固相萃取技术及其研究进展

对固相萃取技术的原理和特点,萃取参数(吸附剂用量、背景体积及洗脱溶剂等)与萃取效率的规律,吸附剂的研究进展与发展趋势,以及目前的固相萃取在线联用技术等方面进行了阐述。该技术比传统液—液萃取用时短、二次污染小、选择性好,是一种很有前途的样品预处理技术。已广泛应用于环境样品中多环芳烃、农药、卤代烃、有机氯化合物、酚类等优先控制污染物的测定。     

Chemically modified silica gel with 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone: Synthesis, characterization and application as an efficient and reusable solid phase extractant for selective removal of Zn(II) from mycorrhizal treated fly-ash samples

1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone functionalized silica gel was synthesized and used as a highly efficient, selective and reusable solid phase extractant for separation and preconcentration of trace amount of Zn(II) from environmental matrices. The adsorbent was characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis,¹³C CPMAS NMR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and BET surface area analysis. The dependence of zinc extraction on various analytical parameters such as pH, type and amount of eluent, sample flow rate and interfering ions were investigated in detail. The material exhibited superior adsorption efficiency for Zn(II) with high metal loading capacity of 1.0 mmol/g under optimum conditions. After adsorption, the recovery (> 98%) of metal ions was accomplished using 1.0 mol/L HNO₃ as an eluent. The sorbent was also regenerated by microwave treatment in milder acidic environment (0.1 mol/L HNO₃). The lower detection limit and preconcentration factor of the present method were found out to be 0.04 μg/L and 312.5 respectively. The modified silica surface possessed excellent selectivity for the target analytes and the adsorption/desorption process remained effective for at least ten consecutive cycles. The optimized procedure was successfully implemented for the extraction of Zn(II) from mycorrhizal treated fly ash and pharmaceutical samples with reproducible results.     

国外水环境标准与监测方法的发展（上）

介绍了国际卫生组织、美国国家环境保护局及日本最新公布的饮用水中污染物的规定标准、重点介绍了日本新增加的１５控制污染物的物理化学性质、产量和用途、在环境中的行为和毒性等。以有机污染物的监测分析方法为重点，评述了水中挥发性、半挥发性和难挥发性有机污染物试样处理的气提一捕集、顶空法、溶剂萃取法和固相萃取法，以及新的监测分析方法体系。并对日本１９９３年实施和１９９４年将要实施的水质监测新方法进行了概述。     

Improved preparation and identification of aristolochic acid-DNA adducts by solid-phase extraction with liquid chromatography-tandem mass spectrometry

Aristolochic acid (AA) is a known nephrotoxin and potential carcinogen, which can form covalent DNA adducts after metabolic activation in vivo and in vitro. A simple method for preparation and characterization of aristolochic acid-DNA adducts was developed. Four AA-adducts were synthesized by a direct reaction of AAI/AAII with 2’-deoxynucleosides. The reaction mixture was first cleaned-up and pre-concentrated using solid phase extraction (SPE), and further purified by a reversed-phase high performance liquid chromatography (HPLC). By the application of developed SPE procedure, matrices and byproducts in reaction mixture could be greatly reduced and adducts of high purity (more than 94% as indicated by HPLC) were obtained. The purified AA-DNA adducts were identified and characterized with liquid-electrospray ionization-quadrupole-time of flight-mass spectrometry (LC-ESI-Q-TOF-MS/MS) and LC-Diode array detector-fluorescence (LC-DAD-FL) analysis. This work provides a robust tool for possible large-scale preparation of AA-DNA adduct standards, which can promote the further studies on carcinogenic and mutagenic mechanism of aristolochic acids.     

阿维菌素发酵废菌丝体对Cu~(2+)吸附机制的研究

文章对阿维菌素发酵的废菌丝体对Cu2+进行吸附的机制进行了研究。结果表明,吸附过程可分为快速吸附和缓慢吸附至平衡两个阶段,第一阶段为被动吸附,5min接近平衡,第二阶段菌丝单位吸附量增加缓慢,反应时间相对较长。吸附过程能很好的用准二级动力学方程描述,相关系数达0.9998。采用Langmuir方程与Freudlich方程对数据拟合,Langmuir方程比Freudlich方程更好的描述对Cu2+吸附平衡行为,表现为单分子层吸附。在pH5.0下的相关系数为0.9771,得到的最大吸附量可达28.82mg/g。通过对吸附前后的红外光谱研究表明,本吸附质含有羟基(-OH)、氨基(-NH)2、酰胺基(-CONH)2、亚甲基(-CH2-)等基团。羟基、氨基、亚甲基吸收峰发生较大变化,推测其与金属离子发生了反应,酰胺基峰形变化较小,参与反应的基团较少。     

