Fractionation and determination of aluminum and iron in soil water samples using SPE cartridges and ICP-AES

The use of commercially available solid phase extraction (SPE) cartridges for the fractionation of Al and Fe in soil water is described. The quantitative determination was done by inductively coupled plasma atomic emission spectrometry (ICP-AES). Different types of SPE cartridges, based on cation exchange, anion exchange, and chelation were studied. To avoid pH changes, the SPE cartridge should be conditioned with a buffer that has a pH close to that of the sample. Both strong cation exchange (SCX) and chelation were found to work well, whereas low recovery was observed for Al when anion exchange was used. For Fe, the sum of the anionic and cationic fractions that passed through the cartridges was nearly 100%. The results obtained for Al for 23 soil water samples using a SPE/SCX cartridge and ICP-AES were compared with equilibrium calculations using the program ALCHEMI and also with a fractionation method that was based on separation on a manually prepared SCX column and detection by molecular spectrophotometry, after complexation with pyrocatechol violet (SCX-PCV method). The SPE/SCX-ICP-AES results for the labile Al fraction (Al bound to the SCX cartridge) showed an acceptable correlation with the results obtained by the equilibrium calculations, except for the samples with the highest DOC concentrations, whereas the values obtained for labile Al by the more traditional SCX-PCV method were much lower. We recommend that the SPE/SCX-ICP-AES procedure described in this work be selected for the fractionation of Al and Fe species in soil and freshwater samples.     

Cetyltrimethylammonium Bromide-coated magnetic nanoparticles for the preconcentration of phenolic compounds from environmental water samples

The research presented in this paper investigates the adsorption of cation surfactants--cetyltrimethylammonium bromide (CTAB) and cetylpyridinium chloride (CPC)--onto magnetic nanoparticles and the application of this mixed hemimicelles solid-phase extraction (SPE) method for the preconcentration of several typical phenolic compounds-bisphenol A (BPA), 4-tertoctylphenol (4-OP), and 4-n-nonylphenol (4-NP)--from environmental water samples. In this novel SPE method, the charged surfactants CTAB and CPC form mixed hemimicelles on Fe3O4 nanoparticles (Fe3O4 NPs), which causes retention of analytes by strong hydrophobic and electrostatic interactions. The SPE method combines the advantages of mixed hemimicelles and magnetic nanoparticles. In order to provide guidelines forthe mixed hemimicelles SPE method development, surfactant adsorption isotherms and zeta-potential isotherms were also investigated. The main factors affecting the adsolubilization of analytes, such as the amount of Fe3O4 NPs and surfactants, the type of surfactants, the solution pH,the sample loading volume, and the desorption conditions, were investigated and optimized. A concentration factor of 800 was achieved by the extraction of 800 mL of several environmental water samples using this SPE method. Under the selected conditions, detection limits obtained for BPA, 4-OP, and 4-NP were 12, 29, 34 ng/L, respectively. The accuracy of the method was evaluated by recovery measurements on spiked samples, and good recoveries (68-104%) with low relative standard deviations from 2 to 7% were achieved. The advantages of this new SPE method include high extraction yields, high breakthrough volumes, short analysis times, and easy preparation of sorbents. To the best of our knowledge, this is the first time that a mixed hemimicelles SPE method based on magnetic separation and nanoparticles has been used for the pretreatment of environmental water samples.     

