污水中新精神活性物质的分析方法优化及验证

随着对传统毒品打击力度的增大,各种为规避现行法律管制而合成的新精神活性物质(new psychoactive substances,NPS)层出不穷.NPS被滥用后,经人体新陈代谢所生成的代谢产物和未被代谢的原药随尿液进入生活污水,从而汇入污水处理厂,经处理后被排入自然水体.因此在国内外以往相关研究的基础上,应用固相萃取和UPLC-MS/MS技术,建立并优化了污水中11种常见NPS的前处理及检测方法.比较了污水前处理条件(如SPE柱、样品p H值、淋洗和复溶等)对目标物回收率的影响.结果表明最优前处理条件为:选用Oasis MCX柱,在p H=2的条件下加载样品,用2 m L p H=2的超纯水和2m L甲醇淋洗SPE柱,400μL 20%的甲醇水溶液复溶.通过对目标物的保留时间、回收率、基质效应、检出限和定量限、精密度等指标的评价,说明优化后的前处理方法和C18-UPLC-MS/MS检测方法高效可靠.应用优化后的方法对北京市11家污水处理厂的进、出水样进行了分析,验证了方法的可靠性,为进一步开展NPS的污水流行病学研究及健康风险评价提供了参考依据.     

超高效液相色谱串联质谱测定地表水中5种磺胺类药物残留研究

建立了一种快速、灵敏、同时定性和定量的固相萃取(SPE)和超高效液相色谱串联质谱法(UPLC-MS/MS)来测定地表水中5种常用磺胺类药物(SAs)残留。100 m L水样经0.45μm滤膜过滤后,利用HLB固相萃取柱来浓缩富集。色谱分离柱选用BEH C18(1.7μm,50×2.1 mm)色谱柱,流动相选用甲酸水溶液/乙腈,0.30m L/min梯度洗脱。在电喷雾-多反应监测正离子模式下,进行定量定性分析。线性范围在0.2~20 ng/m L之间,r2≥0.997。以标准加入法计算回收率和相对标准偏差,在2~10 ng/L添加浓度范围内,平均回收率在75.2%~84.6%之间,相对标准偏差在4.1%~8.6%之间,最低检测限和定量限分别为0.03 ng/L和0.05 ng/L。综合讨论了HLB萃取柱对水和废水中磺胺类药物的浓缩富集作用,探讨了几种影响浓缩富集效果的条件,优化了提取和净化方法。最后应用该方法检测哈尔滨周边地点地表水中5种磺胺类药物的残留情况。     

污水中短长链全氟羧酸检测方法的开发

开发了弱阴离子交换柱固相萃取+高效液相色谱-负电喷雾-串联质联法[WAX-SPE+HPLC-ESI(-)-MS/MS]检测污水中碳链长度在2~14内的全氟羧酸(PFCAs).采用弱阴离子交换(WAX)柱进行固相萃取时,将污水水样用甲酸酸化至pH=3.0,并使用2%甲酸溶液作净化溶剂、1%氢氧化铵甲醇溶液作洗脱溶剂,则可使短长链PFCAs(C2~C14)均具有较高的回收率,并克服了反相固相萃取柱对短链PFCAs(C2~C5)回收率低的缺点.为了验证方法的有效性,对上海市市政污水处理厂A和B的进水进行检测,结果表明各种PFCAs的回收率分别在56%~121%和54%~120%的范围内,相对标准偏差(RSD)分别小于11%和14%,方法检出限和定量限分别在0.2~1.0 ng/L和1.0~5.0 ng/L的范围内,这充分证明了该方法的可靠性.此外,在处理厂A和B内含量最高的PFCAs均为全氟辛酸(分别为743 ng/L和837 ng/L),其次为三氟乙酸(分别为139 ng/L和489 ng/L).     

固相萃取—气相色谱法测定海水中的666、DDT

采用固相萃取技术富集海水中的666、DDT,并使用气相色谱进行测定。主要包括不同填料(C8、C18、C18-N)、SPE柱规格(500 mg/3 mL、500 mg/6 mL)、洗脱试剂、上样流速、水样pH和洗脱试剂体积6个因素对666、DDT富集效率的影响。最终确定最优条件为:采用500 mg/6 mL C18SPE小柱,调节海水pH=6,上样流速4~5mL/min,10 mL二氯甲烷洗脱。优化后的固相萃取-气相色谱方法测定海水中666、DDT加标10 ng/L回收率为75.7%~110.4%,精密度为1.16%~4.00%,方法检出限为0.19~1.20 ng/L。     

SPE-RRLC-MS/MS法测定制药废水中青霉素G

建立了利用固相萃取-高分离度快速液相色谱-串联质谱(SPE-RRLC-MS/MS)测定制药废水中青霉素G残留的方法。水样以30%硫酸锌+20%亚铁氰化钾作为沉淀剂沉淀蛋白质后,上清液采用Oasis HLB固相萃取柱富集和净化,以0.01 mol/L乙酸铵溶液(加0.1%甲酸)+乙腈作为流动相进行等度洗脱,经Agilent Plus C18柱分离后,在串联质谱ESI(+)源下进行MRM检测。该方法的青霉素G检出限(S/N=3)为0.02μg/L,目标物在0.0020～1.0 mg/L范围内线性关系良好,线性相关系数为0.9997。在0.20,1.0,2.0μg/L添加水平平均回收率为74.6%～101.4%,相对标准偏差为4.49%～8.17%。该方法灵敏度高、重现性好、定性定量准确,可满足制药废水中青霉素G残留检测的要求。     