Determination of haloacetic acids concentrations in hospital effluent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction (SPE) method was developed for the analysis of low concentration haloacetic acids(HAAs),a calss of disinfection by-products formed as a result of chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples' turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and were found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L respectively, and the other three are ranging from 0.48 to 0.82 μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid is the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

药物及个人护理品的污染现状、分析技术及生态毒性研究进展

随着医药及洗化行业的快速发展,PPCPs（pharmaceuticals and personal care products,药物及个人护理品）的生产和使用量增长迅速,已经成为自然环境中具有潜在生态风险的一类新型污染物.由于PPCPs在环境中浓度低、检测难度大、生态风险具有潜伏性,高灵敏度的定量检测方法已成为研究的热点.比较了文献中常用的不同预处理方法〔液液萃取（liquid liquid extraction,LLE）、固相萃取（solid phase extraction,SPE）、固相微萃取（solid phase micro extraction,SPME）、超声波溶剂萃取（ultrasonic solvent extraction,USE）、加压液相萃取（pressurized liquid extraction,PLE）、微波辅助溶剂萃取（microwave assisted solvent extraction,MASE）〕和检测方法〔GC/MS（气相色谱-质谱）、GC/MS/MS（气相色谱-双质谱）、HPLC/MS（高效液相色谱-质谱）、HPLC/MS/MS（高效液相色谱-双质谱）〕对地表水、沉积物、饮用水等不同介质中PPCPs检出限和检出浓度的异同,发现水样预处理常采用固相萃取法,其具有高回收和富集倍数、消耗有机溶剂少、省时等优点;固相样品预处理常采用超声溶剂萃取,其具有操作简单、适用性广等优点;HPLC/MS/MS检测方法具有广泛适用性,可检测大多数PPCPs,并且操作简单、灵敏度高.PPCPs会在水生生物体富集,并会表现出抑制酶活性、蛋白质及核酸合成、干扰藻类生长、影响动物活动等毒性效应.建议未来应加强环境中超低浓度PPCPs定量、定性分析技术的研发与应用,同时加强其环境风险研究,为揭示PPCPs的环境归趋行为提供技术支持.      

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。     

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.     

利用MSWI飞灰构建新型填埋固化基质的研究

介绍了以MSWI飞灰为主要组分,利用富铝组分调控所构建的Friedel-ettringite为主导相的新型固化体系,考察了固化体系的抗压强度并用美国EPA毒性浸出实验（TCLP）,评价固化材料中重金属的浸出特性,使用XRD、DTG分析了固化体系的微观矿物相,FTIR图谱对固化体系矿物相的有关基团振动谱带进行比较,通过重金属的化学形态分布了解重金属在其中的赋存状态,结果表明,新体系可以通过矿物相的晶体化合作用对Pb、Cd、Zn重金属进行有效束缚,实现稳定固化这种新型固化体系可望用于MSWI飞灰与其它重金属类危险废物的填埋共处置。     

Evaluation of the adsorptive capacity of peanut hull pellets for heavy metals in solution

This study assessed the potential of peanut hull pellets to capture metal ions from wastewater and compared their performance to that of raw peanut hulls and a commercial grade ion-exchange resin. The uptake of Cu²⁺, Cd²⁺, Zn²⁺, and Pb²⁺ onto these media was investigated using a system of standardized batch adsorbers under steady state and transient rate conditions. The influence of the pelletizing process on the rate of metal ion sorption was evaluated by comparing the rate and extent of metal ion uptake onto peanut hull pellets vs. raw peanut hulls. Although a slight reduction in rate of adsorption was apparent for metal ion adsorption onto the pellets, equilibrium capacity was unaffected. Peanut hull pellets are an effective adsorbent for metal ion removal. Though their capacity is lower than that of commercial grade ion-exchange resins, their low cost makes them an attractive option for the treatment of low-strength metal ion waste streams in once-through fixed bed applications.     

Determination of haloacetic acids in hospital e uent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

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).     

