典型药物及个人护理品在黄东海海域水体中的检测、分布规律及其风险评估

目前对沿海地区存在的药物及个人护理品(PPCPs)的了解十分有限,建立能同时精确检测海水样品中多种PPCPs的方法至关重要.本研究选取非甾体类消炎药、抗生素、脂质调节剂和兴奋剂等类别的9种PPCPs作为检测对象,建立固相萃取-高效液相色谱-质谱联用方法(SPE-HPLC-MS),确定了固相萃取柱的填料、洗脱液组成及用量等最佳实验条件.结果表明,萃取柱为CNW HLB,洗脱液为甲醇∶乙腈(1∶1,体积比),洗脱液体积为6 m L,水样pH为7,流速为5 m L·min~(-1),螯合剂EDTA-Na_2添加量为1 g,且浓缩倍数为500倍时,萃取效果最佳.9种PPCPs的线性回归方程均具有良好线性,相关性系数均大于0. 999,回收率在82%～106%之间,相对标准偏差在1. 6%～14%之间,检出限在0. 01～2 ng·L~(-1)之间,满足海水中痕量分析的要求.于2018年夏季对黄东海表层水体中PPCPs的分布特性、来源和分布规律进行研究.9种PPCPs均被检出,主要污染物是NAP、IBU、GEM、CAF和ASA.在空间分布上,PPCPs浓度整体呈现河口近岸高,远海海域较低的趋势,黄海海域中PPCPs浓度高于东海,这与黄海海域污染源多、其水交换能力与东海相比较弱有关.主成分分析结果显示,表层海水中的PPCPs浓度与盐度和pH之间具有负相关性,与叶绿素a具有一定正相关性,表明PPCPs的主要来源为陆源输入.运用风险熵值法对该海域的PPCPs进行环境风险评估,9种PPCPs的RQ均小于1,其中IBU和NAP的RQ大于0. 1,可能对该海域产生中度风险危害,其余PPCPs的RQ均小于0. 1,表明其目前对黄海及东海海域基本没有危害.     

黄浦江流域典型药物和个人护理品的含量及分布特征

采用固相萃取-高效液相色谱/串联质谱法(SPE-HPLC-MS/MS)分析上海市黄浦江流域7种典型药物和个人护理品(PPCPs)的含量水平.结果表明,所建立的分析方法具备良好的回收率(87%~107%)、相对标准偏差(<14%)及方法定量限(0.1~1.1ng/L),满足水体中微量污染物的检测要求.应用该方法检测得到,上海市黄浦江流域水体中目标 PPCPs的含量在相似文献   

SPE-HPLC法同时测定水中3种典型PPCPs

建立并优化了SPE-HPLC同时测定对乙酰氨基酚(PCT)、碘普罗胺((IOP)和阿莫西林(AMX)3种典型PPCPs的检测方法。当流动相为甲醇和水,检测波长230 nm、柱温30℃、采用连续梯度洗脱程序时,3种目标物质均获得良好的分离,并呈现出良好的线性关系(RSD0.998),检出限(LOD)为10.2~247.3μg/L,样品平均加标回收率为94.97%~102.45%,R~2为0.238%~0.756%。以HLB为固相萃取小柱、上样流速3 mL/min、洗脱液甲醇8 mL时,3种PPCPs可实现80.45%~89.70%的回收率。应用此方法对九江学院污水处理厂的出水进行测定,检出IOP和AMX浓度分别为0.400μg/L和19.866μg/L。     

固相萃取-高效液相色谱法同时测定废水中喹乙醇和3种四环素类抗生素

建立了固相萃取-高效液相色谱法同时检测废水中喹乙醇、土霉素(OTC)、四环素(TC)和金霉素(CTC)的分析方法。实验对前处理方法和色谱条件进行了探讨和优化,结果表明水样pH值为2.5,不加提取剂时Oasis HLB柱的纯化富集效果最好,液相色谱在375 nm处对四种物质的分离性能最佳。该方法具有良好的线性关系(r>0.999),最低检出限为11～26 ug/L。喹乙醇和3种四环素类抗生素的加标回收率分别为91%～95%,90%～91%,86%～90%和81%～86%,相对标准偏差为3.4%～6.3%。     

固相萃取-高效液相色谱-质谱联用法检测环境水样中五种持久性有机污染物

持久性有机污染物(POPs)是指能通过环境降解,持久存在于各种大气、残留物、土壤、水及生物体内,通过生物食物链累积、并对人类健康造成有害影响的化学物质。本文建立了固相萃取(SPE)和高效液相色谱-质谱联用分析方法(HPLC-MS),同时定量测定环境水样中全氟辛酸(PFOA)、全氟辛磺酰酸(PFOS)、全氟己酸(PFHA)、双酚A(BPA)、3-羟基-四溴联苯醚(3-OH-BDE-47)5种持久性有机污染物。该方法在1~1 000 ng·m L-1的范围内具有良好的线性关系,检测限在1~8 ng·L-1,水样加标回收率为93.2%~110.1%,相对标准偏差(RSD)为2.7~9.1%,可以满足复杂水样中相关POPs的分析检测。     