动态微波辅助萃取法快速萃取苹果中8种 氨基甲酸酯类农药

目的 建立一种绿色的动态微波辅助快速萃取法结合高效液相色谱-串联质谱法测定苹果中八种氨基甲酸酯类农药的方法。方法 首先,以水为萃取溶剂,利用动态微波辅助萃取法对苹果中氨基甲酸酯类农药进行快速萃取;之后通过两步固相萃取法对所获得的萃取物进行净化和富集;最后,采用高效液相色谱-串联质谱法对目标化合物进行分析。结果 实验中对影响动态微波辅助萃取和固相萃取效率的实验条件进行了优化,最优的实验条件为：萃取剂为纯水,微波萃取功率为600 W;微波萃取时间为10 min;萃取剂流速为1.0 mL min-1;固相萃取洗脱剂为2 mL的乙醇。八种氨基甲酸酯类农药在8~800 ng g-1范围内成线性关系,相关系数为0.994~0.999;检出限为1.1~4.2 ng g-1;方法的加标(8 ng g-1)回收率为71%~90%。结论 该方法可以用于苹果中氨基甲酸酯类农药的快速检测。     

Determination of Furfural in Beer by High‐Performance Liquid Chromatography with Solid‐Phase Extraction

Furfural is a sensitive indicator of beer staling. A new solid‐phase extraction (SPE) column PEP‐SPE (Polar‐Enhanced Polymer, 500 mg/6 mL) was used to develop a method for extraction of furfural from beer. The PEP‐SPE column retains furfural with higher selectivity than the commonly used C₁₈‐SPE column. Satisfactory precisions were obtained with %RSD (n = 6) less than 2.2% for peak areas. Recovery rates were in the range of 99.7–100.1% due to the simple treatment and good resolution. The detection limit was 5 μg/L. Furfural concentration ranged from 10 to 32 μg/L in twelve fresh beer samples. A noticeable increase in furfural content was found after beer samples were kept at 35°C for seven days. The calculated correlation coefficient between taste panel scores for beer freshness and the furfural content of aged beer samples was ?0.65, which showed a good inverse correlation between freshness marks and furfural content.     

固相萃取-选择离子气质联用法测定液态调味料中的4-甲基咪唑

建立了SPE-SIM-GC-MS测定液态调味料中4-甲基咪唑的新方法。对影响4-甲基咪唑萃取效率的诸因素如溶液的pH、洗脱溶剂和洗脱溶剂的体积等进行了优化。在最佳的萃取条件下,该方法对4-甲基咪唑的检出限为7.27μg/kg;相关系数和相对标准偏差(RSD,n=5)分别为0.99985和7.5%。将该方法用于实际样品中4-甲基咪唑的分析,其加标回收的回收率为80.3~86.2%。     

LC-UV and LC-MS analysis of food and drink products containing kava

A method for the determination of six kava lactones, methysticin, dihydromethysticin, kawain, dihydrokawain, yangonin and desmethoxyyangonin, in solid foods and beverages has been developed. Solid samples were prepared using methanol extraction, while beverages were extracted using a separate solid phase extraction (SPE) method. After sample preparation, the extracts were analysed using LC-UV or atmospheric pressure photoionization (APPI) LC-MS in the positive mode. Using the method, 10 beverage products, two chocolate products, three unbrewed tea products, three dietary supplements and a drink mix product were analysed. The results obtained using the LC-UV were comparable to those obtained using APPI-LC-MS for most products. Using the SPE method in conjunction with LC-MS, individual kava lactones were detected in drink products at ppb concentrations. Concentrations of total kava lactones ranged between 135-0.035 mg per serving in the food and beverage products tested and between 40-61 mg per serving for the dietary supplement products tested. Results of these analyses as well as extraction efficiency and reproducibility data are reported.     

Analysis of volatile compounds of eucalyptus honey by solid phase extraction followed by gas chromatography coupled to mass spectrometry

Solid-phase extraction (SPE) followed by gas chromatography coupled to mass spectrometry has been used for the analysis of volatile compounds of eucalyptus honey. Different amounts of honey and dichloromethane were employed to optimize solid-phase extraction conditions. The best result was obtained with 20 g of honey eluted with 60 mL of dichloromethane. This method presented a good precision for volatile compounds usually found in honeys and allowed the quantification of 35 volatile compounds (terpenes and derivatives, furan and pyran compounds, ketones, benzene compounds, acids, and norisoprenoids) of eucalyptus honey.     

