加速溶剂萃取-固相萃取-硅胶吸附色谱-电喷雾质谱法测定纺织品中的烷基酚聚氧乙烯醚

建立了测定纺织品中壬基酚聚氧乙烯醚和辛基酚聚氧乙烯醚的硅胶吸附色谱-电喷雾质谱分析方法.不同类型的纺织品样品采用加速溶剂萃取法,以无水乙醇为提取溶剂,在10.3 MPa和100 ℃下静态循环提取2次,提取液经Sep-Pak Carbon/NH2石墨化碳黑/氨基复合型固相萃取柱净化,以Waters Spherisorb S3W(150 mm×2.0 mm, 3 μm)色谱柱为分离柱,乙腈-水体系为流动相梯度洗脱,在电喷雾质谱正离子模式下进行定性及定量分析.壬基酚聚氧乙烯醚的方法检出限为10～40 μg/kg,在1～20 mg/kg的3个添加水平范围内的平均回收率为81.4%～95.9%,相对标准偏差均小于12.5%.辛基酚聚氧乙烯醚的方法检出限为10～30 μg/kg,在1～20 mg/kg的3个添加水平范围内的平均回收率为80.2%～96.8%, 相对标准偏差均小于13.0%.本方法准确、简便、快速,可用于纺织品的实际检验工作.     

液质联用法测定纺织品中烷基酚和烷基酚聚氧乙烯醚

采用高效液相色谱-质谱法测定了纺织品中残留的辛基酚、壬基酚、辛基酚聚氧乙烯醚和壬基酚聚氧乙烯醚,对提取方式、提取溶剂等前处理条件进行了优化,对质谱监测离子进行了选择。该方法检出限(S/N=5)为0.010~0.025 mg/kg,回收率为93%~106%,相对标准偏差为1.0%~5.0%,方法简便、准确,灵敏度高。     

凝胶过滤色谱-串联质谱法测定纺织品中的烷基酚聚氧乙烯醚

建立了纺织品中烷基酚聚氧乙烯醚的凝胶过滤色谱-串联质谱(GFC-MS/MS)分析方法。纺织品样品采用加速溶剂萃取法,以无水乙醇为提取溶剂进行提取,提取液经Sep-Pak Carbon/NH2石墨化碳黑/氨基复合型固相萃取柱净化。烷基酚聚氧乙烯醚经Shodex MSpak GF-310 2D色谱柱(150×2.0 mm)分离后,在多反应监测(MRM)模式下进行串联质谱定性及定量分析。方法对壬基酚聚氧乙烯醚(NPnEO)和辛基酚聚氧乙烯醚(OPnEO)的定量限均为0.2 mg/kg,在0.2～5 mg/kg的3个添加水平范围内,NPnEO的平均回收率为84.2%～93.5%,相对标准偏差(RSD)为3.9%～7.5%;OPnEO的平均回收率为85.5%～96.1%,RSD为3.4%～8.1%。该方法能够满足纺织品中烷基酚聚氧乙烯醚的检测要求。     

内墙涂料中烷基酚聚氧乙烯醚的高效液相色谱-质谱测定

建立了高效液相色谱-质谱法(HPLC-MS)测定内墙涂料中烷基酚聚氧乙烯醚(辛基酚聚氧乙烯醚和壬基酚聚氧乙烯醚)含量的方法。样品经甲醇超声提取,采用Agilent Eclipse Plus C18柱(4.6 mm×100 mm,3.5μm),以5 mmol/L乙酸铵溶液-甲醇作为流动相进行梯度洗脱分离,柱温35℃,流速0.3 m L·min-1,进样量5μL。质谱采用选择离子(SIM)方式进行检测,电喷雾离子源(ESI),正离子模式,基质匹配标准溶液定量,以A和B两种内墙涂料为代表进行加标回收实验。结果表明,辛基酚聚氧乙烯醚(OPEO)和壬基酚聚氧乙烯醚(NPEO)在0.1~5.0 mg/L浓度范围内线性关系良好(r0.99),回收率为83.8%~114.5%,相对标准偏差为1.3%~9.8%,定量下限为4.0~5.5 mg/kg。该方法操作简便、耗时短、有机试剂用量少、灵敏度高、稳定性好,应用于日常检测可大大降低检测成本,缩短检测周期,具有实际应用价值。     

