Evaluation of an on-line coupled continuous flow liquid membrane extraction and precolumn system as trace enrichment technique by liquid chromatographic determination of bisphenol A

An on-line coupled continuous flow liquid membrane extraction (CFLME) and C₁₈ precolumn system was developed for sample preconcentration in liquid chromatography determination. After preconcentration by CFLME, which is based on the combination of continuous flow liquid–liquid extraction and supported liquid membrane, bisphenol A (BPA) was enriched in 960 μl of 1 mol l⁻¹ NaOH used as acceptor. This acceptor was on-line neutralized and transported onto the C₁₈ precolumn where analytes were absorbed and focused. Then the focused analytes were injected onto a C₁₈ analytical column for separation and detected at 220 nm with a diode array detector. CFLME related parameters such as flow rates, pH of donor and acceptor, and enrichment time were optimized. The proposed method presents a detection limit of 0.03 μg l⁻¹ (S/N=3) when 60 ml samples was enriched with an enrichment time of 30 min. Compared with C₁₈ based column-switching procedure, this proposed procedure presents similar sample throughput and lower detection limits. The proposed method was successfully applied to determine BPA in tap water, river water, and municipal sewage effluent samples.     

Continuous flow liquid membrane extraction: a novel automatic trace-enrichment technique based on continuous flow liquid-liquid extraction combined with supported liquid membrane

Combining the continuous flow liquid-liquid extraction (CFLLE) and supported liquid membrane (SLM) extraction, a novel aqueous-aqueous extraction technique that we termed continuous flow liquid membrane extraction (CFLME) is developed for trace-enrichment. The analyte was firstly extracted into the organic phase in the CFLLE step, then transported onto the organic liquid membrane that formed on the surface of the micro porous membrane of the SLM equipment. Finally, it passed through the liquid membrane and was trapped by the acceptor. Aspects related to CFLME were studied by using dichloromethane as liquid membrane, and sulfonylurea herbicides as model compounds. An enrichment factor of over 1000 was obtained when 10 μg l⁻¹ of MSM was enriched for 120 min by this technique. The drawbacks of only a few organic solvents can be selected as liquid membrane with a limited lifetime in SLM operation was overcome. In this CFLME method, almost all solvents that used in the conventional liquid-liquid extraction (LLE) can be adopted and the lifetime of liquid membrane is no longer a problem.     

Supported liquid membrane work-up in combination with liquid chromatography and electrochemical detection for the determination of chlorinated phenols in natural water samples

Summary A sample preparation method has been developed for the determination of chlorinated phenols in water. The method is based on a supported liquid membrane extraction system connected on-line to liquid chromatography with electrochemical detection. The supported liquid membrane technique utilizes a porous PTFE membrane. The membrane is impregnated with an organic solvent which forms a barrier between two aqueous phases and enables selective extraction. The technique can easily be coupled in a flow system. In this investigation five chlorinated phenols (1–5 chlorine atoms) were extracted from natural water samples. Extraction for 30 minutes resulted in detection limits of approximately 25 ng L^–1.     

Direct determination of chlorophenols present in liquid samples by using a supported liquid membrane coupled in-line with capillary electrophoresis equipment

Actually there is a great trend on the development of effective analytical methods for monitoring trace levels of various phenols which can indicate, among others compounds, the water quality. A simple, inexpensive supported liquid membrane (SLM) device was used in combination with commercially available capillary electrophoresis (CE) equipment for the direct determination of chlorophenols in surface water samples. The manifold was used simultaneously to extract and preconcentrate the analytes from liquid samples. In the extraction set-up, the donor phase (4 mL) was placed in the CE vial, where a micro-membrane extraction unit (MMEU) accommodating the acceptor phase (100 μL) in its lumen was immersed. The supported liquid membrane was constructed by impregnating a porous Fluoropore Teflon (PTFE) membrane with a water-immiscible organic solvent (dihexyl ether). The extraction process was optimized with regard to the pH of the donor and acceptor phases, membrane liquid, extraction time and voltage applied to the inlet or outlet vial during extraction. The chlorinated phenols pentachlorophenol (PCP), 2,3,6 trichlorophenol (TCP) and 2,6 dichlorophenol (DCP) were thus efficiently separated by CE, using tris(hydroxymethyl)aminomethane (Tris) and an NaH₂PO₄ solution containing 1% (v/v) methanol at pH 10.5 as running buffer.     