HPLC-integrated solid-phase extraction with photochemical post-column derivatization for the determination of oxacillin, cloxacillin and dicloxacillin in raw milk

 An automated reversed-phase high-performance liquid chromatography (HPLC) method with UV detection at 300 nm after on-line coupled solid-phase extraction (SPE) and photochemical post-column derivatization was developed for the residue analysis of oxacillin, cloxacillin and dicloxacillin in raw milk. After a centrifugation step for defatting and ultrafiltration, a HPLC-integrated SPE using a restricted access sorbent, is performed. By operating the system in parallel mode, SPE and HPLC run are performed simultaneously. The procedure allows the analysis of about 30 samples within 24 h and was used to investigate the milk of cows which had been treated with oxacillin. The detection limit was 3 μg/kg for oxacillin and cloxacillin and 5 μg/kg for dicloxacillin. The recoveries were between 66% and 81% with coefficients of variation between 3.3% and 7.7%. Using an acetonitrile extraction procedure better recoveries of ≥90% were obtained with fortified samples, but more or less identical results were obtained for the samples with incurred residues after correction for recovery. Received: 16 February 1998     

Polycyclic aromatic hydrocarbons in meat smoked with different types of wood

The influence of the wood used for the smoking of meat on the formation of polycyclic aromatic hydrocarbons (PAH) has been studied. Ten types of wood and charcoal were used for preparation of smoked meat samples. The analytical sample preparation method implied extraction of PAH with cyclohexane, liquid–liquid extraction with N,N-dimethylformamide/water, back extraction with cyclohexane, followed by clean-up on silica solid phase extraction (SPE) column and quantification by gas chromatography–mass spectrometry. It was found that the type of wood has a significant influence on the amount of PAH in smoked meat. The samples smoked with apple-tree and alder contained the smallest PAH concentrations. The samples smoked with spruce had the highest concentrations of PAH. The difference in content of benzo[a]pyrene (from 6.04 till 35.07 μg/kg) and total PAH (from 47.94 till 470.91 μg/kg) indicates that choice of wood for smoking is one of the critical parameter to be controlled in order to diminish the contamination of food products.     

HPLC测定亚麻籽油苦味肽的纯化富集前处理研究

比较了高效液相色谱(HPLC)定量测定亚麻籽油苦味肽(CLE)的溶剂萃取法和固相萃取法(SPE)纯化富集前处理效果,并对不同规格SPE硅胶小柱填料的前处理效果作了对比。结果表明,通过溶剂萃取法和固相萃取法前处理的亚麻籽油样品,进行HPLC定量测定时,CLE均可以在液相色谱中得到良好的分离,前处理方法并不影响CLE的出峰时间及峰形。但与溶剂萃取法相比,SPE所提取的环肽样品中甘油三酯及其他杂质显著减少,这有利于保护液相色谱柱、提高柱效。随着SPE硅胶小柱填料量的增加,CLE测定值减小,使用填料规格为0. 5 g的SPE硅胶小柱可以得到较好的分离及富集效果。SPE硅胶小柱预处理所得物经超高效液相色谱-质谱联用分析证实为CLE。SPE可有效提取富集亚麻籽油所含的CLE,适用于HPLC定量检测CLE的前处理,该方法样品加标回收率为92. 62%,组内精密度相对标准偏差为0. 62%,组间精密度相对标准偏差为1. 79%。     

