On-line enrichment and determination of polycyclic aromatic hydrocarbons in atmospheric particulates using high performance liquid chromatography with fluorescence as detector

Seven polycyclic aromatic hydrocarbons （PAHs） in atmospheric particulates were determinated by high performance liquid chromatography （HPLC） with fluorescence detector using direction injection and an on-line enrichment trap column. The method simplified the sample pretreatment, saved time and increased the efficiency. With the on-line trap column, PAHs were separated availably even underground injecting 1.0 ml sample with relatively high column efficiency. The recoveries of the seven PAHs were from 85% to 120% for spiked atmospheric particulate sample. The limit of detection was 15.3-39.6 ng/L （S/N=3.3）. There were good linear correlations between the peak areas and concentrations of the seven kinds of PAHs in the range of 1-50 ng/ml with the correlation coefficients over 0.9970. Furthermore, it also indicated that the method is available to determine PAHs in atmospheric particulates well.

Ionic liquid based dispersive liquid-liquid microextraction of aromatic amines in water samples

In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid （IL） phase was injected directly into the high performance liquid chromatography （HPLC） system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection （LOD, S/N = 3） for the four analytes were in the range of 0.45-2.6 μg L^-1. The relative standard deviations （R.S.D., n = 6） were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.

Optimization of Ultrasonic Extraction and Clean-up Protocol for the Determination of Polycyclic Aromatic Hydrocarbons in Marine Sediments by High-performance Liquid Chroma-tography Coupled with Fluorescence Detection

The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were purified with a miniaturized silica gel chromatographic column and analyzed with high performance liquid chromatography (HPLC) with a fluorescence detector. Ultrasonication with methanol-dichloromethane (2:1, v/v) mixture gave higher extraction efficiency than that with dichloromethane. Among the three elution solvents used in clean-up step, dichloromethane-hexane (2:3, v/v) mixture was the most satisfactory. Under the optimized conditions, the recoveries in the range of 54.82% to 94.70% with RSDs of 3.02% to 23.22% for a spiked blank, and in the range of 61.20% to 127.08% with RSDs of 7.61% to 26.93% for a spiked matrix, were obtained for the 15 PAHs studied, while the recoveries for a NIST standard reference SRM 1941b were in the range of 50.79% to 83.78% with RSDs of 5.24% to 21.38%. The detection limits were between 0.75 ng L-1 and 10.99 ng L-1for different PAHs. A sample from the Jiaozhou Bay area was examined to test the established methods.

Exposure of university students to polycyclic aromatic hydrocarbons measured from urinary monohydroxy metabolites

Internal exposure of university students to polycyclic aromatic hydrocarbons (PAHs) was assessed through urinary PAHs metabolites. Eight monohydroxylated PAHs (OH-PAHs) were detected with high performance liquid chromatography (HPLC). The detectable frequencies were 59%-100% for different analytes. Major components in the subjects’ urine were 2-hydroxynaphthalene (2-OHNap, 0.60 μg/mmol creatinine), followed by hydroxyphenanthrene (ΣOH-Phe, 0.38 μg/mmol creatinine) and 2-hydroxyfluorene (2-OHFlu, 0.25 μg/mmol creatinine). Excretion of 1-hydroxypyrene (1-OHPyr, 0.08 μg/mmol creatinine) was almost one order of magnitude lower than the 2-OHNap level in the urine samples. Phenanthrene can be metabolized to five monohydroxy metabolites in human urine. In the present study, 1-or 9-hydroxyphenanthrene (1-or 9-OHPhe) was the dominant component (79%), followed by 2-+3-OHPhe (18%) and 4-OHPhe (3%). The study indicates that 1-OHPyr may not be a good marker for total PAHs exposure, and monitoring of 2-OHNap, 2-OHFlu, 1-or 9-OHPhe and 1-OHPyr as multiple biomarkers are more suitable than only using 1-OHPyr. The levels of OH-PAHs detected in urines of students living in Shanghai are higher those of people in other countries or regions. The concentrations of urine OH-PAHs are directly related to the exposure to PAHs in the environment, indicating that Shanghai residents are at high health risk.

