HPLC-UV测定水中微量溴酸根的方法

针对水中微量溴酸盐的测定问题,建立了一种用苯酚为衍生试剂、用HPLC-UV检测的柱外衍生测定方法.本方法的检出限为0.82μg·L-1,在溴酸根浓度为5～50μg·L-1范围内具有良好的线性关系(R2=0.9986).测定系列溴酸根浓度的相对偏差(RSD)均小于5%,样品加标平均回收率为99.8%～110.9%.     

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol (OP) in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry (GC-MS) coupled with solid phase extraction (SPE). Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio (S/N = 3) was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations (RSD) was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows: 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.     

Microwave-Assisted Solvent-Free or Aqueous-Based Synthesis of Biodegradable Polymers

Microwave radiation was used as the energy source for various types of chemical derivatizations of polysaccharides and for the synthesis of biodegradable polyesters in solvent-free or aqueous-based reaction systems. A medium to high degree of substitution was obtained for starch acetates, starch succinates, carboxymethyl konjac, aminated starch, and aminated chitosan. Ring-opening polymerization of lactide and -caprolactone proceeded rapidly even at low power output in the presence of tin octanoate catalyst. Complete monomer conversion and high molecular weight were achieved in less than 6 minutes under nonisothermal conditions. The yield rapidly increased with increasing power output and showed no significant change in a wide range of batch sizes. Polycaprolactone was successfully grafted from starch and konjac acetate in 3 minutes, yielding as high as 24% grafting efficiency and 25% grafting degree.     

类固醇雌激素分析方法研究进展

类固醇雌激素因其对野生动物、人类健康及生态环境安全造成危害而受到全世界的普遍关注,并成为环境科学和生态毒理学研究的重点和热点之一.针对4种典型的类固醇雌激素(雌激素酮、17-β-雌二醇、雌三醇和17-α-乙炔基雌二醇),对其羟基和酮基衍生化技术、水和固体样品的前处理技术及仪器检测方法进行了综述,总结了类固醇雌激素分析方法的研究动态和进展.     

污水分析方法监测城市毒品滥用长期趋势

毒品滥用问题是全球广泛关注的社会问题,对城市毒品滥用情况进行长期监测具有重要意义.采用污水流行病学的方法,对大连市毒品的滥用情况进行连续长期调查.2020～2021年采集大连市22个污水处理厂的进口污水,通过气相色谱衍生化方法分析测定甲基苯丙胺、海洛因、氯胺酮、摇头丸和可卡因的生物标志物的浓度,即其尿液代谢产物甲基苯丙胺、吗啡、氯胺酮、摇头丸和苯甲酰芽子碱.结果表明,2020年p(甲基苯丙胺)、p(吗啡)和p(氯胺酮)均值分别为23.69、23.21和2.40 ng·L-1;2021年均值分别为20.64、20.92和0.47 ng·L-1,在所有的污水样品中均未检测出摇头丸和苯甲酰芽子碱,根据相关信息估算5种毒品的人均滥用量,并结合往年监测数据分析大连市这5种毒品的滥用趋势.甲基苯丙胺和海洛因滥用量均在2019年有上升趋势,2020大幅度下降,2021年基本保持不变;氯胺酮的滥用则一直处于较低水平.本研究为大连市实时监控毒品滥用情况提供科学依据,对防治毒品犯罪具有重要意义.     

衍生化气相色谱法测定黄磷诱发氧化水中苯酚降解产物

利用衍生化气相色谱法对黄磷诱发氧化苯酚降解产物进行了研究，在磷酸存在下，以甲醇作酯类衍行生试剂，分别和ＳＥ－５２和ＨＰ－１７石英毛细管双柱结合ＧＣ－ＭＳ进行分离定性定量，黄磷诱发氧化苯酚降解产物以羧酸为主，在反应温度５０℃时，表现为一级反应特征，速率常数（Ｋ）：０．０７７ｍｉｎ＾－１，半衰期（ｔ１／２）：９．０ｍｉｎ。     

气相色谱法测定固定污染源废气中氯甲基甲醚和二氯甲基醚的研究

氯甲基甲醚(CMME)和二氯甲基醚(BCME)属于确认人类致癌物,因此,建立精准、绿色的CMME和BCME检测分析方法十分必要。基于2,4,6-三氯苯酚+乙醇钠+乙醇衍生化体系,利用气相色谱法(电子捕获检测器)测定了固定污染源废气中的CMME和BCME,并且系统地优化了采样条件、衍生化条件,确定了衍生化产物的结构及衍生比率。结果表明：工作曲线相关系数均大于0.990;当采样量为10 L时,检出限均为0.003 mg/m³;当实际样品加标量分别为0.010、0.100、1.00 mg/m³时,测定结果的相对标准偏差分别为15%～16%、8.9%～13%、10%～11%,加标回收率分别为89.2%～90.8%、75.3%～78.6%、76.5%～77.2%。     

猪粪中典型类固醇雌激素的固相萃取/GC-MS检测

以猪粪中常见且具有较大潜在危害的E1(雌酮),17α-E2(17α-雌二醇),17β-E2(17β-雌二醇)和E3(雌三醇)为研究对象,建立了猪粪中这4种典型类固醇雌激素的GC-MS(气相色谱-质谱)分析检测方法.着重优化了样品的前处理方法,包括对超声提取剂、超声提取时间、固相萃取淋洗剂、衍生化温度和时间的优化选择.结果表明:在优化的试验条件下,猪粪中的典型雌激素E1,17α-E2,17β-E2和E3检出限分别为8.0,2.5,5.1和3.3 μg/kg,平均加标回收率在92.3%～137.4%之间.      

类固醇类内分泌干扰物羟基衍生化条件的优化

以N-甲基-N-三甲基硅基三氟乙酰胺(MSTFA)为衍生化试剂,采用气相色谱-质谱联用技术(GC-MS)系统研究了4种类固醇类内分泌干扰物雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)、17α-乙炔基雌二醇(EE2)的羟基衍生化,主要考察了MSTFA用量、衍生化温度、衍生化时间对类固醇类内分泌干扰物衍生化效果的影响以及衍生化产物的稳定性、标准曲线、仪器检出限等.结果表明:100μl浓度为0.01μg.μl-1的标准混合溶液,MSTFA的最佳用量为20μl;最佳衍生化条件为70℃下反应30min;衍生化产物的稳定性较好,在-20℃下放置48h,相对响应因子(RRF)基本没有降低;在优化的实验条件下,各待测物具有良好的线性相关性,E1和E2的仪器检出限为0.1pg.μl-1,EE2和E3的仪器检出限为1pg.μl-1.