电化学分析法检测动物源食品中氯丙嗪的3种前处理方法比较

目的对猪肉、鸡肉、牛肉、猪肝、虾肉、蜂 蜜、鱼肉、鸡蛋和牛奶共9种动物源食品中氯丙嗪电化学检测的前处理方法进行了选择和优化,方法 样品分别采用溶剂提取法、QuECHERS法（Quick、Easy、Cheap、Effective、Rugged、Safe,QuEChERS法）和固相萃取法（solid-phase extraction,SPE）进行了电化学检测比较分析。结果表明,猪肉、鸡肉、牛肉、猪肝、虾肉和蜂蜜可用溶剂提取法进行处理,氯丙嗪的加标回收率均在81.6%以上;而鱼肉和鸡蛋样品需采用QuECHERS法进行处理,回收率分别达到88.5%～95.8%和89.7%～98.2%;牛奶样品用溶剂提取法和QuECHERS 法处理时均有基质干扰,采用固相萃取法进行净化后,回收率达到80.6%～93.0%。不同类型的动物源食品由于肌肉的纤维组织、脂肪含量、水分含量、蛋白质的种类和含量等存在差别,需分别采用适宜的前处理方法才能获得满意的测定结果。结论 该研究可为不同类型动物源食品中氯丙嗪电化学检测方法的应用提供参考。     

Application of Graphene-based Solid-Phase Extraction Coupled with Ultra High-performance Liquid Chromatography-Tandem Mass Spectrometry for Determination of Macrolides in Fish Tissues

A novel analytical protocol for the determination of five macrolides (MLs) in crucian carp tissues has been developed. Two-dimensional (2D) planar graphene powder was utilized as the solid-phase extraction (SPE) sorbent for analyte enrichment and cleanup. The target analytes were separated by ultra high-performance liquid chromatography (LC) and quantified by a triple–quadrupole linear ion trap mass spectrometer. The proposed analytical procedures were carefully optimized and validated. Average recoveries of MLs were between 81.7 and 110.5 %, which was the highest comparing with the conventional sorbents including C18 silica and multiwalled carbon nanotubes (MWCNTs). Method validation proved the feasibility of the developed nanoparticles for the quantificatation of the investigated analytes at trace levels obtaining low limit of quantitation values in the microgram per kilogram range. Good precision with coefficients of variations always lower than 10 % was obtained. The proposed method has been successfully applied to the analysis of ML in several aquaculture product samples, indicating that graphene was a potential SPE sorbent for the enrichment of trace residues in food samples.     

Comparison of Different Extraction Methods to Determine Phenolic Compounds in Virgin Olive Oil

A comparison between different extraction methods has been performed in order to assess their effectiveness for the analysis of total phenols (liquid–liquid extraction (LLE), liquid–liquid micro extraction (LLME), and ultrasound liquid–liquid extraction (USE)) and individual phenols (LLME, USE, and solid-phase extraction (SPE)) from virgin olive oil (VOO). Statistical analysis of the analytical data obtained for the total phenol content of a VOO, showed that LLME and USE can represent a reliable alternative to the traditional procedure based on LLE that needs more amount of sample, generates more wastes, and is more time consuming. When an olive oil spiked with phenols was used to test the efficiency of LLME, USE, and SPE methods, the statistical analysis of the data obtained for each individual phenol, again proved LLME and USE methods to be the most suitable, in terms of precision and recoveries, for this purpose. The analysis of real samples (Arbequina and Picual cultivars) confirmed the results obtained for the spiked oil.     

Sample preparation for photometric determination of histamine in foodstuffs compared with capillary electrophoresis