Development of an on-line preconcentration system for zinc determination in biological samples

An on-line preconcentration system for zinc determination in 24-h urine, blood plasma and erythrocyte matrices by flame atomic absorption spectrometry (FAAS) was used. This procedure was based on adsorption of Zn(II) ions onto a minicolumn filled with silica gel, chemically modified with niobium(V) oxide (Nb₂O₅-SiO₂). The determination of the optimum conditions for Zn(II) preconcentration was done using two-level full factorial and Doehlert designs. In the optimization procedure, four variables (sample pH, eluent concentration, sample flow rate and eluent flow rate) were investigated. The results obtained from the full factorial design demonstrated that the sample pH and sample flow rate variables, and their interactions, were statistically significant. A Doehlert matrix was used in order to determine the optimum conditions for the sample pH and sample flow rate. The optimized conditions for sample pH and flow rate sampling were 6.6 and 7.1 ml min⁻¹, respectively, to obtain the maximum Zn(II) preconcentration and determination in the biological samples studied. Parameters of analytical curve, precision, effect of other ions in the proposed system and accuracy were achieved to assess the proposed method. The accuracy was confirmed by analysis of certified reference materials (urine Seronorm™ Trace Elements) and recovery tests in blood plasma and erythrocyte samples. Detection limit (3σ/S) of 0.77 μg l⁻¹, precision (calculated as relative standard deviation) of 1.5% for Zn(II) concentration of 10 μg l⁻¹ (n = 7) and a sampling frequency of 27 samples/h were obtained from the proposed system.     

Speciation of alkyllead in aqueous samples with application of liquid membrane probe for extraction and preconcentration

Lead is known to be toxic, especially in its organic forms (organolead, OL). In the environment tetraalkyllead species are rapidly degraded by sunlight and atmospheric constituents like ozone or hydroxyl radicals. Such breakdown yields the soluble forms such as trialkyllead and dialkyllead and finally ionic lead species. The liquid membrane extraction probe (LMP) device has been developed and used as an extraction and preconcentration tool for the speciation analysis of organolead compounds by GC/MS. It allows analysis of OL species at low concentrations in complicated matrices of environmental samples. The effect of pH, stirring rate, and time that influence the extraction efficiency of OL extraction by the LMP method were optimized. The transformation of tetramethyllead in aqueous media at different concentrations of major ions K(+), Na(+), Ca(2+), Mg(2+), Cl(-), SO(4)(2-) and the application of LMP to environmental samples are presented. It was found that degradation of tetramethyllead takes between 24 and 37 days. The detection limit (LOD) of the method for all organolead species investigated is around 4.7 microg/L, with a limit of quantitation of 15 microg/L.     

Determination of linuron in water samples by high performance liquid chromatography after preconcentration with octadecyl silanized magnetite

A sensitive and selective batch adsorption method is proposed for the preconcentration and determination of linuron. Linuron was preconcentrated on octadecyl silanized (ODS) magnetite as an adsorbent and then determined by high performance liquid chromatography (HPLC). Several parameters on the recovery of the analyte were investigated. The experimental results showed that it was possible to obtain sufficient preconcentration efficiency when the solution pH was 6 using 100 mL of sample solution containing 1.0 μg of linuron and 3 mL of ethanol as a desorption solution. Recovery of linuron was 50.7 ± 1.9% with a relative standard deviation for five determinations of 3.0% under optimum conditions. The calibration curve of linuron was linear up to 200 ng mL^− 1 with a correlation coefficient of 0.998 and the detection limit (3S/N) was 1.0 ng mL^− 1. The capacity of the adsorbent was also examined and found to be 0.15 mg g^− 1 for linuron. ODS-magnetite is suitable for repeated use without decreasing recovery at least 4 adsorption–desorption cycles. The proposed method was successfully applied to the determination of linuron in river water with high precision and accuracy.     

Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography

The 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) ionic liquid was immobilized in the pores of a polypropylene hollow fiber for hollow fiber-protected liquid-phase microextraction. Analytes including 4-chlorophenol (4-CP), 3-chorophenol (3-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were extracted into this ionic liquid membrane, and back extracted into 10microL sodium hydroxide acceptor solution in the lumen of the hollow fiber. Then, the acceptor solution was withdrawn into the high-performance liquid chromatography (HPLC) microsyringe connected to the hollow fiber, and directly injected into the HPLC system for analysis. Some parameters that might affect the extraction efficiency were optimized, and low detection limits (0.5microgL(-1) for 4-CP, 3-CP, DCP and 1.0microgL(-1) for TCP) were obtained. Good repeatability was achieved because of the stability of the hollow fiber-supported ionic liquid membrane. The proposed procedure was applied for direct determination of the four chlorophenols in some real water samples including groundwater, river water, wastewater and tap water. All of the four chlorophenols in these water samples were under the limits of determination, and the recoveries were in the range of 70.0-95.7% at 5microgL(-1) spiked level.     

Molecularly imprinted polymers for on-line preconcentration by solid phase extraction of pirimicarb in water samples

The synthesis and performance of a molecularly imprinted polymers (MIPs) as a selective solid phase extraction sorbent for the preconcentration of the carbamate pirimicarb from water samples is described. The MIP was prepared using pirimicarb as the template, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer, and using chloroform as the solvent. The detection of pirimicarb was carried out by differential pulse voltammetry (DPV) at a hanging mercury drop electrode (HMDE) in 0.1 mol l⁻¹ HCl. Solvents of different polarities were checked for the polymer synthesis, and different experimental variables (sample pH, selection of the eluent used, eluent volume, analyte and eluent flow rates and sample volume) associated with the rebinding/extraction process were optimised. For a 25 ml sample, the process took about 13 min and resulted in a nominal enrichment factor of 50 (eluent MeOH:H₂O:HAc, 7:2:1; 0.5 ml) for pirimicarb. A limit of detection of 4.1 μg l⁻¹ was obtained, and a good reproducibility of the measurements using different MIP microcolumns was found. Furthermore, the MIP selectivity was evaluated by checking several substances with similar and different molecular structures to that of pirimicarb. As an application, pirimicarb was determined in water samples of diverse origin which were spiked at a concentration level of 71.5 μg l⁻¹.     

Preparation and evaluation of a molecularly imprinted sol-gel material for on-line solid-phase extraction coupled with high performance liquid chromatography for the determination of trace pentachlorophenol in water samples

A highly selective imprinted amino-functionalized silica gel sorbent was prepared by combining a surface molecular imprinting technique with a sol-gel process for on-line solid-phase extraction-HPLC determination of trace pentachlorophenol (PCP) in water samples. The PCP-imprinted amino-functionalized silica sorbent was characterized by FT-IR, SEM, nitrogen adsorption and the static adsorption experiments. The imprinted functionalized silica gel sorbent exhibited high selectivity and offered a fast kinetics for the adsorption and desorption of PCP. The prepared sorbent was shown to be promising for on-line solid-phase extraction for HPLC determination of trace levels of PCP in environmental samples. With a sample loading flow rate of 5 ml min(-1) for 2 min, an enhancement factor of 670 and a detection limit (S/N = 3) of 6 ng l(-1) were achieved at a sample throughput of five samples h(-1). The precision (RSD) for nine replicate on-line sorbent extractions of 10 microgl(-1) PCP was 3.8%. The sorbent also offered good linearity (r = 0.9997) for on-line solid-phase extraction of trace levels of PCP. The method was applied to the determination of PCP in local lake water, river water and wastewater samples.     