Association between polycyclic aromatic hydrocarbons and human rectal tumor or liver cancer

Objective: The aim of this study was to investigate the effect of polycyclic aromatic hydrocarbons (PAHs) in rectal carcinoma and hepatocarcinoma genesis. Methods: The PAHs in the human rectal cancer and liver cancer tissues, the adjacent tissues and homologous tissues without rectal cancer or liver cancer were extracted by ultrasonic wave. The extracts were then cleaned up and enriched by solid phase extraction, analyzed by high performance liquid chromatography (HPLC) with fluorescence spectroscopy. Results: Four kinds of PAHs were detected in human rectal and hepatic tissues. The contents of pyrene, 2-methylanthracene and benzo (a) pyrene in both rectal cancer tissues and adjacent homologous tissues were higher than rectal tissues without rectal cancer, the differences were statistically significant (P < 0.05). The contents of phenanthrene in the three kind of tissue were not significant (P > 0.05). The differences of the content of each PAHs between rectal cancer and adjacent tissue were not significant (P > 0.05). The contents of the four PAHs in the three kinds of liver tissues were not statistically significant (P > 0.05). Conclusion: PAHs are found in human rectal tissues or hepatic tissues. The contents of PAHs in human rectal tissue may have an effect on the occurrence of human rectal cancer while the contents of PAHs in human hepatic tissues may have not ones.

The detection and significance of polycyclic aromatic hydrocarbons in human pancreatic cancer

Objective:The aim of this study was to investigate the effect of polycyclic aromatic hydrocarbons (PAHs) on the occurrence of human pancreatic cancer.Methods:PAHs in human pancreatic cancer,adjacent pancreatic cancer tissues and tissues without pancreatic cancer were extracted by ultrasonic extraction (UE).And then the extracts were cleaned up by solid phase extraction and analyzed by high performance liquid chromatography (HPLC) with fluorescence spectroscopy.Results:Four kinds of PAHs were detected,which were chrysene,2-methylanthracene,pyrene and benzo (a) pyrene.The contents of the four PAHs were not statistically significant between pancreatic cancer and adjacent tissues (P > 0.05).The contents of 2-methylanthracene,pyrene and benzo (a) pyrene in pancreatic cancer and adjacent tissues were higher than tissues without pancreatic cancer,the differences were statistically significant (P < 0.05).The contents of chrysene in the three kinds of pancreatic tissues were not statistically significant (P > 0.05).Conclusion:PAHs were found in human pancreatic tissues.Human pancreatic tissues have extremely strong ability of bio-concentrating PAHs.PAHs might play an important role in the occurrence of human pancreatic cancer.

超高效液相色谱-三重四极杆质谱法同时测定纺织品中30种芳香胺类化合物的含量

取0.1 g 5 mm×5 mm的纺织品小片,加入17 mL(70±2)℃柠檬酸盐缓冲溶液(pH 6.0),参考GB/T 17592—2011进行还原裂解、萃取、浓缩,加适量甲醇稀释,采用超高效液相色谱-三重四极杆质谱法同时测定30种芳香胺类化合物的含量。以ZORBAX Eclipse Plus C18色谱柱作固定相,不同体积比0.1%(体积分数)甲酸溶液和甲醇的混合溶液作流动相进行梯度洗脱,电喷雾离子源正离子(ESI+)模式电离,外标法定量。结果显示:各目标物的质量浓度在50~2000μg·L^(-1)内和峰面积呈线性关系,检出限(3S/N)为0.05~1.69μg·kg^(-1);按照标准加入法进行回收试验,测定值的相对标准偏差(n=6)为3.0%~7.0%,回收率为60.3%~96.5%。方法用于两个质控样品的分析,测定值和指定值基本一致。

液液萃取--超高效液相色谱串联质谱法同时测定尿中11种羟基多环芳烃

目的建立可同时测定尿中11种羟基多环芳烃(hydroxy-polycyclic aromatic hydrocarbons,OH-PAHs)的超高效液相色谱串联质谱分析(ultra-high performance liquid chromatography tandem with mass spectrometry,UPLC-MS/MS)法。方法尿液样品在pH=5.5条件下,在37℃水浴中经β-葡萄糖苷酸酶—芳基硫酸酯酶避光水解16 h,3.0 mL正己烷萃取、涡旋、离心,取上层有机相,重复萃取两次,合并萃取液,氮吹至近干,再复溶于20%乙腈水溶液中。流动相为水和10%异丙醇甲醇溶液,梯度洗脱模式洗脱,CORTECS C18色谱柱分离,ESI-模式测定尿液中11种羟基多环芳烃浓度,内标法定量分析。结果11种羟基多环芳烃线性关系良好,相关系数(r)均大于0.997。方法的检出限为0.01~0.10 ng/mL;日间回收率为79.8%~97.3%,精密度为1.9%~4.7%(n=3);日内回收率为78.6%~92.3%,精密度为3.7%~7.1%(n=3)。结论该方灵敏度高,准确可靠,适用于人群中多种羟基多环芳烃的监测。

