在线固相萃取-超高效液相色谱/串联质谱法测定水中的11种精神活性物质

采用在线固相萃取-超高效液相色谱/串联质谱技术,建立了地表水中广泛存在的11种精神活性物质的检测方法.样品经微孔滤膜过滤后,用甲酸调节至pH=3.0,直接进入在线固相萃取-超高效液相色谱/串联质谱仪进行分析.样品以Oasis HLB萃取柱净化富集,被流动相反冲出萃取柱后进入UPLC系统,采用Waters ACQUITY BEH C18色谱柱分离.上样泵(四元泵)的流动相为纯水和体积分数为0.5%的甲酸乙腈溶液,分析泵(二元泵)的流动相为乙腈和体积分数为0.1%的甲酸水溶液.以电喷雾正离子(ESI+)多反应监测模式(MRM)进行定性定量分析.该方法分析时长13.0 min,11种精神活性物质在0—10 ng·L~(-1)范围内线性关系良好,线性相关系数R~2≥0.9877,检出限≤0.1 ng·L~(-1),6次平行测定峰面积RSD≤10.80%.该方法前处理简单、快速、重现性好,可用于环境水体和饮用水中痕量精神活性物质的测定.将建立的方法应用于北京市城市地表水及污水处理厂采集的水样分析,地表水中未检测到苯丙胺,污水处理厂水样中检测出11种精神活性物质,其中浓度最高的为可替宁,在进水中最高可达到2035.28 ng·L~(-1).     

太湖入湖河流中精神活性物质污染特征与生态风险

精神活性物质是一类摄入人体后对中枢神经系统具有强烈兴奋或抑制作用的新型污染物,其在水环境中的存在可能对水生生物、水生态系统甚至人体健康产生潜在的危害。为评价太湖中精神活性物质的污染水平和生态风险,利用超高效液相色谱-质谱联用法检测了太湖19条入湖河流中13种典型精神活性物质的质量浓度和空间分布规律。结果表明,在太湖19条入湖河流中除苯甲酰牙子碱(BE)和去甲氯胺酮(NK)外,其余11种目标物均有检出,质量浓度范围为n.d.～43.2 ng·L~(-1)。其中麻黄碱(EPH)的检出率和中间浓度最高,分别为100%和11.0 ng·L~(-1);其次为甲基苯丙胺(METH),检出频率为58%,浓度中值为1.0 ng·L~(-1);苯丙胺(AMP)在东部湖区均未检出。大部分精神活性物质浓度水平较高的河流分布在竺山湾和西太湖,而海洛因(HR)的高值区主要在南太湖。运用风险熵方法对其进行风险评估,结果显示,太湖流域地表水中检出的13种精神活性物质的风险熵值均<0.1,生态风险较低,但其对水生生态系统的长期和综合风险值得关注。     

以污水流行病学监测广西某市12个污水处理厂服务区域精神活性物质的消耗量

精神活性物质滥用和使用量逐年递增正成为社会稳定、环境健康新的关注点。准确地估算某一地区这类化合物的消耗总量是管理这类物质的关键。本研究对中国广西某市12个污水处理厂(wastewater treatment plants,WWTPs)服务区域中的8种精神活性物质消耗量进行了调查。首先,采用固相萃取-液相色谱-串联质谱法测定了广西某市12个WWTPs进水中8种精神活性物质的浓度,检测到在<方法检测(method detection limit,MDL)至170.9 ng·L^-1范围内的5种精神活性物质。然后,依据污水流行病学(wastewater-based epidemiology,WBE)进行消耗量反算。结果表明,氯胺酮(ketamine,KET)、吗啡(morphine,MOR)、冰毒(methamphetamine,METH)、摇头丸(3,4-methylenedioxymethamphetamine,MDMA)是主要检出的精神活性物质,平均消耗量分别为682.4、167.8、44.6、11.3 mg·d^-1·1000inh^-1;而可卡因(cocaine,COC)、苯甲酰爱康宁(benzoylecgonine,BE)、甲卡西酮(methcathinone,MC)没有被检出。对WWTPs进水中精神活性物质的残留进行分析,估算这些物质在特定区域的消耗量,为防控风险提供支持。     