固相微萃取技术及其应用现状综述

固相微萃取技术（SPME）在固相萃取（SPE）基础上发展而来。作为一种较新的样品前处理技术,固相微萃取技术具有操作简单、快速、集采样、萃取、浓缩和进样于一体等诸多优点,目前已被广泛应用。阐述了 SPME 的技术原理、操作流程、影响因素、应用领域和新的进展。着重指出 SPME 在环境有机污染物分析中具有广泛的应用前景。     

固相萃取技术在环境水质监测方法开发中的应用

固相萃取技术非常适用于环境水质中痕量有机污染物的监测分析。文章从选择固相萃取柱到萃取液进入色谱分析这样一个完整的过程,并以使用该技术萃取环境水样中的硝基苯类化合物为例,具体阐述了如何使用固相萃取技术建立一个方便实用的环境水质监测分析方法。     

基于固相萃取的水中多种有毒有害有机污染物富集方法优化

以降低固相萃取杂质、提高目标化合物的回收率为目的,提出了一种基于固相萃取的水中多种有毒有害有机污染物富集方法.用丙酮和二氯甲烷等溶剂洗脱未上样的固相萃取柱,评价了固相萃取各个环节对正构烷烃、酞酸酯等杂质浓度的贡献值,发现85%杂质来自填料的溶出物(以Waters Oasis HLB为例).填料经二氯甲烷、丙酮、甲醇依次索氏提取24 h后,填料的溶出物明显减少,气相色谱图中杂质峰的数量和强度均明显降低.比较了6种常用固相萃取填料在索氏提取后对lgKow1.46～8.1之间的农药、多环芳烃、酚、酞酸酯等40种目标化合物的回收率,发现Waters Oasis HLB在改性聚苯乙烯-二乙烯基苯填料中回收率最高,平均为77%;Waters SepPak AC-2在活性炭填料中回收率最高,对农药的平均回收率为74%.WatersOasis HLB和Waters SepPak AC-2固相萃取柱串联后,目标化合物的回收率明显提高,平均为87%.     

超高效液相/串联质谱法测定水中苯甲酰脲类农药残留

建立了固相萃取(SPE)-超高效液相色谱/大气压化学电离源/三重四极杆串联质谱(UPLC-MS/MS)同时测定水中7种苯甲酰脲类杀虫剂残留的方法。过滤后的样品经HLB固相萃取柱富集净化后,目标化合物经10 mL二氯甲烷洗脱并浓缩,1 mL甲醇定容后,采用BEH C18柱,以水(5 mmol/L乙酸铵)-乙腈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。7种苯甲酰脲类杀虫剂在相关线性范围内线性良好(r=0.999 1～0.999 5),回收率为71.8%～114%,相对标准偏差为3.3%～18.8%,方法检出限为7.0～16.0 ng/L。该方法快速,灵敏度高,适用于测定水体中7种苯甲酰脲类杀虫剂的残留。     

水中壬基酚的去除研究进展

壬基酚是环境内分泌干扰物质中具有代表性的物质,非离子表面活性剂壬基酚聚氧乙烯醚在环境中的降解产物,对生物体造成很大危害。目前检测水样中壬基酚的主要方法是采用GC—MS和HPLC,预处理主要采用固相萃取和液一液萃取。研究表明自来水厂的常规处理工艺对于水中壬基酚的去除有限;近年来倍受关注的深度处理工艺如活性炭吸附等物理方法...     

A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase

A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques,including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of 96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.     

Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS)and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS)

Two sample preparation methods were introduced and compared in this paper to establish a simple, quick and exact analysis of geosmin and 2-methylisoborneol. LC-18 column was employed in solid phase extraction (SPE), 1.0 mL of hexane was adopted in liquid-liquid extraction (LLE), and the extracts were analyzed by gas chromatograph mass spectrum (GCMS) in selected ion mode. Mean recoveries of SPE were low for 2-methylisoborneol (2-MIB) and geosmin (GSM) with values below 50%. For LLE, the recoveries were satisfyingly above 50% for 2-MIB and 80% for GSM. Detection limits of the LLE method were as low as 1.0 ng/L for GSM and 5.0 ng/L for 2-MIB. A year-long investigation on odor chemicals of drinking water in Shanghai demonstrated that in the summer, there was a serious odor problem induced by a high concentration of 2-MIB. The highest concentration of 152.82 ng/L appeared in July in raw water, while GSM flocculation was minimal with concentrations below odor threshold.