皮革及纺织品中烷基酚与烷基酚聚氧乙烯醚的液相色谱-质谱测定

建立了液相色谱-质谱法测定皮革及纺织品中辛基酚(OP)、壬基酚(NP)、辛基酚聚氧乙烯醚(OPEO)及壬基酚聚氧乙烯醚(NPEO)的分析方法。样品经超声波振荡萃取,C18反相色谱柱进行分离,甲醇-水为流动相,离子源为ESI。OP和NP采用负离子模式,定量离子分别为m/z205、219;OPEO和NPEO采用正离子模式,定量离子分别为m/z229+44nEO和m/z243+44nEO(nEO=3~16)。在优化实验条件下,方法的定量下限为0.25~2.5 mg/kg,样品加标回收率为92%~107%,相对标准偏差为5.3%~9.5%(50 mg/kg,n=6)。方法简单、快速、灵敏度高,可满足欧盟等地区对皮革及纺织品中OP、NP、OPEO、NPEO的测定要求。     

加速溶剂萃取-液相色谱-质谱/质谱法分析动物组织中的壬基酚、辛基酚和双酚A

建立了测定内分泌干扰物质烷基酚、双酚A的液相色谱-电喷雾串联质谱(负离子模式)分析方法,优化了样品前处理方法。以二氯甲烷作提取溶剂,采用加速溶剂萃取法萃取动物组织样品,萃取液用500 mg OASIS氨基固相萃取柱进行浓缩净化。对流动相组分和流动相添加剂对质谱的离子化效率进行了考察,测得3种化合物在高、中、低3个添加水平的回收率为88%~101%,相对标准偏差小于15%;双酚A、壬基酚和辛基酚的方法检出限分别为0.3, 0.05和0.1 μg/kg。对从北京市场上采集的27份动物组织样品进行检测,结果表明壬基酚广泛存在于各种动物源性食品中,检出含量为0.49~55.98 μg/kg,其中鱼肉组织中都检出壬基酚,而且其含量也较高(9.13~55.98 μg/kg)。     

磁性石墨烯分散固相萃取结合液相色谱-串联质谱法测定水基胶中的双酚A和烷基酚

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)与磁性石墨烯相结合测定水基胶中双酚A、壬基酚和辛基酚的方法。样品提取后,以磁性石墨烯分散固相萃取净化,经BEH C18色谱柱分离。分析物的回收率在81.5%～97.9%之间,日间相对标准偏差(RSDs)小于8.0%。所有化合物均获得了良好的线性系数(r≥0.9996),检出限(LOD)和定量限(LOQ)范围分别为3～8μg/kg和10～26μg/kg。采用该方法对20个水基胶实际样品进行检测,仅有1个样品检出4-正壬基酚。该方法可用于测定水基胶中双酚A和4种烷基酚的含量。     

超高效液相色谱–串联质谱法测定食品接触材料中烷基酚物质迁移量

建立了超高效液相色谱-串联质谱法测定食品接触材料中双酚A、四溴双酚A、壬基酚和辛基酚迁移量的方法。样品经蒸馏水、3%乙酸溶液、10%乙醇溶液、20%乙醇溶液、50%乙醇溶液和异辛烷6种食品模拟物浸泡处理,浸泡液经C18色谱柱分离,以多反应监测(MRM)模式进行定性和定量。检测结果表明:在水基、酸性、酒精类食品模拟物中,双酚A、四溴双酚A、壬基酚、辛基酚的质量浓度均在0.001~0.50μg/mL范围内与其质谱响应值具有良好的线性关系,相关系数均不小于0.9995,方法检出限为0.01~0.25μg/kg,定量限为0.03~0.83μg/kg;在油基食品模拟物中,双酚A、四溴双酚A、壬基酚、辛基酚的线性范围均为0.01~0.50μg/mL,相关系数均不小于0.9989,方法检出限为0.10~2.50μg/kg,定量限为0.33~8.32μg/kg。双酚A、四溴双酚A、壬基酚、辛基酚的加标回收率为87.2%~101.2%,相对标准偏差为1.5%~3.4%(n=6)。该法样品处理步骤简单,准确度高,灵敏度好,可用于食品接触材料中烷基酚类化合物的检测。     