 To determine levels of histamine, two methods were used, photometry in conjunction with two sample clean-up procedures, and capillary zone electrophoresis (CZE). The two sample clean-up procedures used were liquid liquid extraction (LLE) with n-butanol and solid phase extraction (SPE). Using CZE, the separation of histamine from the matrix was good. The other method, photometry, represents a classic and simple method, that can be employed for in situ measurement of histamine. We found that it was necessary to clean up the samples prior to photometry; if this was not done, the recorded levels of histamine were higher than those determined by CZE. In order to determine levels of histamine, both of these rapid tests were applied to ten different foodstuffs. The levels of histamine measured using photometry following either LLE or SPE were compared. The results indicated that photometry is a suitable method for the measurement of histamine, although the sample solutions have to be purified by either LLE or SPE. Samples do not need to be cleaned up before CZE because there is no interference between histamine and attendant material. Both sample clean-up procedures were applied to the following foodstuffs: tomatoes, sauerkraut, tuna, leaf spinach, cream spinach, white wine and mackerel. The differences of the measured values vary between 3% and 18% for LLE and 6% and 27% for SPE. For the other foodstuffs, such as beef, beer and non-alcoholic beer, only one sample clean-up procedure is suitable. LLE used for beef and beer leads to differences in measured levels of histamine between 18% and 50%, respectively, whereas SPE used for non-alcoholic beer leads to differences of 20%. Received: 3 September 1997 / Revised version: 23 October 1997     

罐头食品中双酚A和双酚F环氧衍生物残留的高效液相色谱分析

建立了一种高效液相色谱分析罐头食品中双酚A(BPA)和双酚F(BPF)环氧衍生物的方法。样品经微波辅助萃取后过PPL(填料为苯乙烯-二乙烯苯(SDVB)聚合物)固相萃取柱进行净化试验。结果表明,微波辅助萃取法的提取效果理想;采用PPL固相萃取回收率在73.26%~104.98%,除杂效果明显。将微波辅助—PPL固相萃取净化法应用于多种食品进行分析,结果表明该方法适用于食品中双酚A和双酚F环氧衍生物残留分析。     

Sample preparation for photometric determination of histamine in foodstuffs compared with capillary electrophoresis

 To determine levels of histamine, two methods were used, photometry in conjunction with two sample clean-up procedures, and capillary zone electrophoresis (CZE). The two sample clean-up procedures used were liquid liquid extraction (LLE) with n-butanol and solid phase extraction (SPE). Using CZE, the separation of histamine from the matrix was good. The other method, photometry, represents a classic and simple method, that can be employed for in situ measurement of histamine. We found that it was necessary to clean up the samples prior to photometry; if this was not done, the recorded levels of histamine were higher than those determined by CZE. In order to determine levels of histamine, both of these rapid tests were applied to ten different foodstuffs. The levels of histamine measured using photometry following either LLE or SPE were compared. The results indicated that photometry is a suitable method for the measurement of histamine, although the sample solutions have to be purified by either LLE or SPE. Samples do not need to be cleaned up before CZE because there is no interference between histamine and attendant material. Both sample clean-up procedures were applied to the following foodstuffs: tomatoes, sauerkraut, tuna, leaf spinach, cream spinach, white wine and mackerel. The differences of the measured values vary between 3% and 18% for LLE and 6% and 27% for SPE. For the other foodstuffs, such as beef, beer and non-alcoholic beer, only one sample clean-up procedure is suitable. LLE used for beef and beer leads to differences in measured levels of histamine between 18% and 50%, respectively, whereas SPE used for non-alcoholic beer leads to differences of 20%. Received: 3 September 1997 / Revised version: 23 October 1997     

Fast and simple determination of moroxydine residues in pig and chicken samples by ultra-performance liquid chromatography-tandem mass spectrometry

ABSTRACT

A general solid-phase extraction (SPE) method using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for the determination of moroxydine residues in pig and chicken samples has been developed. After extraction and purification of real samples, moroxydine residues were detected using a hydrophobic interaction liquid chromatography column with an optimised mobile phase composition. The extraction reagents, the kind of SPE columns and the type of eluents were optimised to achieve the maximum extraction efficiency. The matrix effects from the animal tissue influenced the quality of the quantitative data obtained. Under the optimised conditions, the moroxydine residues in pig and chicken samples spiked at three levels (1.0 μg/kg, 5.0 μg/kg and 10.0 μg/kg) were determined with good recoveries (61.5%–105.4%) and adequate relative standard deviations (3.2%–13.0%). In pig and chicken samples, the limit of detection (LOD) was 0.3 μg/kg, and the limit of quantification (LOQ) was 1.0 μg/kg. A sufficiently linear relationship in the range of 1.0 μg/kg–20.0 μg/kg was achieved with a good correlation coefficient (R² ≥ 0.99).     