支撑液膜在线萃取流动注射光度法测定水中挥发酚

酚类污染物是一类重要的污染物,对很多水生生物有毒,并且可通过食物链进行生物富集,因此,挥发酚的检测对环境污染控制和环境保护具有重要意义。苯酚是中国环境优先监测物中6种酚类物质之一。酚类物质的测定方法主要有气相色谱法、液相色谱法、光度法等。4-氨基安替比林（4-AAP）分光光度法是目前国际上普遍采用的标准方法,但该方法操作繁琐。如将此法应用于流动注射自动分析,虽然可以省去繁琐的操作,但废水中其它离子的干扰严重,必须进行预蒸馏才能进行测定,且检测限高,不能满足低浓度分析检测的需要。     

柱前衍生-超高效液相色谱法测定鱼卵中的17种氨基酸

建立了一种快速、灵敏的柱前衍生-超高效液相色谱-光电二极管阵列检测器(UPLC-PDA)测定史氏鲟(Acipenser schrenckii)、达氏鳇(Huso dauricus)和小体鲟(Acipenser ruthenus)鱼卵中17种氨基酸含量的方法。采用6.0 mol/L的盐酸水解鱼卵,提取液经低压浓缩、碱性中和,然后以6-氨基喹啉-N-羟基琥珀酰亚胺基氨基甲酸酯(AQC)为衍生试剂在pH 8.8硼酸盐缓冲溶液中衍生化。采用的色谱分离柱为Waters BEH C18柱(100 mm×2.1 mm, 1.7 μm),流动相为30 mmol/L乙酸铵水溶液(pH 3.5)和乙腈(含0.15%(v/v)甲酸及30 mmol/L乙酸铵),梯度洗脱,流速为0.7 mL/min,在260 nm波长下检测。17种氨基酸在5.0～1000 μmol/L浓度范围内,峰面积与浓度之间的线性关系良好(r2≥0.9950)。以标准加入法测定回收率和相对标准偏差(RSD),在100、500、750 μmol/L的添加水平下,17种氨基酸的平均回收率为75.4%～107.3%, RSD为2.19%～12.3%。以3倍信噪比(S/N＞3)计方法的检出限,17种氨基酸的检出限为0.94～4.04 μmol/L。应用该方法检测了3种鲟鳇鱼鱼卵中的17种氨基酸含量。结果表明,该方法简便、准确、快速、可靠。     

柱前衍生-高效液相色谱法同时测定血清中氨基酸类及单胺类神经递质

以邻苯二甲醛（o-phthalaldehyde，OPA）为衍生试剂，建立了柱前衍生-高效液相色谱（HPLC）同时测定血清中氨基酸类神经递质牛磺酸（Tau）、谷氨酸（Glu）、甘氨酸（Gly）、γ-氨基丁酸（γ-GABA）和单胺类神经递质多巴胺（DA）含量的分析方法。血清与乙醇以1：2的体积比混合，进行蛋白质沉淀后离心，取其上清液，氮吹至近干。前处理后的样品与OPA进行柱前衍生，衍生化产物采用Luna 5u C18色谱柱（250 mm×4.6 mm，5 μm）分离，以柠檬酸-乙酸钠缓冲溶液（pH 3.73）为流动相A、乙腈为流动相B进行梯度洗脱，流速为1.0 mL/min，柱温为30℃，检测波长为338 nm。5种神经递质在各自范围内线性关系良好（r²≥0.9866），检出限为0.10~0.40 μmol/L，不同加标水平下目标物的加标回收率为87.57%~115.31%，相对标准偏差均低于7.80%。方法操作简单，灵敏度高，精密度、线性关系和回收率等方法学指标较好，可实现血清中氨基酸类及单胺类神经递质的同时检测。     