几种发酵食品生物胺含量检测与食用安全性分析

生物胺是一类人体所需、具有生物活性的小分子含氮化合物,过量摄入可造成人体出现不良反应。该研究利用高效液相色谱法对食用酱,泡菜、奶酪和腐乳等四类发酵食品进行生物胺含量检测与分析。结果表明食用酱中主要存在的生物胺种类为苯乙胺、腐胺、组胺和酪胺,生物胺总含量范围在331.40~624.42 mg/kg之间;某些腐乳产品中生物胺含量较高,总含量可达2355.32和1091.05 mg/kg。相比于食用酱和腐乳,泡菜和奶酪中检测出的生物胺含量较低,其中泡菜中生物胺含量最高的为酸豆角,总生物胺为126.65 mg/kg,最低的为泡藕节,总生物胺含量为22.32 mg/kg。另外,本研究还基于发酵食品食用特性、组胺和酪胺生物学毒理学性质,结合食用场景和危害风险评估分析食用酱和腐乳而引起的生物胺食用安全性,结果表明摄食这几种食品生物胺毒性危害风险较低,食用安全性高。该文为消费者深入了解我国传统发酵食品的食用安全性提供了重要依据。

高效液相色谱-内标法测定香辛料中15种多环芳烃类污染物(PAHs)

该研究建立了高效液相色谱(High Performance Liquid Chromatography,HPLC)同时分析香辛料中15种多环芳烃类污染物(Polycyclic Aromatic Hydrocarbons,PAHs)含量的内标检测方法。样品经氢氧化钠溶解,乙腈萃取,正己烷复溶后,过弗罗里硅土(Florisil)小柱净化浓缩,供HPLC检测,苯并[a]芘-D12作为内标定量。该方法在0~100 ng/mL内线性关系良好,辣椒中PAHs检出限:0.5~3.0μg/kg;定量限2.0~10.0μg/kg;花椒中检出限:0.5~1.0μg/kg;定量限2.0~3.0μg/kg。在2.0、10.0、50.0μg/kg 3个浓度水平,辣椒中回收率范围为60.58%~119.48%,相对标准偏差(Relative Standard Deviations,RSD)(n=6)为1.25%~9.61%,花椒中回收率为60.46%~119.24%,RSD(n=6)为1.10%~8.56%。5种地产香辛料中∑PAHs含量由高到低为:青花椒(561.2μg/kg)>二荆条(448.8μg/kg)>红花椒(358.3μg/kg)>石柱红(353.6μg/kg)>小米辣(243.5μg/kg),区县种植基地污染较严重的为璧山、江津和荣昌,∑PAHs分别为721.5、626.6和621.0μg/kg,PAHs中污染较严重的化合物为菲、荧蒽和芘,平均含量分别为215.10、80.25和75.35μg/kg。该研究建立的内标法准确度高,重复性好,适用于香辛料及制品中PAHs检测。

红曲橙色素降低食品中生物胺含量的机制

过量的生物胺影响食品品质,同时危害人体健康。为探索降低食品中生物胺含量的新方法,采用高效液相色谱分析红曲色素提取物对不同食材中生物胺含量的影响。结果显示,添加富含红曲橙色素的提取物或仅添加一种橙色的红斑红曲素均可有效降低不同食材中8种生物胺的含量。金枪鱼、纳豆和红方腐乳中的总生物胺分别降低34.0%、23.1%和42.8%。青方腐乳中的总生物胺降低26.7%,红斑红曲素和红曲玉红素通过胺化反应将酪胺转化为红色的衍生色素L1和L2,分子量分别为473.220 6 Da和501.251 3 Da。添加橙色素不仅降低青方腐乳中的生物胺含量,还具有着色功能。