超高效液相色谱-串联质谱同步检测艾比湖中14种抗生素

采用超高效液相色谱-串联质谱法(UPLC-MS/MS),建立了同时检测水样中三类共计14种抗生素的分析方法。水样经HLB小柱萃取富集后,用10%甲醇含0.1%的甲酸溶液定容,以高效液相色谱-串联质谱对目标物进行分析。在最优实验条件下,14种抗生素的线性范围为1.0~500μg/L,相关系数均大于0.99,方法的检出限为0.30~1.23 ng/L。将建立的方法应用于检测艾比湖湖水中14种抗生素的残留分析,结果表明:14种抗生素中共检测出12种,其中氧氟沙星、洛美沙星、环丙沙星、土霉素的检出率为100%,洛美沙星的浓度最高。     

药品和个人护理用品类污染物（PPCPs）在北江流域的浓度分布特性初探

采集了北江流域10个点位的水样,经过固相萃取、氮吹、重构等预处理后,将水样浓缩2000倍,采用高效液相色谱-串联质谱法测定8种典型PPCPs的浓度。结果表明,在所取的10个点位的水样中,均检出了不同浓度的PPCPs,其中,在五星测点水样中检出了高达356 ng/L的咖啡因。就PPCPs含量高低而言,五星、丰年以及新花港测点水质较差,紫洞、新境、沙口、石湾和润石大桥测点的水质相对较好。     

垃圾填埋场渗滤液中药物和个人护理品的存在与去除

采用固相萃取–高效液相色谱/串联质谱法,分析上海市某生活垃圾填埋场渗滤液中7种典型药物和个人护理品（PPCPs）的浓度水平,并考察该填埋场的渗滤液处理工艺对目标PPCPs的处理效果.结果表明,所建立的分析方法具备较好的回收率（89%~173%）、相对标准偏差（<20%）和方法检出限（0.025~1.0μg/L）,能满足实际环境样品的分析需要.应用该方法检测到渗滤液中目标PPCPs的含量在低于检出限（90%,总去除率可达到97%以上,出水PPCPs浓度范围为     

析因设计DLLME-SFO同时萃取水中EDCs的应用

采用全析因设计对分散液液微萃取-上浮溶剂固化(DLLME-SFO)同时萃取水中五种环境内分泌干扰物包括雌酮(E1)、雌三醇(E3)、双酚A(BPA)、己烯雌酚(DES)和壬基酚(NP)的条件进行优化,建立了预测回归方程,并分析了因素对DLLME-SFO萃取回收率的影响。利用SAS软件分析得到的最优条件为盐浓度(m/v)15%、水样体积3 mL、分散剂(甲醇)体积0.5 mL以及萃取剂(十二醇)体积120μL。在优化萃取条件下,E1、E3、BPA、DES和NP萃取回收率的预测值分别为46.17%、74.38%、79.20%、69.62%和73.05%,实验验证值分别为44.15%、87.76%、77.83%、77.68%和70.01%,实验值与预测值的相对偏差小于10%。将建立的DLLME-SFO方法用于测定实际水样中的目标化合物,结果显示实际水样中E3、BPA、DES、E1和NP同时萃取回收率分别为64.81%~76.18%,88.09%~83.15%,68.38%~70.08%,66.37%~68.72%,68.35%~72.80%,相对标准偏差(n=3)在1.47%~8.09%之间。     

北京城区水体中PPCPs的分布特征及潜在风险

采集北京城区河流34个表层水样和23个沉积物样品,采集后海、前海和西海这3个城市湖泊10个表层水样和5个沉积物样品,应用HPLC-MS/MS技术对表层水样及沉积物样品中10种药物及个人护理品(PPCPs)进行检测分析,发现河流表层水样和城市湖泊表层水样中PPCPs的浓度范围分别为N.D.~655 ng·L~(-1)和N.D.~252 ng·L~(-1).在河流表层水样中,10种PPCPs的检出率范围为0~100%,其中咖啡因的检出率为100%,磺胺甲唑、地尔硫卓和泰乐菌素均未检出;在湖泊表层水样中,10种PPCPs的检出率范围为0~100%,其中对乙酰氨基酚、林可霉素、咖啡因和阿奇霉素的检出率为100%,磺胺甲唑、地尔硫卓、泰乐菌素及卡马西平都未检出;河流沉积物和城市湖泊沉积物中PPCPs的含量范围分别为N.D.~1 709ng·g~(-1)和N.D.~35.9 ng·g~(-1),在河流表层沉积物中,10种PPCPs的检出率范围为4%~96%,其中甲氧苄啶的检出率最高,泰乐菌素的检出率最低;在湖泊表层沉积物中,10种PPCPs的检出率范围为0~100%,其中地尔硫卓的检出率最高,咖啡因、泰乐菌素和卡马西平均未检出.从各河流看,永定引水渠、凉水河、通惠河及坝河表层水体及沉积物中PPCPs的含量较高,永定河、昆玉河表层水体中PPCPs的含量较低.应用风险商值(RQ)模型评价北京城区各河流及湖泊表层水体与沉积物中PPCPs残留对生态环境的影响,发现北京城区河流及湖泊表层水体中的10种PPCPs的RQ值均低于0.1,对河流生态环境具有低风险.城区河流及湖泊沉积物中,对乙酰氨基酚对永定引水渠、通惠河及坝河底栖生态环境具有中等风险;林可霉素对永定引水渠、温榆河、通惠河、护城河、坝河、凉水河及后海底栖生态环境具有中等风险;甲氧苄啶对永定引水渠、清河、温榆河、通惠河、护城河、坝河、亮马河、凉水河及后海底栖生态环境具有中等风险;阿奇霉素对亮马河及凉水河底栖生态环境具有中等风险,对永定引水渠、清河、温榆河、通惠河、坝河及后海底栖生态环境具有高风险.     

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.