High-performance liquid chromatographic determination of phenolic compounds in natural water coupled with on-line flow injection membrane extraction-preconcentration

A liquid chromatographic method for determination of trace phenolic compounds has been established, coupled with an on-line supported liquid membrane extraction-preconcentration flow-injection system. Tributyl-phosphate dissolved in kerosene was used as the carrier of the supported liquid membrane. Four phenolic compounds (phenol, catechol, resorcinol and hydroquinone) were chosen as the model compounds and the experiment conditions were optimized. Under the optimum conditions, calibrations were linear in the range of 1-500 microg/L, with good correlation coefficients (r > 0.999). The total analysis time of the system was 22 min, including the membrane extraction, liquid chromatographic separation and equilibration times.     

Determination of phenolic compounds in river water with on-line coupling bisphenol A imprinted monolithic precolumn with high performance liquid chromatography

The bisphenol A (BPA) imprinted monolithic precolumn has been prepared by in situ polymerization using 4-vinylpyridine (4-VP) and ethylene dimethacrylate (EDMA) as functional monomer and cross-linker, respectively. The column with good flow-through property was obtained by changing the molar ratio of the porogens (toluene and dodecanol). The selectivity and retention properties of the monolith for the BPA and other phenolic compounds were evaluated. The results show that the hydrophobic and hydrogen-bonding interaction plays important roles in the recognition process. The determination of BPA and other phenolic compounds with on-line solid-phase extraction (SPE) by monolithic precolumn coupled with conventional particulates packed and monolithic reversed-phase columns, respectively, was performed. The method was successfully applied to the analysis of phenolic compounds in river water.     

基于十八烷基三甲基溴化铵修饰的磁性粒子在线磁性固相萃取-高效液相色谱法测定水样中磺酰脲类农药

采用溶胶-凝胶法制备表面修饰了十八烷基三甲基溴化铵的磁性粒子作为萃取剂，研制了一种在线磁性固相萃取（on-line MSPE）装置，建立了on-line MSPE与高效液相色谱联用测定水样中两种磺酰脲类农药（氯磺隆、苄嘧磺隆）的方法。实验优化了在线磁性固相萃取条件并进行方法学考察，证明该方法具有良好的线性关系（两种目标物的线性相关系数均≥ 0.9997）和较低的检出限（两种目标物的检出限分别为0.32和1.12 μg/L）。将此法用于3种环境水样中两种磺酰脲类农药的检测，水样中均检出氯磺隆，均未检出苄嘧磺隆。两种目标物加标回收率为70.0%~113.4%。该方法高效、简便，在分离富集环境水样中磺酰脲类农药方面有一定的应用前景。     

Development of a static and exhaustive extraction procedure for field passive preconcentration of chlorophenols in environmental waters with hollow fiber-supported liquid membrane

A static and exhaustive extraction mode of hollow fiber-supported liquid membrane was developed for field sample passive pretreatment of environmental water samples. The extraction device was prepared by immobilizing dihexyl ether in the wall of a polypropylene hollow fiber membrane (60 cm length, 50 μm wall thickness, and 280 μm id) as liquid membrane and filling the fiber lumen with 0.1 M NaOH as acceptor, and closing the two ends of the fiber with an aluminum foil. Passive extraction was conducted by immersing the device into 15 mL water samples modified with 0.01 M HCl and 20% m/v NaCl. Model analytes including 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol were transferred into acceptor with extraction efficiencies over 79% in 10 h at room temperature, and determined by high-performance liquid chromatography. The proposed method has the enrichment factor of 394-498 and LOD of 0.3-0.4 μg/L for the three chlorophenols. Humic acid and salinity in the environmentally relevant range had no significant influence on the extraction, and chlorophenols in various environmental waters were determined with spike recoveries between 71.6 and 120%. The static passive extraction nature benefited field sample pretreatment without power, whereas the exhaustive extraction mode effectively eliminated the sample matrix effects.     