柱前衍生-气相色谱/质谱-选择离子法测定纺织品中烷基酚的方法研究

建立了纺织品中壬基酚和辛基酚的提取与含量测定方法.纺织品样品经以CH2Cl2为萃取液的超声提取、衍生化后,采用气相色谱/质谱-选择离子定量分析方法,对4-壬基酚同分异构体总量和4-n-辛基酚进行了定量检测.通过实验对前处理条件、衍生化条件、色谱条件、选择离子等作了优化.该方法的加标回收率为80.73%～99.78%,相对标准偏差小于5%.方法适用于纺织品中烷基酚的含量分析.     

正相液相色谱法测定洗涤用品中的烷基酚聚氧乙烯醚

建立了正相液相色谱法测定洗涤用品中烷基酚聚氧乙烯醚的分析方法.洗涤用品样品以正己烷.异丙醇混合溶液超声提取后,采用Agilent ZORBAX NH2(5μm,250 mm×4.6 mm i.d.)色谱柱,以A(90%正己烷.10%异丙醇,V/V)和B(90%异丙醇-10%水,V/V)为流动相进行梯度洗脱,不同聚合度的烷基酚聚氧乙烯醚色谱峰实现了理想的分离效果.在低、中、高3个添加水平下,烷基酚聚氧乙烯醚的平均回收率为92.3%～95.7%,相对标准偏差在3.9%～5.7%之间.     

Dispersive liquid–liquid microextraction applied to isolation and concentration of alkylphenols and their short-chained ethoxylates in water samples

Dispersive liquid–liquid microextraction (DLLME) coupled with high-performance liquid chromatography with fluorescence detector was applied for the determination of alkylphenols and their short-chained ethoxylates in water samples. Development of DLLME procedure included optimisation of some important parameters such as kind and volume of extracting and dispersing solvents. Under optimised conditions 50 μL of trichloroethylene in 1.5 mL of acetone were rapidly injected into 5 mL of a water sample. After centrifuging the organic phase containing the analytes was taken for evaporation with a gentle nitrogen purge and reconstituted to 50 μL of acetonitrile. The aliquot of this solution was analysed with the use of HPLC. For octylphenol (OP) and octylphenol ethoxylates (OPEOs) linearity was satisfactory in the range 8–1000 μg L⁻¹ and for nonylphenol (NP) and nonylphenol ethoxylates (NPEOs) linearity was in the range from 50 to about 3000 μg L⁻¹. Limit of quantitation was 0.1 μg L⁻¹ for OP and OPEOs and 0.3 μg L⁻¹ for NP and NPEOs. Satisfactory recoveries between 66 and 79% were obtained for environmental samples. The results showed that DLLME is a simple, rapid and sensitive analytical method for the preconcentration of trace amounts of alkylphenols and their ethoxylates in environmental water samples.     

Determination of Alkylphenols Originated from Alkylphenol Ethoxylates by Cleavage Treatment Combined with GC-MS

A chemical cleavage technique was developed for the determination of alkylphenol ethoxylates (APEOs) in environmental samples involving the conversion of APEOs to alkylphenols (APs). Aluminum triiodide (AlI₃) and trimethylsilyl iodide were selected as cleavage reagents and the former was found to be highly reactive and suitable. With AlI₃ as cleavage reagent, nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) were equivalently converted to the corresponding origins—nonylphenol (NP) and octylphenol (OP), which were detected by gas chromatography—mass spectrometry (GC-MS). The cleavage process was completed under refluxing condition. Water and methanol influenced the cleavage reaction significantly and should be removed prior to the cleavage reaction. The analytical approach was applied for the estimation of APEOs contents in wastewater by normalizing to APs and presented satisfactory recovery and reproducibility. This cleavage technique provides a common and reliable means to assess the environmental significance of samples contaminated by APEOs based on the presence of APs.     