Optimization of a multiresidual method for the determination of waterborne emerging organic pollutants using solid-phase extraction and liquid chromatography/tandem mass spectrometry and isotope dilution mass spectrometry

A high-throughput, liquid chromatography/tandem mass spectrometry (LC/MS-MS) method has been developed for the determination of 51 emerging organic pollutants (EOPs) in environmental waters. The method was validated for the analysis of 38 pharmaceutically active, 10 endocrine disrupting, and three perfluoroalkylated compounds. Method performance parameters, including sample preservatives, pH values used in the solid-phase extraction (SPE), sample storage, sample extract storage time, and matrix effects were discussed in detail for different aquatic matrices, including drinking water, wastewater, and surface water. Isotope-labeled compounds were used as injection internal standards (IIS) or isotope dilution quantitation standards (IDQS) to improve the data quality, investigate the behavior of matrix effects during SPE sample preparation and LC/MS-MS analysis, and to validate isotope dilution mass spectrometric (IDMS) determination of selected compounds. Method detection limits were determined to be in the low ng/L range forthe compounds evaluated. By application of this method to the analysis of effluents and samples downstream of a wastewater treatment plant, more than 35 target EOPs were quantified. We demonstrated method ruggedness by quality control and quality assurance (QC/QA) data, showed that matrix effects were dependent on modes of electrospray ionization, and could not be removed via SPE or cleanup procedures, exerting the same effect to target compounds in both raw and extracted samples. Both 13C- and 2H-labeled IDQS could be added to samples before sample extraction, and their recoveries used to correct matrix effects in LC/MS-MS EOP analyses.     

Development and validation of a liquid chromatographic-tandem mass spectrometric method for determination of eleven coccidiostats in milk

A reversed phase liquid chromatographic–tandem mass spectrometric method with simple solvent extraction and purification by solid phase extraction (SPE) has been developed for the determination of coccidiostats in milk. For sample preparation matrix solid phase dispersion, extraction by organic solvent and SPE with different cartridges were also tested. The compounds determined include lasalocid, narasin, salinomycin, monensin, semduramicin, maduramicin, robenidine, decoquinate, halofuginone, nicarbazin and diclazuril. Main steps of the method are addition of acetonitrile to the milk samples, centrifugation, removal of matrix by SPE, concentration by evaporation and LC–MS–MS determination. During a 15 min time segmented chromatographic run compounds are ionised either positively or negatively. Calculated recoveries range between 77.1% and 118.2%. Maximum levels are in the range of 1–20 μg/kg. The developed method was validated in line with the requirements of Commission Decision 2002/657/EC (2002). It is applicable for control of coccidiostat residues in milk as indicated in Regulation 124/2009/EC (2009).     

固相萃取与气相色谱-质谱联用分析调味料中3-氯-1,2-丙二醇

建立固相萃取与气相色谱-质谱联用(solid phase extraction with gas chromatography-mass spectrometry,SPE-GC-MS)测定调味料中3-氯-1,2-丙二醇的新方法。对影响分析物SPE萃取效率的诸因素如洗脱溶剂、洗脱溶剂的体积和上样体积等进行详细考察和优化。最佳萃取条件为5.0g样品与5mol/L氯化钠溶液混匀,经SPE萃取净化、衍生后,以GC-MS进行测定,该方法对3-氯-1,2-丙二醇的检出限为0.15μg/kg,线性范围为0.51～6144μg/kg,相关系数和相对标准偏差(relative standard deviation,RSD)(n=5)分别为0.9998和8.8%。该方法成功应用于调味料3-氯-1,2-丙二醇的分析,加标回收的回收率为87.2%～109.4%。