废物焚烧炉中,以烧废物矿油的立式筒焚烧炉的二噁英含量远大于以焚烧电路板为主的回转窑焚烧炉.不同焚烧炉飞灰中二噁英异构体的浓度分布具有相类似的特征,高氯代二噁英的含量明显高于低氯代二噁英同系物.不同的PCDD/Fs单体对I-TEQ的贡献率在不同的焚烧设备中十分相似,2,3,4,7,8-Pe CDF、1,2,3,7,8-Pe CDD、2,3,4,6,7,8-Hx CDF 3种单体是TEQ浓度的主要贡献单体.在布袋除尘器前喷淋活性炭能有效吸附烟气中二噁英,将其转移到飞灰中.本研究是首次针对深圳市运行中的废弃物焚烧炉进行飞灰中二噁英排放分析,为二噁英排放监控提供重要的基础数据.     

我国苏南地区香樟树皮赋存的二噁英类污染特征及来源

为分析长江下游经济高速发展区的POPs污染特征,于2012年8月在苏南地区典型城市10个采样点采集香樟树皮,应用高分辨气相色谱-高分辨质谱(HRGC-HRMS)联用技术对二噁英(PCDD/Fs)浓度水平进行监测,同时采用主成分分析(PCA)法探讨其可能来源.结果表明:苏南地区香樟树皮中二噁英的毒性当量(I-TEQ)浓度(以干质量计,下同)为5.6~12.2 pg/g,平均值为7.2 pg/g;4~8氯代二噁英同族体质量分数(以干质量计)范围为418~938 pg/g,平均值为635 pg/g.由于二噁英在大气中的长距离迁移潜力较强,在研究的苏南地区区域尺度上,其含量在城市中心区和对照区之间的差异性并不明显;苏南地区香樟树皮二噁英质量分数及毒性当量浓度均高于国外报道的背景区及典型城市中树皮的水平.对比典型二噁英排放源及树皮中二噁英特征谱图,可推断苏南地区香樟树皮中二噁英可能主要来源于危险(医疗)废物焚烧、机动车尾气排放和工业燃烧源.     

济南市道路尘中类二噁英类多氯联苯残留情况

通过采集济南市区主要路段道路尘样品,用气相色谱-电子俘获检测器(GC-ECD)方法分析了济南市区主要路段道路尘中毒性较高的12种类二噁英类多氯联苯(DL-PCBs)的残留情况,并对样品中DL-PCBs的含量、污染水平及同系物的组成进行了详细研究。结果发现,DL-PCBs在各采样点均有检出,残留总浓度在0.20～22.84ng/g(干重)范围内,平均值为0.0051ng/kg,同系物PCB81的检出率最高为90%,而同系物PCB189未被检出。计算的毒性当量(TEQ)值显示,对毒性当量贡献最大的是同系物PCB126,其TEQ值高达117.100pg/g(干重)。由平均残留百分含量较大的同系物结构分析可知,济南市区主要路段道路尘中非邻位氯取代的剧毒类二噁英类PCBs含量相对较大。     

空调滤网和风扇积尘中二噁英类污染特征及暴露风险

选取广州和东莞地区的普通住宅和工厂内常用风扇、排气扇叶片和空调滤网上的积尘为研究对象,利用同位素稀释高分辨气相色谱高分辨磁质谱方法分析积尘样品中17种2,3,7,8氯取代二噁英类浓度,揭示室内风扇和空调滤网积尘中二噁英类的污染水平与单体特征并计算暴露风险.结果表明,样品中PCDD/Fs的质量浓度为316～13266 ng·kg^-1,平均值为3122 ng·kg^-1,贡献最大的单体是OCDD;PCDD/Fs的毒性当量浓度为5.19～561 ng·kg^-1,平均值为99.8 ng·kg^-1,贡献最大的单体是2,3,4,7,8-PeCDF.相较于其他城市住宅区灰尘,本研究样品的毒性当量浓度处于较高水平,个别点位高于工业区住宅灰尘.风扇和空调滤网积尘中儿童和成人的总估计日摄入量分别为1.49×10^-5～1.61×10^-3 ng·kg^-1·d^-1和1.26×10^-6～1.36×10^-4     

焦炉烟气中二（口恶）英类物质排放水平研究

二噁英和类二噁英多氯联苯属于《关于持久性有机污染物的斯德哥尔摩公约》规定的非故意产生的持久性有机物,统称为二噁英类物质.焦化生产过程中具备二噁英类物质生成所需的前体物、温度、催化剂等条件,但目前国内外对焦化行业焦炉烟气二噁英类物质排放研究仍属空白,为进一步明确焦化行业排放水平和影响因素,针对性地提出行业减排和控制措施,利用高分辨气相色谱-高分辨质谱法对4个不同规模的典型焦化企业焦炉烟气中二噁英类物质排放情况进行现场采样和实验室分析.结果表明,二噁英类物质毒性当量(以WHO-TEQ计)范围为3.9~30.0 pg·m-3,处于较低水平,检出较多的PCDD/Fs同系物主要是高氯代的.另外,烟气中此类物质的排放量与焦化生产工艺关系密切,捣鼓炼焦、较高的炭化室高度有利于减少二噁英类物质的排放.     

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.     

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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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.     

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.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

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.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.