Determination of free and ethoxylated alkylphenols in leather with gas chromatography-mass spectrometry

An analytical approach was developed to determine nonylphenol (NP), octylphenol (OP), nonylphenol ethoxylates (NPEO(n)) and octylphenol ethoxylates (OPEO(n)) in leather samples involving the conversion of NPEO(n) and OPEO(n) into the corresponding NP and OP. The four targets were extracted from samples using ultrasonic-assisted acetonitrile extraction. NP and OP in the extracts were directly isolated with hexane and quantitatively determined with 4-n-nonylphenol as internal standard by gas chromatography-mass spectrometry (GC-MS). For NPEO(n) and OPEO(n) in the extracts, they were first converted into NP and OP with aluminum triiodide as cleavage agent, and the yielded NP and OP were determined by GC-MS. The contents of NPEO(n) and OPEO(n) were calculated by normalizing to NPEO(9) and OPEO(9), respectively. This method was properly validated and the real sample tests revealed the pollution significance of leather by NPEO(n) and OPEO(n).     

Practical Method for Accurate Determination of Alkylphenol Ethoxylates in Household Detergents by Aluminum Iodide Cleavage Pretreatment Followed by GC–MS

A practical procedure was developed for detecting nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in household detergents by gas chromatography–mass spectrometry (GC–MS) with the introduction of a cleavage technique using aluminum iodide (AlI₃) to convert NPEOs and OPEOs to their parent nonylphenol and octylphenol. The reliability of the cleavage process was evaluated using Igepal-210, Triton X-15, Tergitol NP-9, and Triton X-100 as substrates, demonstrating satisfactory efficiency. The effect of the sample matrix on the cleavage process was investigated, and the optimized dose of AlI₃ was estimated. The major advantage of this method is the use of a common analytical tool (GC–MS) for accurate monitoring of APEOs after elimination of the ethoxylate chain, with detection limits of 12.5 mg/kg and 5.0 mg/kg for NPEO₉ and OPEO₉, respectively. Analytical results revealed that NPEOs and OPEOs were found in 12.6 % of 182 household detergents in the concentration range of 18–800 mg/kg.     

Determination of nonylphenol and octylphenol in paper by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry

A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1).     

Determination of nonylphenol ethoxylates in the aquatic environment by normal phase liquid chromatography-electrospray mass spectrometry

A comprehensive analytical method based on normal-phase liquid chromatography–electrospray ionization mass spectrometry (NPLC–ESI-MS) has been established for determination of nonylphenol ethoxylates (NPEOs) in the aquatic environment. Extraction and cleanup of samples were performed on graphitized carbon black (GCB) solid-phase extraction cartridges. Complete separation between each individual NPEOs was achieved by combining a C₁₈ pre-column with a silica analytical column and using acetonitrile–water as eluent. Quantitative determination by LC–ESI-MS was achieved in the positive ionization (PI) mode at a ramped cone voltage for NPEOs using selected ion monitoring. Recoveries for NPEOs ranged between 91.9 and 117.5%, and the limits of detection varied between 0.5 and 2 ng/l for individual NPEOs with n longer than 2, and between 5 and 0.5 μg/l for NP1EO and NP2EO. This method was successfully applied to the investigation of residual NPEOs with n>2 in the Chongqing area of the Changjiang river. NPEOs with n ranging from 1 to 22 were found to vary between 0.1 and 2900 ng/l with a distribution depending on the depth of water.     