高效液相色谱-三重四极杆/复合线性离子阱质谱法同时测定液态发酵食品中14种生物胺及其代谢物

目的基于高效液相色谱-三重四极杆/复合线性离子阱质谱法(high performance liquid chromatography-triple quadrupole/composite linear ion trap mass spectrometry,HPLC-QTRAP MS)建立同时测定液态发酵食品中14中生物胺及其代谢物的分析方法。方法采用Waters Atlantis Premier BEH Z-HILIC色谱柱(100mm×2.1mm,1.7μm),以0.025%(V/V)甲酸水和0.1%(V/V)甲酸乙腈进行梯度洗脱,电喷雾离子源(electrospray ionization,ESI)正离子模式、多反应监测(multiple reaction monitoring,MRM)离子扫描模式、信息依赖性采集(information dependent acquisition,IDA)、增强子离子扫描(enhanced ion scanning,EPI)和EPI谱库搜索的复合模式进行测定。结果在0.05~200.00μg/L质量浓度范围内,14种生物胺及其代谢物的线性关系良好,相关系数均大于0.99;方法检出限(S/N=3)为0.15~6.00μg/L;在不同添加质量浓度(2.0、10.0、50.0μg/L)下,其回收率为75.2%~107.9%,相对标准偏差在1.98%~9.07%之间。结论该方法具有操作简便、快速、准确、灵敏等优点,可满足液态类发酵食品中14种生物胺的定性定量分析需要,为液态发酵类食品中生物胺的检测分析奠定基础。

液相色谱-串联质谱法定量检测油脂中16种多环芳烃

目的建立液相色谱-串联质谱法同时测定食用油中16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)含量的方法。方法油脂经乙腈提取处理后,采用柱纯化技术对PAHs进行富集,通过液相色谱-串联质谱仪进行检测。重点优化离子源的选择,色谱柱的优化,提取溶剂和提取溶剂体积以及洗脱溶液的选择等。确定最优前处理方法为5 mL乙腈提取,PAH固相萃取柱净化并用15 mL乙酸乙酯:二氯甲烷(V:V=1:1)洗脱。最优检测条件为使用大气压化学电离源在正离子模式下进行离子化,使用EclipsePAH液相色谱柱进行分离。结果16种PAHs在0.1~500.0μg/L的质量浓度范围内呈现良好的线性关系,检出限在0.04~1.72μg/kg,定量限在0.11~17.01μg/kg,加标回收率有最优值为75.71%~117.60%,日内相对标准偏差为0.09%~8.00%,日间相对标准偏差为0.10%~8.18%。结论该方法可准确提取并检测出16种PAHs,提高食用油中PAHs的检测效率,为食用油的安全性评价提供了方法支撑。

高效液相色谱法对长链烷基芳烃的组分分析研究

烷基化芳烃作为第四代合成油系列产物,因其性能优异而受到广泛关注,其中长链烷基芳烃由于碳数较大、沸点较高而难以气化、相对成分较为复杂,给组分分析带来很大困难。利用高效液相色谱法对长链烷基芳烃的各组分进行了分析,分别探讨了紫外检测波长、流速以及流动相的极性等参数对色谱分析结果的影响,并总结出一种适于长链烷基芳烃组分分析的方法。研究结果可为分析长链烷基芳烃相关产品提供一定的理论指导。

冷藏时间对大黄鱼、鲳鱼中生物胺含量变化的影响

目的:建立一种以高效液相色谱法测定9种生物胺含量的方法,研究冷藏时间对大黄鱼、鲳鱼生物胺含量的影响。方法:大黄鱼、鲳鱼样品经高氯酸溶液溶解提取,丹磺酰氯衍生剂衍生,氨水终止衍生反应,避光静置,乙腈定容。利用Agilent Eclipse XDB-C18色谱柱(4.6 mm×250 mm,5μm)分离,以5 mmol/L乙酸铵和乙腈为流动相进行梯度洗脱,流速为0.8 mL/min,二极管阵列检测器在波长254 nm下检测。结果:此方法可将9种生物胺在35 min内有效分离;在0.1~80.0 mg/L范围内,9种生物胺混合标准溶液质量浓度与峰面积呈良好的线性关系,相关系数均大于0.995;方法检出限为0.5 mg/kg,定量限为1.0 mg/kg;加标回收率介于75.70%~105.40%之间,相对标准偏差≤5%(n=6)。结论:所建立的方法能够对大黄鱼、鲳鱼中9种生物胺含量进行简便、准确、可靠的分析;利用该方法研究大黄鱼和鲳鱼中生物胺含量随冷藏时间的变化规律,结果表明,腐胺、尸胺和酪胺含量变化较明显,亚精胺和精胺含量变化平缓,冷藏30 d的大黄鱼,腐胺、尸胺和酪胺含量分别增加161、143、49.2 mg/kg,冷藏30 d的鲳鱼,腐胺、尸胺和酪胺含量分别增加168、192、221 mg/kg,同一贮藏条件下,鲳鱼比大黄鱼更易产生酪胺,含量变化最明显。

