我国24个典型饮用水源地中14种酚类化合物浓度分布特征

研究了14种酚类化合物在我国五大流域(黄河、海河、辽河、长江、淮河)24个典型饮用水源地水源水中的浓度水平.结果显示:14种酚类化合物在我国饮用水源地中的浓度在nd～213 ng·L-1范围内,浓度均值在2.44～31.2 ng·L-1范围内,浓度中位数在nd～40.0 ng·L-1范围内.14种酚类化合物中,硝基苯酚类化合物浓度最高,浓度中位数为37.9 ng·L-1,浓度平均值为27.4 ng·L-1.其次为苯酚、五氯酚、二氯苯酚(2,4-二氯苯酚和2,6-二氯苯酚)和三氯苯酚(2,4,6-三氯苯酚和2,4,5-三氯苯酚);四氯苯酚(2,3,5,6-四氯苯酚、2,3,4,6-四氯苯酚、2,3,4,5-四氯苯酚)和烷基苯酚(邻甲基苯酚、间甲基苯酚和对甲基苯酚)浓度较低.通过商值法对14种酚类化合物进行生态风险评价后发现,14种酚类化合物的风险商均远小于1,表明其对我国饮用水源地的生态风险较低.对8种已报道健康参考剂量或致癌斜率因子的酚类化合物进行健康风险评价,结果显示,7种酚类化合物的最大非致癌风险在10-6到10-4范围内,2,4,6-三氯酚和五氯酚的致癌风险在10-6量级以下,表明其健康危害较弱.     

微波消解-原子荧光法测定茶叶中的微量汞和砷

建立微波消解-原子荧光法测定茶叶中的微量汞和砷的方法,汞浓度在0μg/L-5．0000μg/L范围内与荧光强度呈线性关系,线性方程y=966．1232x,相关系数r=0．9992,汞的检出限为0．026μg/L;砷浓度在0μg/L-10．00μg/L范围内与荧光强度呈线性关系,线性方程为y=62．1511x,相关系数r=0．9993,砷的检出限为0．087μg/L。样品6次测定结果,汞的相对标准偏差为9．66％,加标回收率为96．4％～101．3％;砷的相对标准偏差为1．45％。加标回收率为91．4％～105．1％。环境标准样品测定结果与标准值相吻合。所测样品中汞、砷含量均在国标限值范围之内。该法简便快捷,灵敏度高,测定结果准确可靠。     

包头牧业区氟化物大气质量基准的研究

用石灰滤纸法测定了包头地区大气中氟化物的浓度分布;找出了大气中氟浓度(x)与牧草中氟浓度(y)的相关方程 y=0.38+0.0679x;牧草含氟量(x)与羊羔斑釉齿发病率(y)的相关方程 y=-9.24+1.07x;山羊骨氟增量(y)与摄氟积(xt)之间的相关方程 y=-46.2+0.129xt。根据这些结论确认包头牧业区的氟污染主要由包钢等工业排氟使大气受到污染所造成;找出了氟化物大气质量基准为30μg/dm~2/月。据此划定包头地区八○年的污染面积约为3800km~2。建议以石灰滤纸法测定值30μg/dm~2月作为制定氟化物大气质量标准时的依据。     

太子河中游河段有机污染物分布特征研究

串联极性和非极性固相萃取柱对太子河中游水样进行富集,应用气相色谱-质谱联用仪(GC-MS)定量测定了近百种有机污染物,结果显示,太子河中游河段污染物种类繁多,苯系烃浓度为1.77~11.20μg/L;常见多环芳烃(PAHs)总浓度为2.72~13.89μg/L,与国内污染较重水体中的浓度相当;一元苯酚总浓度为8.31~20.86μg/L,部分超过国家《地表水环境质量标准》(GB 3838-2002)Ⅳ类水限值;硝基苯类物质虽未超过国家GB 3838-2002限值,但普遍高于国家其他水体浓度。应用改进潜在风险指数法筛选出40种优先控制污染物,其中萘、荧蒽、间甲酚、对硝基甲苯为中国水中优先控制污染物黑名单中物质;PAHs来源解析显示,PAHs主要来源于化石燃料燃烧和石油源。     

辛基酚在模拟水生态系统中的归趋与迁移动态

模拟水生态系统构建了室内微宇宙系统,包括水相、沉积物、苦草和斑马鱼,并利用高效液相色谱-串联质谱法研究了典型烷基酚类化合物辛基酚(OP)在其中的动态变化过程。结果表明,在模拟水生态系统中加入200μg/L的OP后,在各相中的暴露浓度随时间的变化而变化,试验结束时(23 d)水相、沉积物、苦草和斑马鱼中的平均浓度分别为7.98μg/L、16.7 ng/g、10.9μg/g和0.67μg/g;不同环境介质对OP的富集存在较大差异,其富集能力为苦草斑马鱼沉积物。     

典型内分泌干扰物在太湖及其支流水体和沉积物中的污染特征

采用固相萃取-高效液相色谱/串联质谱法(SPE-HPLC-MS/MS)对太湖及支流表层水和沉积物中双酚A(BPA)、四溴双酚A(TBBPA)和3种烷基酚类化合物的浓度水平及分布特征进行调查,并对其潜在风险进行评估.结果表明,表层水体中壬基酚(NP)和BPA是主要检出组分,平均含量分别为29.6ng/L(0~121ng/L)和17.5ng/L(0~55.1ng/L);沉积物中NP的浓度含量最高,平均值为240ng/g(0~2045ng/g),其次为TBBPA,平均值为81.0ng/g(0~901ng/g),且目标物总含量与沉积物中TOC含量具有正相关性,整体污染趋势表现为太湖支流和北太湖较严重.生态风险评价结果表明,太湖及其支流水体中目标物的联合毒性风险熵相对较高,其生态风险不容忽视;另外,5种目标物对于人体健康风险评估表明,健康风险总EEQt值1ng E2/L,对于人体健康不具有明显的风险.     