金鸡菊(Coreopsis drummondii)的抗TMV活性物质

采用活性跟踪法从金鸡菊根中分离获得抗病毒活性物质,经质谱和核磁共振分析,鉴定该物质为1-苯基-1,3,5-三庚炔.采用半叶枯斑法、叶圆盘法测定了该物质对烟草花叶病毒的抑制效果,结果表明,0.2 mg/mL的该化合物对TMV表现出较好的体外抑制侵染和增殖活性,其对TMV侵染和复制的抑制率分别为73.5%和84.3%.实时荧光定量PCR测定结果表明,该化合物对TMV外壳蛋白基因的表达有明显的抑制作用,0.2 mg/mL的该化合物对TMV外壳蛋白基因表达的抑制率为79.8%.图6表1参19     

链霉菌S227抗耐药性物质的分离及其活性研究

在抗耐药性活性筛选过程中,发现分离自四川峨嵋山森林土壤的一株链霉菌S227(Streptomyces sp.)的发酵液具有抗细菌抗生素耐药性生物活性.利用已建立的抗耐药性的活性检测方法(专利号:ZL01128969.4)[1]为跟踪手段,采用有机溶剂萃取、硅胶柱层析以及薄层层析等方法,对该菌发酵液中抗耐药性活性物质进行分离纯化,得到了具有抗耐药性的活性单体S227-4,初步鉴定为四聚糖.利用MIC法对该样品的抗耐药活性进行研究:在证明该样品本身不具有抗菌活性的基础上,以临床分离的耐药菌株为指示菌,考察了该样品与抗生素联合使用时对耐药菌抗生素MIC(最小抑菌浓度)值的影响,结果表明,S227-4在不影响耐药菌生长的浓度下与不同的抗生素联合使用,可以明显提高不同耐药菌对不同抗生素的敏感性,如S227-4(200μg/mL)可以使S.aureus12334对红霉素的敏感性提高128倍.图2表2参8     

QuEChERS-超高效液相色谱-串联质谱法同时测定斑马鱼中多种激素生物标志物

本文建立了一种同时测定斑马鱼体内23种激素生物标志物的快速分析方法.该方法采用QuEChERS方法对样品进行提取和净化,待测物采用超高效液相色谱-串联质谱法(UPLC-MS/MS)分析,检测的23种激素生物标志物均采用同位素内标法定量.仪器检测限(IDL)范围为0.01-0.19 ng· mL-1,方法定量限(MQL)...     

SUMMA罐捕集-GC/MS法测定空气中挥发性有机物

采用预冷冻浓缩系统进样和气相色谱-质谱(GC-MS)联用检测,建立了测定空气中13种挥发性有机化合物的分析方法,该方法利用苏玛(SUMMA)罐采集空气样品,经过零下160℃冷冻浓缩后解析进样,用GC-MS检测.分析结果表明,该方法对空气样品分析的精密度很高,重复性好.SUMMA罐捕集的空气样品具有很好的代表性,样品无污染,可应用于各种复杂环境条件下的样品采集,还可以与多种仪器串联检测不同种类的污染物质.     

通过式固相萃取净化/超高效液相色谱-串联质谱法测定畜禽肉中19种除草剂残留

建立了一种快速测定畜禽肉中19种除草剂残留的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法.样品以乙腈提取,经Oasis PRiME HLB固相萃取柱通过式净化,采用ACQUITY UPLC BEH C_(18)柱(2.1 mm×50 mm, 1.7μm)进行液相色谱分离,以乙腈和0.1%甲酸溶液作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定量分析,以基质配制标准溶液外标法定量.结果表明,19种除草剂在0.2—50μg·L~(-1)范围内线性关系良好(R~20.999),方法检出限为0.5—2.0μg·kg~(-1),定量限为1.7—6.7μg·kg~(-1),在3个添加水平的加标回收率为70.2%—127.5%,相对偏差为4.1%—10.9%.该方法前处理简便快速,且准确性好、灵敏度高,适用于畜禽肉中19种除草剂残留的测定.     