Determination of chlormequat and mepiquat in pear,tomato, and wheat flour using on-line solid-phase extraction (Prospekt) coupled with liquid chromatography-electrospray ionization tandem mass spectrometry

A new methodology based on pressurized liquid extraction (PLE) followed by LC-MS is presented for the simultaneous and unequivocal determination of alkylphenol ethoxylates (APEOs) and their degradation products, alkylphenols (APs) and alkylphenoxy carboxylates (APECs), in sediment samples. The protocol, applicable to a full range of APEO oligomers and degradation products, permits the sensitive and selective determination of APEOs (nEO = 1-15), APECs (nEO = 0-1) and APs at low ppb levels (LODs = 1-5 microg/kg) in sediment samples. Optimization of the operational parameters of PLE clearly demonstrates that significant thermal losses of APs occur during extraction at elevated temperatures. The loss of octylphenol (OP) at 100 degrees C was 61.2% and of nonylphenol (NP) 40.0%, whereas other compounds were completely recovered. Thus, to avoid losses due to the volatility of alkylphenols, a low extraction temperature should be applied. The conditions that gave the best results for all target compounds were as follows: extraction solvent mixture, methanol-acetone (1:1, v/v); temperature, 50 degrees C; pressure, 1500 p.s.i.; two static cycles. Using PLE and a subsequent clean-up with solid-phase extraction (SPE), the simultaneous extraction of APEOs, APs and APECs from sediment samples was achieved yielding recoveries >70% and producing low MS background noise. The developed methodology was applied on a routine basis to the analysis of alkylphenolic compounds in sediment samples. APEOs and their persistent degradation products were detected in significant concentrations in sediments from Portuguese rivers, especially at sites situated in the proximity of industrial plants (mainly the textile industry). The total concentration of alkylphenolic compounds (APEOs+APs+APECs) ranged from 155 to 2400 microg/kg. Of all the alkylphenolic compounds, NP comprised 40 to 50% with concentrations up to 1172 microg/kg.     

液相色谱-电喷雾质谱法同时测定水体中的壬基酚聚氧乙烯醚及其代谢产物

利用液相色谱-电喷雾质谱法同时分析水体中的壬基酚聚氧乙烯醚(NPEOs)及其代谢产物壬基酚聚氧乙烯醚乙酸(NPECs)和壬基酚(NP),用Waters Symmetry ShieldTMRP 18色谱柱,甲醇和乙酸铵溶液作为梯度洗脱的流动相,结果表明3类物质的分离效果良好,并可通过选择离子记录(SIR)模式实现NPEOs和NPECs各单体的定量。仪器的检出限为1~50 pg,选用Oasis HLB小柱进行固相萃取,回收率达75%~98%,平均标准偏差小于12%。该方法用于污水处理厂的水样测定,所取各水样中都测出了NP和NPEOs,并从氧化沟上清液中检测到NPECs。     

Determination of phenolic xenoestrogens in environmental samples by liquid chromatography with mass spectrometric detection

A method is proposed for the determination of several phenolic xenoestrogens in aqueous and solid environmental samples. The method uses solid-phase extraction (preceded by ultrasonic solvent extraction for solid samples), reversed-phase liquid chromatographic separation, and mass spectrometric detection using both atmospheric pressure chemical ionization and electrospray ionization. This method was developed to support several studies undertaken to obtain aquatic and sedimentary data for rivers and seashores in Spain that are likely to be contaminated by endocrine-disrupting compounds (EDCs) as a consequence of wastewater discharge. Nonylphenol polyethoxylates (NPEOs), nonylphenoxy carboxylates (NPECs), nonylphenol (NP), octylphenol (OP), and bisphenol A (BPA) were determined in various samples of surface water and sediment, collected at different locations upstream and downstream from outfalls of municipal wastewater treatment plants (WWTPs). Seawater and marine sediments were collected in different harbor areas in Spain. Additionally, WWTP influent and effluents were analyzed to monitor the occurrence and transformation of phenolic EDCs during physicochemical and biological treatment. Rather high concentrations of the compounds investigated were found in some samples. Concentrations of NP were < or = 590 microg/kg in sediments and < or = 15 microg/L in water samples. NPEOs and NPECs were found in water samples in concentrations < or = 41 and < or = 35 microg/L, respectively. In solid samples (river sediment), concentrations of NPEO were < or = 818 microg/kg and those of NP1EC were 95 microg/kg.