固相萃取-超高效液相色谱串联质谱法测定城市污水中5种β-受体阻断剂

β-受体阻断剂是一类常用的心血管疾病治疗药物. 建立了城市污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔5种β-受体阻断剂的超高效液相色谱-串联质谱联用检测方法. 水样经MCX固相萃取小柱富集、净化,采用0.1%甲酸水溶液与乙腈为流动相进行梯度洗脱,经BEH C18色谱柱分离,通过多反应监测模式进行测定. 该方法对5种β-受体阻断剂的线性范围为0.1～100.0 μg/L,相关系数(R2)均大于0.99. 污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔的定量限为0.2～2.0 ng/L,加标回收率为54.1%～113.4%,相对标准偏差小于22%,可用于城市污水中相关物质的分析测定.      

SPE-UFLC-MS/MS法测定制药废水中四环素类抗生素

文章建立了利用固相萃取-超快速液相色谱-串联质谱(SPE-UFLC-MS/MS)测定制药废水中四环素类抗生素(土霉素、四环素和金霉素)残留的方法。水样经(30%硫酸锌+20%亚铁氰化钾)溶液作为沉淀剂沉淀蛋白质后,上清液采用Oasis HLB固相萃取柱富集和净化,以(0.1%甲酸溶液+乙腈)为流动相进行梯度洗脱,经Agilent ZORBAX SB C18柱分离后,在串联质谱ES(I+)模式下进行MRM检测。该方法四环素类抗生素检出限(S/N=3时)0.02μg/L,3种目标物在0.010¹.0 mg/L范围内线性关系良好,线性相关系数在0.998 21.0 mg/L范围内线性关系良好,线性相关系数在0.998 2⁰.999 8之间。在0.20、0.40和0.60μg/L添加水平,各组分的回收率在80.8%0.999 8之间。在0.20、0.40和0.60μg/L添加水平,各组分的回收率在80.8%⁹7.2%之间,相对标准偏差在5.31%97.2%之间,相对标准偏差在5.31%⁹.92%之间。该方法可满足制药废水中四环素类抗生素残留检测的要求。     

基于ICP-AES法测定太湖溶解态有机磷的初步研究

以2010年5月27日太湖水样为测试对象,进行典型溶解性有机磷(草甘膦和植酸)的ICP-AES加标回收试验验证C18柱去除有机磷的能力,探讨了样品消解在ICP-AES法测定TSP过程的作用,使用ICP-AES法测定水样中不同形态磷含量间接定量太湖DOP水平,并与传统方法测得的DOP含量作对比。结果表明,过C18柱可去除水样中96%以上的有机磷,能实现过滤前后水样有机物差异的效果;水样经过消解后测定值(TSP)为0.025~0.095 mg/L,大大高于未消解系列测得值(0.009~0.030 mg/L),ICP-AES法测定有机磷含量较高的水样时需要经过消解的预处理步骤;使用ICP-AES与C18柱相结合的方法测得太湖DOP含量为0.014~0.069 mg/L之间,大大高于传统比色法DOP测得值0.026~0.083 mg/L,前法能更准确的间接定量水体中DOP水平,而后法可能会大大高估DOP在水环境中的实际含量。     

高效液相色谱法测定联苯菌胺生产废水中联苯类物质

建立了废水中联苯菌胺和三氟硝基联苯的高效液相色谱分析方法.采用Kromasil - C18 (150 mm×4.6mm,5μm)色谱柱,流速1 mL/min,柱温30℃,进样体积10μL,流动相为V(乙腈):V(0.1％磷酸溶液)=60:40,测定波长205 nm.结果线性范围为:0.05～ 10mg/L,联苯菌胺的平均加标回收率为104.1％,相对标准偏差为1.65％.三氟硝基联苯的平均加标回收率为106.8％,相对标准偏差为1.37％.     

SPE-UPLC-MS/MS测定水中不同类别的9种抗生素

建立了固相萃取-超高效液相色谱/电喷雾离子源/三重四极杆串联质谱(SPE-UPLC-MS/MS)同时测定水中不同类别的9种抗生素的方法。水样经HLB固相萃取柱富集净化,6 m L酸化甲醇(φ(甲酸)=0.5%,先加入3 m L洗脱液,过柱完全后,再空抽至抽干,再加3 m L洗脱液)洗脱、浓缩,用V(甲醇)︰V(甲酸)=8︰2的水溶液1 m L定容后,采用BEH C18柱,以φ(甲酸)=0.01%的甲酸溶液-甲醇作为流动相进行梯度洗脱,采用串联质谱作为检测器进行检测。方法快速、灵敏,适用于水体中抗生素残留的测定。     

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.     

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.     

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.     

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.     

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.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.