顶空固相微萃取-气质联用法同时测定城市水源水中的九种嗅味物质

建立了顶空固相微萃取-气相色谱-质谱联用(HSPME-GC-MS)的分析方法同时检测城市水源水中的9种痕量嗅味物质,具体包括6种土霉味物质(2-甲基异莰醇、土嗅素、2-异丙基-3-甲氧基吡嗪、2-异丁基-甲氧基吡嗪、2-甲基苯并呋喃和2,4,6-三氯苯甲醚)及3种其他种类的嗅味物质(1种鱼腥味物质反,反-2,4-庚二烯醛,1种干草味物质β-环柠檬醛和1种芳香味物质β-紫罗兰酮).在水浴加热搅拌的条件下,利用固相微萃取纤维顶空吸附水中挥发出的嗅味物质,随后在GC-MS上进行物质解吸并检测.本研究对比了不同HSPME萃取纤维的萃取效果,并优化了萃取时间、萃取温度及解吸温度等前处理及仪器条件.研究得到的最优检测条件为:2cm 50/30μm DVB/CAR/PDMS萃取纤维,在65℃下加热30 min,并于GC进样口解吸3 min.9种嗅味物质在1—200 ng·L~(-1)范围内线性良好,方法检出限为1.36—7.70 ng·L~(-1),其中8种嗅味物质的检出限均低于3.3 ng·L~(-1),对水源水的加标回收率为57.7%—94.8%.测定3个不同城市水源水样品中的嗅味物质浓度,9种物质在水源水中均有检出.除太湖中所含的MIB外,其余水体中MIB及所有水体中的GSM均超过了《生活饮用水卫生标准》(GB5749—2006)中所规定的值.实验证明,HSPME-GC-MS可满足城市水源水中9种痕量嗅味物质的同时检测.     

高效液相离子交换色谱-脉冲积分安培检测法检测新霉素B及其杂质

新霉素是水溶性的氨基糖苷类抗生素复合体,新霉素B(也被称为弗式菌丝)是新霉素复合体中含量最高、活性最强的一类.一般情况下,新霉素B及其杂质(新霉素A、新霉素C、新霉素D、新霉素E和新霉素F)的浓度都必须被检测出来,而这些浓度都必须符合相应指标后,才能进行临床使用.用紫外-可见光检测器,灵敏度达不到要求.而且紫外-可见光检测器直接进样分析会干扰新霉素B及其杂质.用脉冲积分安培检测法对这些特定物质进行有选择性地检测,是一种非常实用的检测技术,具有很宽的线性范围和非常高的灵敏度,是一种非常适合于分析氨基糖苷类抗生素的理想检测方法.高效液相离子交换色谱(HPAE)可以做为一种分离新霉素B及其杂质的手段.     

Ozone kinetics of dimethyl sulfide in the presence of water vapor

The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide （DMS） and ozone （O3） under conditions of relative humidity 55.0%-67.8% at （296±2）K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be （10.4±0.2） × 10^-19 cm^3·molecule^-1·s^-1 at relative humidity of 67.5%±0.3% at 298K, （10.1±0.1） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 66.5%±0.5% at 296K, （7.75±0.39） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 64.8%± 0.1% at 294K and （3.42±0.21） × 10^-19cm^3·molecu- le^-1·s^-1at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O3/ DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.     

高效液相色谱-串联质谱法同时检测水体中26种药物及个人护理品

通过优化固相萃取条件和高效液相色谱-串联质谱参数,建立了可以同时检测地表水和地下水中26种典型药物及个人护理品(pharmaceuticals and personal care products,PPCPs),包括磺胺类、大环内酯类、喹诺酮类、酰胺醇类、精神类、消炎止痛类以及个人护理品的检测方法.通过将水样pH值调节...     

湛江红树林湿地沉积物中多溴联苯醚(PBDEs)的污染特征与生态风险评价

近年来,红树林有机污染物(POPs)污染逐渐加重,其生态环境保护压力日趋加大.湛江红树林保护区是中国面积最大的红树林自然保护区,对生态系统稳定具有重要作用,准确评估湛江红树林湿地多溴联苯醚(PBDEs)的污染现状及潜在生态风险,对了解湛江红树林有机污染物的污染状况、红树林的生态环境保护等具有重要意义.采用索氏抽提法和气...     