化学解偶联剂对污泥产率的比较研究

研究比较了8种化学物质--邻氯苯酚 (oCP),间氯苯酚 (mCP),2,4-二氯苯酚 (DCP), 2,4,5-三氯苯酚 (TCP),对硝基苯酚 (pNP),间硝基苯酚 (mNP),2,4-二硝基苯酚 (DNP)和3,3',4',5-四氯水杨酰苯胺(TCS)对污泥产率的影响.结果表明:8种化学物质都能有效地控制污泥产率,均可以做为解偶联剂.硝基酚类化合物比氯酚类化合物的污泥减量化效果要好,DNP和pNP的污泥减量化效果最好,分别达到89.16% 和83.77%.解偶联剂效果的差异与其酸性大小有关,其pK_a越低,污泥的减量化效果越好.随着解偶联剂质量浓度的升高,污泥产率逐渐减小. 解偶联剂质量浓度固定不变时,随着污泥质量浓度的升高,污泥产率逐渐提高.高污泥浓度将弱化解偶联剂的效果,因此建议采用比解偶联剂浓度(解偶联剂质量浓度/污泥质量浓度)来选择解偶联剂.      

典型酚类化合物水相光氧化产物光谱特征分析

生物质燃烧可直接排放棕色碳类物质(BrC),也可通过排放的亲水性酚类化合物的水相光解生成BrC,但初始浓度对光氧化产物光谱特征的影响研究较少。该研究选择3,5-二羟基苯甲酸、4-甲基邻苯二酚、2-甲氧基苯酚和2,6-二甲氧基苯酚进行水相溶液直接光照模拟,考察不同分子结构和不同初始浓度(0.1、0.5、1和5 mmol/L)对光解产物的影响。结果表明,在300 W高压汞灯光源照射下,溶液颜色都表现为从无色变为浅黄色,紫外-可见吸收随波长单调递减,显示有BrC的生成;0.1 mmol/L低浓度溶液出现了先变黄加深后变浅的光漂白现象,而其他高浓度溶液在365 nm处的吸光度呈逐渐增加趋势;光解速率呈现3,5-二羟基苯甲酸大于4-甲基邻苯二酚,以及2-甲氧基苯酚大于2,6-二甲氧基苯酚的差异,表明酚类化合物结构对光解过程有重要影响。结合三维荧光中心红移分析,推测酚类化合物的直接光解过程为有机自由基反应驱动的低聚过程。     

上海某石化园区周边区域VOCs污染特征及健康风险

为了解石化周边区域大气VOCs污染特征,使用在线GC-FID监测仪于2017年10月对上海市某近石化周边居民区大气VOCs进行了为期1个月的连续观测;通过最大增量反应活性(MIR)法估算了VOCs对臭氧(O_3)生成的贡献,并进行了健康风险研究.结果表明,观测期间VOCs总质量浓度的范围16. 4～1 947. 8μg·m~(-3),平均浓度为40. 7μg·m~(-3);烷烃、烯/炔烃和芳香烃的平均占比分别为66. 2%、25. 9%和7. 9%. VOCs总浓度日变化特征呈现单峰型变化,峰值浓度为127. 9μg·m~(-3)(07:00). VOCs总浓度的平均臭氧生成潜势(OFP)为249. 7μg·m~(-3),烯、炔烃对OFP的贡献最高,达到153. 4μg·m~(-3);丙烯、反-2-丁烯、乙烯是关键的活性组分.己烷、苯、甲苯、乙苯、邻-二甲苯和间/对-二甲苯的健康风险较小.     

悬浮泥沙对酚类化合物的吸附特性研究

研究了4种分别取自长江口和杭州湾的悬浮泥沙样品对苯酚、邻氯酚和2,4-二氯酚的吸附特性.结果表明,在12 h内可以达到对酚类化合物的吸附平衡,对苯酚的吸附量小,且不同样品间无显著差别,样品对酚类化合物吸附量随着酚类化合物氯化程度的提高而增大,与样品粒径分布、比表面积、有机物含量有关.在酚类化合物初始浓度＜2.0 mg/L时,样品对酚类化合物的等温吸附可以用Freundlich吸附等温式来表征,计算得到吸附常数Koc分别为622～1 410、3 287～3 707、6 444～8 787.挥发酚国家二级排放标准限定浓度为0.5 mg/L以下,此浓度下水体中悬浮泥沙能够有效吸附挥发酚,但高盐度不利于酚类化合物的吸附.     

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.     

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.     

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.     

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.     

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.     

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.     

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.