黄河干流表层水体和沉积物中PBDEs和NBFRs的分布特征

研究分析了2012年黄河干流表层水体及沉积物中10种多溴联苯醚(PBDEs)和6种新型溴代阻燃剂(NBFRs)的浓度水平及分布特征。BDE 209是主要的PBDEs同族体,其次是BDE47和BDE99。黄河水中的BDE47/BDE99与商用产品中的比例相似,然而黄河沉积物中的BDE47/BDE99与商用产品中却大有不同。对所测各PBDEs的同系物进行主成分分析后显示,黄河中PBDEs分布组成复杂,且当地的工业生产活动可能是黄河干流PBDEs积累的主要原因。黄河河水和沉积物中NBFRs检出率及其浓度水平较低,但六溴苯(HBB)在所有沉积物样品中均有检出,而且五溴甲苯(PBT)和五溴苯(PBBz)在所有的河水及沉积物样品中均有检出,这意味着黄河干流HBB、PBT和PBBz的污染十分普遍。与中国其他河流的数据相比,黄河的溴代阻燃剂(BFRs)水平较低,但是黄河经流的10个地区中,经济发达地区的BFRs浓度要显著高于欠发达区域。此外,河水中PBDEs的水平与人均工业产出存在很强的关联性,表明PBDEs的浓度与当地的经济发展水平显著相关。     

典型地区大气中多溴联苯醚和新型溴代阻燃剂的水平及组成分布

溴代阻燃剂被广泛应用于工业和商业产品中,广泛存在于各种环境介质中,可能会对环境和人体产生潜在的危害.本研究选取我国溴代阻燃剂生产源区山东省潍坊市滨海开发区为生产源区域,广西壮族自治区南宁市作为对照区域,测定两地大气中8种多溴联苯醚(PBDEs:BDE-28,-47,-100,-99,-154,-153,-183,-209)和新型溴代阻燃剂(NBFRs:PBT,PBEB,HBB)的浓度.结果表明,潍坊和南宁大气中Σ8PBDEs算术平均浓度分别为1.4×105pg·m-3和323.0 pg·m-3,Σ3NBFRs算术平均浓度分别为4.2×103pg·m-3和11.9 pg·m-3.与其他城市相比,生产源区大气中溴代阻燃剂浓度在全球范围内处于较高污染水平,南宁市则与我国其他城市的水平相当,生产源区大气中PBDEs的分布特征异于南宁,PBEB、PBT、HBB及BDE-209之间的相关性在两城市也具有一定的差异.     

Concentrations and distribution of novel brominated flame retardants in the atmosphere and soil of Ny-Ålesund and London Island, Svalbard, Arctic

Novel brominated flame retardants (NBFRs) were investigated in Arctic air and soil samples collected from Ny-Ålesund and London Island, Svalbard, during Chinese scientific research expeditions to the Arctic during 2014–2015. The concentrations of Σ₉NBFRs in the Arctic air and soil were 4.9–8.7 pg/m³ (average 6.8 pg/m³) and 101–201 pg/g dw (average 150 pg/g dw), respectively. The atmospheric concentration of hexabromobenzene (HBB) was significantly correlated with that of pentabromotoluene (PBT) and pentabromobenzene (PBBz), suggesting similar source and environmental fate in the Arctic air. No significant spatial difference was observed among the different sampling sites, both for air and soil samples, indicating that the effects of the scientific research stations on the occurrence of NBFRs in the Arctic were minor. The fugacities from soil to air of pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE), and decabromodiphenylethane 1,2-bis (pentabromophenyl) ethane (DBDPE) were lower than the equilibrium value, indicating a nonequilibrium state of these compounds between air and soil, the dominant impact of deposition and the net transport from air to soil. The correlation analysis between the measured and predicted soil-atmosphere coefficients based on the absorption model showed that the impact of the soil organic matter on the distribution of NBFRs in the Arctic region was minor. To the best of our knowledge, this work is one of the limited reports on atmospheric NBFRs in the Arctic and the first study to investigate the occurrence and fate of NBFRs in the Arctic soil.     

中国大气环境中溴代阻燃剂污染特征研究进展

根据近年来大气环境中溴代阻燃剂(brominated flame retardants,BFRs)污染问题的研究成果,综述了溴代阻燃剂在中国大气环境中的污染特征。重点分析了多溴联苯醚(polybrominated diphenyl ethers,PBDEs)和部分Non-PBDE溴代阻燃剂(Non-PBDE类BFRs)在不同类型大气环境中的含量水平及分布特征。文献研究结果表明,中国的室内空气、电子垃圾拆解地、特殊工业园区和经济较发达城市大气环境PBDEs污染较严重,含量水平在102~103pg/m~3。中等发达地区城市大气中PBDEs含量处于世界中等水平,含量为10~102pg/m~3。最主要PBDEs同系物为BDE-209,其次是BDE-47、BDE-99和BDE-28。中国针对大气环境中Non-PBDE类BFRs污染问题的研究较少,现有结果表明,部分地区该类污染物的含量较高,达到103pg/m~3。主要的Non-PBDE类BFRs包括HBCDD、BTBPE及DBDPE。文章最后对中国大气环境中BFRs相关研究中存在的问题进行了简要的总结和展望。     

长江中游沉积物中多溴联苯醚的污染特征及风险评价

多溴联苯醚(PBDEs)具有高毒性和生物累积性,进入水体后易与有机质相结合,成为PBDEs污染物的重要归宿,对人类健康和水生生态系统造成潜在的危险.为揭示多溴联苯醚(PBDEs)在长江中游流域的污染现状,通过采集该地区流域内13个表层沉积物样品,采用高分辨气相色谱/高分辨质谱法(HRGC/HRMS)对沉积物中9种PBDEs同类物进行分析.结果表明该地区沉积物中9种PBDEs的含量范围(干重)约为46.1~326 pg·g~(-1),而BDE-99是其中最主要的贡献单体,平均贡献率约为51.6%;其次是BDE-47,约为19.6%.与国内外其他海域的研究相比,长江中游沉积物中PBDEs残留量处于较低水平.通过测定沉积物中总有机碳(TOC),研究结果发现PBDEs含量与TOC无明显的正相关关系.结合商值法对PBDEs的健康风险进行初步评估,结果表明,本研究中PBDEs对人体产生的健康风险较小.     