Determination of atrazine and simazine in water samples by high-performance liquid chromatography after preconcentration with heat-treated diatomaceous earth

A sensitive and selective column adsorption method is proposed for the preconcentration and determination of atrazine and simazine. Atrazine and simazine were preconcentrated on heat-treated diatomaceous earth as an adsorbent and then determined by high-performance liquid chromatography (HPLC). Several parameters on the recoveries of the analytes were investigated. The experimental results showed that it was possible to obtain quantitative analysis when the solution pH was 2 using 100 mL of validation solution containing 1.5 μg of triazines and 5 mL of ethanol as an eluent. Recoveries of atrazine and simazine were 95.7 ± 4.2% and 75.0 ± 1.9% with a relative standard deviation for seven determinations of 4.7% and 2.7% under optimum conditions. The maximum preconcentration factor was 100 for triazines when 500 mL of sample solution volume was used. The linear ranges of calibration curves for atrazine and simazine were 1-150 ng mL⁻¹ and 1-300 ng mL⁻¹, respectively, with correlation coefficients of 0.999 and the detection limits (3Signal-to-Noise) were 0.24 ng mL⁻¹ and 0.21 ng mL⁻¹ for atrazine and simazine. The capacity of the adsorbent was also examined and found to be 0.8 mg g⁻¹ and 1.3 mg g⁻¹ for atrazine and simazine, respectively. The proposed method was successfully applied to the determination of triazines in river water and tap water samples with high precision and accuracy.     

Trace analysis of sulfonylurea herbicides in water by on-line continuous flow liquid membrane extraction--C18 precolumn liquid chromatography with ultraviolet absorbance detection

An on-line system that consists of continuous-flow liquid membrane extraction (CFLME), C18 precolumn, and liquid chromatography with UV detection was applied to trace analysis of sulfonylurea herbicides in water. During preconcentration by CFLME, five target compounds, including metsulfuron methyl, bensulfuron methyl, tribenuron methyl, sulfometuron methyl, and ethametsulfuron, were enriched in 960 microl of 0.5 mol l(-1) Na2CO3-NaHCO3 (pH 10.8) buffer used as acceptor. This acceptor was on-line neutralized and transported to the C18 precolumn where the analytes were absorbed and focused. Then the focused analytes were injected onto a C18 analytical column for separation and detection at 240 nm. The proposed method was applied to determine sulfonylurea herbicides in water, river, and reservoir water with detection limits of 10-50 ng l(-1) when enriching a 120-ml sample. Throughput is typically one sample per hour.     

分子印迹固相萃取-高效液相色谱法测定饲料中莱克多巴胺

以莱克多巴胺为模板分子,丙烯酰胺为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了对莱克多巴胺具有高选择性的分子印迹聚合物。考察了甲醇、乙腈、丙酮和氯仿-甲醇与三乙胺构成致孔剂合成的聚合物性能及其形貌特征。通过正交试验优化的聚合反应配方为: 1.0 mmol莱克多巴胺,4.0 mmol丙烯酰胺,20.0 mmol乙二醇二甲基丙烯酸酯,6.0 mL乙腈-三乙胺(30:1, v/v), 50.0 mg偶氮二异丁腈。建立的基于分子印迹固相萃取-高效液相色谱测定饲料试样中莱克多巴胺的方法,在0.50～100 mg/L质量浓度范围内有良好的线性关系(r=0.9994);饲料试样中1.0、10及100 mg/kg 3个添加水平的莱克多巴胺平均回收率大于80%;批内、批间测定的相对标准偏差小于10%;检出限(信噪比为3)达到0.1 mg/kg。该方法灵敏、可靠,用于饲料等复杂基质中莱克多巴胺检测的效果优于相关标准分析方法。