Influence of aeration intensity on the performance of A/O-type sequencing batch MBR system treating azo dye wastewater

Among the numerous parameters affecting the membrane bioreactor (MBR) performance, the aeration intensity is one of the most important factors. In the present investigation, an anoxic/aerobic-type (A/O-type) sequencing batch MBR system, added anoxic process as a pretreatment to improve the biodegradability of azo dye wastewater, was investigated under different aeration intensities and the impact of the aeration intensity on effluent quantity, sludge properties, extracellular polymeric substances (EPS) amount generated as well as the change of permeation flux were examined. Neither lower nor higher aeration intensities could improve A/O-type sequencing batch MBR performances. The results showed 0.15 m³·h^-1 aeration intensity was promising for treatment of azo dye wastewater under the conditions examined. Under this aeration intensity, chemical oxygen demand (COD), ammonium nitrogen and color removal as well as membrane flux amounted to 97.8%, 96.5%, 98.7% and 6.21 L·m^-2·h^-1, respectively. The effluent quality, with 25.0 mg·L^-1COD, 0.84 mg·L^-1 ammonium nitrogen and 8 chroma, could directly meet the reuse standard in China. In the meantime, the sludge relative hydrophobicity, the bound EPS, soluble EPS and EPS amounts contained in the membrane fouling layer were 70.3%, 52.0 mg·g^-1VSS, 38.8 mg·g^-1VSS and 90.8 mg·g^-1VSS, respectively, which showed close relationships to both pollutant removals and membrane flux.     

Simultaneous analysis of five taste and odor compounds in surface water using solid-phase extraction and gas chromatography-mass spectrometry

In this paper, a method using solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) was developed to simultaneously analyze five taste and odor compounds in surface water, i.e., 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (TCA), 2-isopropyl-3-methoxy pyrazine (IPMP), 2-isobutyl-3-methoxy pyrazine (IBMP), and trans-1,10-dimethyl-trans-9-decalol (geosmin, GSM). The mass spectrometry was operated in selective ion monitoring (SIM) mode. Three kinds of SPE columns and three eluting solvents were compared, the C18 column was chosen as optimum SPE column, and methanol was chosen as the optimum eluting solvent. It was found that the method showed good linearity in the range of 1–200 ng·L^-1 and gave detection limits of 0.5–1.5 ng·L^-1 for individual compounds. Good recoveries (93.5%–108%) and relative standard deviations (1.58%–7.31%) were also obtained. Additionally, concentrations of these taste and odor compounds in Jinan’s surface and drinking water were analyzed by applying this method, and the results showed that GSM and 2-MIB were the dominant taste and odor compounds in Jinan’s raw water.     

同位素内标-高效液相色谱-串联质谱法测定畜禽粪便中6种雌激素

为了研究畜禽粪便中雌激素的污染特征及其环境影响,建立了一种同时提取、分离和检测畜禽粪便中雌酮(E1)、17α-雌二醇(17α-E2)、17β-雌二醇(17β-E2)、雌三醇(E3)、17α-炔雌醇(17α-EE2)和己烯雌酚(DES)共6种雌激素的高选择性和高灵敏性方法——同位素内标-固相萃取-高效液相色谱-串联质谱法。对提取剂、淋洗剂、洗脱剂、色谱分离条件和质谱测定条件等进行了优化。最终的优化方法为:粪便样品加入100 ng同位素内标后,先后用乙腈重复超声提取3次(每次10 mL,每次15 min),离心后合并上清液,旋转蒸发近干再复溶于1 mL甲醇,加7 mL纯水稀释并超声混匀后离心,上清液过0.45μm滤膜后用HLB固相萃取柱净化,经10 mL 15%乙腈水溶液淋洗后,用10 mL的甲醇进行洗脱,氮吹浓缩定容至1 mL,过0.22μm滤膜后测定。用2 mM氟化铵-甲醇为流动相,经TAB色谱柱分离后采用电喷雾离子源和选择反应监测负离子扫描模式进行检测,同位素内标定量。在5、50、200、1000 ng·g^?1加标水平下,6种雌激素的平均回收率为90.2%—103.2%,相对标准偏差为0.09%—9.08%,方法检出限(LOD)和方法定量限(LOQ)分别为0.25—0.95 ng·g^?1和1.00—3.82 ng·g^?1。应用此方法检测了6个猪粪、3个牛粪和3个鸡粪样品中6种雌激素的含量,结果为?1(干质量)。该方法灵敏度高,定量准确且定量范围广,适用于畜禽粪便中6种雌激素的定性定量分析。     