环南四湖区地下水中重金属健康风险评价

为评价环南四湖区地下水中重金属对人体健康的潜在危害,使用电感耦合等离子体发射光谱仪(ICP-OES)测定环南四湖区35个地下水体中重金属Cd、Cr、Fe、Mn、Zn的含量水平,并采用美国环保署(USEPA)推荐的健康风险评价模型对其通过饮水和皮肤暴露途径所引起的健康风险进行评价。结果表明:地下水中重金属Cd、Cr、Fe、Mn、Zn含量分别为0. 28,13. 56,0. 88,1. 43,2. 27μg/L,其中重金属Cr是该地区地下水中的主要污染物,超标率为90. 2%。健康风险评价结果表明:重金属对成人的致癌风险高于儿童,饮水暴露途径产生的致癌风险远大于皮肤暴露途径,5种重金属的潜在健康风险顺序为Cr>Cd>Mn>Fe>Zn。重金属Cr、Cd通过饮水暴露途径对成人和儿童产生的潜在风险值分别为1. 10×10~(-4)、2. 95×10~(-5)和2. 91×10~(-5)、7. 75×10~(-6),研究表明该地区饮水和用水途径下重金属对人体不会产生明显的健康风险。     

婴儿脐带血和母亲血中多溴联苯醚的研究

为研究环境污染物多溴联苯醚(PBDEs)在人体的含量,采集了21对婴儿脐带和母亲静脉血样,用气相色谱和质谱法进行测定.结果表明,在所检测的7个PBDEs同系物(BDE-28,-47,-99,-100,-153,-154和-183)中,BDE-47和BDE-153为最主要的同系物.总PBDEs的含量分布于1.5~17ng/g;略高于挪威报道的含量水平,但低于瑞典和德国,远低于美国所报道的水平.      

电视机外壳热解油中1,2,4,5-四溴苯催化脱溴研究

电视机外壳热解油中含有的2,4,6-三溴苯酚、1,2,4,5-四溴苯、五溴二苯醚（P5BDE）等会严重影响其质量,为了净化电视机外壳热解油,试验用纯的1,2,4,5-四溴苯作原料,在单金属Pd/C作催化剂, 异丙醇作氢源条件下进行催化脱溴研究.同时,研究了反应体系pH值（NaOH加入量）对1,2,4,5-四溴苯脱溴效率的影响,最后探讨了1,2,4,5-四溴苯催化脱溴的反应机理.结果表明,当温度设定为50℃,搅拌速度设定为900 r·min-1,反应4h,脱溴效率可达100%;pH值在0~9之间时,pH越大,1,2,4,5-四溴苯脱溴效率越高; pH值≥9时, pH值增大,脱溴效率保持不变.实验用Pd/C作催化剂,经处理后可重复使用,并且产物为苯,在工业上的应用非常广泛,该实验具有很高的实用性.     

珠江三角洲沉积物钻孔中多溴联苯醚的垂直变化规律研究

采用GC/MS分析方法测定了珠江三角洲水体5个钻孔(分别采自东江东莞段、珠江广州段、北江中段、西江入海口和顺德段)80个样品中10种多溴联苯醚(PBDEs,BDE209和∑9BDEs)的含量,对其沉积规律进行研究和探讨.∑9BDEs含量范围为1.54~94.8 ng·g-1,平均值为15.4 ng·g-1.BDE209含量范围为14.4~588 ng·g-1,平均值为136 ng·g-1,占总PBDEs含量的70%以上.钻孔中PBDEs含量从底部到表层呈现上升趋势,表明近年来珠江三角洲PBDEs环境排放仍在增加.5个钻孔中低溴代∑9BDEs从表层至底部逐渐增加,而高溴代∑9BDEs逐渐减少,意味着钻孔中可能存在脱溴降解行为.     

滇池沉积物中主要污染物含量时间分异特征研究

基于滇池10个监测点(1991~2010年)表层沉积物中主要污染物(Cd、Cr、Cu、Hg、Pb、Sn、Zn、TP以及KN)含量数据,利用SOM自组织映射神经网络对污染物时间演变特征进行识别.将1991~2010年分为4个阶段,1991~1995年低含量阶段;1996~2001年高含量阶段;2002~2006年含量波动阶段;2007~2010年含量回落阶段.各沉积物中污染物的变化模式不尽相同,但各类重金属含量峰值多集中出现在1996~1999年、2005~2007年2个时间段内.在污染物含量变化的时序分析基础上,参考入湖污染负荷、污染源普查数据等相关资料,分析人类活动对滇池沉积物中主要污染物的影响,发现人类活动对沉积物中污染物含量变化的影响很大,在污染物排放量大的时期,沉积物中污染物含量也会随之出现明显升高,在采取污染控制及治理措施后,沉积物中污染物含量会随之下降.     

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.     

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.     

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.     

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.     

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.     

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.     

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.