固相萃取-液相色谱测定水中多环芳烃和邻苯二甲酸酯

在单独检测邻苯二甲酸酯类和多环芳烃的基础上,优化前处理方式,采用固相萃取膜对16种多环芳烃和5种邻苯二甲酸酯类化合物同时进行前处理萃取。串联二极管阵列检测器和荧光检测器,筛选色谱柱和流动相,优化梯度洗脱条件和荧光波长变化时间表,建立了固相萃取-液相色谱法同时测定生活饮用水中16种多环芳烃和5种邻苯二甲酸酯类化合物的方法。该方法根据相对保留时间定性,外标法定量。16种多环芳烃线性值为0~0.5 mg/L,5种邻苯二甲酸酯类化合物线性值为0~10.0 mg/L,标准曲线的相关系数(r)均大于0.99,平均回收率为70.4%~119.0%,相对标准偏差(RSD)<10%,21种目标物的检出限均小于相关标准限值。该方法节约检测成本的同时,简单高效且灵敏度高,各项指标都比较理想。

示差折光检测器高效液相色谱法测定中间馏分芳烃含量的不确定度分析

采用示差折光检测器高效液相色谱法测定中间馏分芳烃含量,使用不确定度评估方法来建立数学模型,对不确定性来源进行分析,计算各个不确定度分量的结果,然后评估合成标准不确定度和扩展不确定度。评定结果表明,标准溶液配制过程产生的不确定度分量最大,其中以质量称量过程中的不确定度最大,其次是定容和标准物质纯度引入的不确定度;标准曲线拟合引入的不确定度次之。此外,值得关注的还有数值修约和测量重复性引入的不确定度。取置信区间为95%,包含因子k=2,总多环芳烃质量分数测定结果为10.4%±1.1%,总芳烃质量分数测定结果为23.9%±2.7%。

超高效液相色谱快速分离26种致癌芳香胺

文章选择一种长度小、直径小以及粒径小的C18液相色谱柱,利用甲醇-水体系流动相进行分析,建立一种快速的高效液相色谱分离技术。这种新的超高效液相色谱分析方法能在15.000 min内分离26种芳香胺类化合物,在s/n为3的条件下,检测限为0.1~0.5 mg/kg。各芳香胺在0.5~10.0 mg/kg内都具有良好的线性关系(R2≥0.9990),相对标准偏差(RSD)小于1.500%。与标准提供的液相色谱分析致癌芳香胺的方法相比,其缩短了检测时间的同时,节约了溶剂用量,在日常纺织品检测工作过程中,既提高了工作效率,又节约了成本。

液相色谱法在泡菜生物胺含量检测中的应用研究

本研究通过优化样品前处理和色谱条件,建立了生物胺的标准曲线,结果表明,组胺、酪胺、腐胺、尸胺、色胺、β-苯乙胺、亚精胺和精胺等生物胺在0.10~2000 ng·mL-1的浓度范围内均表现出良好的线性关系,相关系数均在0.995以上。实验结果显示,平均加标回收率范围为76%~100%,相对标准偏差在1.5%~6.1%之间,表明该方法具有较高的准确性和精密度。综上所述,本研究所开发的HPLC法适用于泡菜中生物胺的快速、准确检测,为泡菜的安全性评估和品质控制提供了可靠的技术支持。

焦化废水多环芳烃微萃取及高效色谱分析方法

建立测定焦化废水中16种多环芳烃分散液相微萃取-高效液相色谱法。确定最佳色谱条件,对萃取剂、分散剂的种类及比例、萃取时间、加盐量、废水pH等条件进行优化。在最佳实验条件下,建立各组分的工作曲线,线性相关系数均达到0.999,线性范围0.1~10.0μg/L,检出限0.02~0.03μg/L,测定下限0.08~0.12μg/L,样品加标平均回收率96.3%~106%,相对标准偏差1.3%~2.9%。