Occurrence and removal of selected polycyclic musks in two sewage treatment plants in Xi’an, China

Polycyclic musks are widely used for cosmetics and other personal care and household cleaning products. The occurrence and removal of two representative polycyclic musks, galaxolide (HHCB) and tonalide (AHTN) were investigated in three different processes of two sewage treatment plants (STPs) in Xi’an, China. The samples were preconcentrated by solid phase extraction procedure and analyzed using a gas chromatography mass spectrometry (GC/MS) by a modified procedure. The HHCB was in the range of 82.8 to 182.5 ng·L^-1 in the influents and 22.6 to 103.9 ng·L^-1 in the effluents. The AHTN ranged from 11.0 to 19.3 ng·L^-1 in the influents and 2.2 to 8.8 ng·L^-1 in the effluents. The removal efficiency of the two musks varied in the ranges of 43.1%–70.4% for HHCB and 54.2%–84.4% for AHTN. Concentrations of the two musks in aqueous phase of three processes slightly increased along the primary process, and significantly removed during the biologic treatment processes, revealing that the selected musks could be remarkably removed in varied activated sludge processes. Advanced processes of activated sludge did not show a significant superiority on selected musk removal compared to the conventional process. The selected musk removal mainly resulted from the adsorption function of activated sludge. There was no significant change of HHCB/AHTN ratios along the treatment flow, indicating that each sewage treatment structure had a similar removal efficiency for the two musks.     

Occurrence of estrogenic endocrine disrupting chemicals concern in sewage plant effluent

The purpose of this study was to give a worldwide overview of the concentrations of typical estrogenic endocrine disrupting chemicals （EDCs） in the effluent of sewage plants and then compare the concentra- tion distribution of the estrogenic EDCs in ten countries based on the survey data of the estrogenic EDCs research. The concentrations of three main categories （totally eight kinds） of estrogenic EDCs including steroidal estrogens （estrone （El）, estradiol （E2）, estriol （E3） and 17a- ethynylestradiol （EE2））, phenolic compounds （nonylphe- nol （NP） and bisphenol A （BPA）） and phthalate esters （dibutyl phthalate （DBP） and dibutyl phthalate （2- ethylhexyl） phthalate （DEHP）） in the effluents of sewage plants reported in major international journals over the past decade were collected. The statistics showed that the concentration distributions of eight kinds of EDCs were in the range of ng·L^-1 to μg·L^-1. The concentrations of steroidal estrogens mainly ranged within 50.00 ng. L-1, and the median concentrations of El, E2, E3 and EE2 were 11.00, 3.68, 4.90 and 1.00 ng·L^-1, respectively. Phenolic compounds and phthalate esters were found at pg. L-1 level （some individual values were at the high level of 40.00 μg·L^-1）. The median concentrations of BPA, NP, DBP and DEHP were 0.06, 0.55, 0.07 and 0.88 μg·L^-1, respectively. The concentrations of phenolic compounds and phthalate esters in the effluents were higher than that of steroids estrogens. The analysis of the concentration in various ten countries showed that steroids estrogens, phenolic compounds and phthalate esters in sewage plant effluents were detected with high concentration in Canada, Spain and China, respectively.     

Biodegradation of 2-methylisoborneol by bacteria enriched from biological activated carbon

One of the most common taste and odour compounds (TOCs) in drinking water is 2-methylisoborneol (2-MIB) which cannot be readily removed by conventional water treatments. Four bacterial strains for degrading 2-MIB were isolated from the surface of a biological activated carbon filter, and were characterized as Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp. based on 16S rRNA analysis. The removal efficiencies of 2-MIB with initial concentrations of 515 ng·L^-1 were 98.4%, 96.3%, 95.0%, and 92.8% for Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp., respectively. These removal efficiencies were slightly higher than those with initial concentration at 4.2 mg·L^-1 (86.1%, 84.4%, 86.7% and 86.0%, respectively). The kinetic model showed that biodegradation of 2-MIB at an initial dose of 4.2 mg·L^-1 was a pseudo-first-order reaction, with rate constants of 0.287, 0.277, 0.281, and 0.294 d^-1, respectively. These degraders decomposed 2-MIB to form 2-methylenebornane and 2-methyl-2-bornane as the products.