| 摘要: |
| 应用广泛且具有毒性的有机磷酸酯(organophosphate esters,OPEs)类阻燃剂,通过水、气输送等多种途径进入海洋环境,可能会导致人类和海洋生物面临潜在的健康风险。因此,建立高效可靠的分析方法对于揭示OPEs在海洋环境中的赋存状况,评估其生态风险具有重要的科学意义。文章建立了同时测定沉积物中27种OPEs的超声提取、固相萃取(SPE)净化以及高效液相色谱-串联质谱(HPLC-MS/MS)检测的分析方法。结果表明:30mL乙酸乙酯(EA)和乙腈(ACN)混合溶剂(体积比为3︰7)的提取效果明显优于单独使用甲醇(MeOH)、二氯甲烷(DCM)、EA和ACN;用5mL EA经LC-C18固相萃取小柱洗脱两次回收率最好;以MeOH和含0.0025%甲酸的水溶液作为流动相时,质谱离子丰度最高。27种OPEs的线性范围为5~500 ng/g (R2>0.99),方法检出限(MDL)范围为0.004~1.250 ng/g,定量限(LOQ)为0.01~4.17 ng/g。三个加标水平(低、中、高)基质加标样品的平均回收率在45%~130%之间,相对标准偏差(RSD)最高11.0%,表明此方法可靠,精密度和灵敏度较高。采用优化的方法分析我国长江口、杭州湾入海口以及东海和黄海交界处海域表层沉积物中OPEs的含量,共检出了21种OPEs,浓度范围为9.83~48.70 ng/g,平均浓度为28.40 ng/g。该方法检测结果高效准确,可用于海洋沉积物中27种OPEs的同时测定。 |
| 关键词: 有机磷酸酯 高效液相色谱-串联质谱 超声萃取 固相萃取 沉积物 |
| DOI：10.11693/hyhz20220200030 |
| 分类号:O65 |
| 基金项目:国家自然基金项目,22076112号。 |
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| SIMULTANEOUS DETERMINATION OF 27 ORGANOPHOSPHATE ESTERS IN MARINE SEDIMENTS IN HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY-TANDEM MASS SPECTROMETRY |
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SHI Ren1, ZHANG Peng1, CAO Sheng-Kai1, XING Rong-Guang1, JI Hao1, GE Lin-Ke1, ZHANG Cui-Rong2
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1.School of Environmental Science and Technology, Shaanxi University of Science & Technology, Xi'an 710021, China;2.Xianyang Ecology and Environment Bureau, Xianyang 712099, China
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| Abstract: |
| Organophosphate esters (OPEs) are a group of widely used flame retardants and highly toxic to organisms. They enter marine environment via several paths, including water, air transportation etc., which would pose potential risks to human health and marine organisms. Therefore, establishment of an efficient and reliable analysis method is pivotal to reveal the contents of OPEs and assess their ecological risks in a marine environment. A method for simultaneous determination of 27 OPEs in marine sediments was established, and consists of ultrasonic extraction, solid phase extraction (SPE) purification, and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis. Results indicate that the extraction efficiency of 30 mL mixture solvents, composing by ethyl acetate (EA) and acetonitrile (ACN) (3︰7, V︰V) was obviously better than that those of methanol (MeOH), dichloromethane (DCM), EA, and ACN alone. An aliquot of 5 mL EA was used in eluting target compounds from LC-C18 cartridges twice were the optimized SPE method. The majority of ions abundance peaks were the highest with MeOH and 0.0025% formic acid solution used as the mobile phases. The linear range of 27 OPEs were 5~500 ng/g (R2>0.99). The method detection limits and the limits of quantification were 0.004~1.250 ng/g, and 0.01~4.17 ng/g, respectively. The mean recoveries of matrix spiked samples at three spiked levels (low, medium, and high) fall into the range of 45%~130%, and the maximum relative standard deviation was 11.0%. High precision and sensitivity attested to the method was valid and practical. The OPEs concentrations in surface sediments of the Changjiang (Yangtze) River estuary, the mouth of Hangzhou Bay, the junction of the Yellow Sea and East China Sea was analyzed by the optimized method. Twenty-one OPEs were detected, and the concentrations ranged 9.83~48.7 ng/g on average of 28.4 ng/g. The method was efficient and accurate, and can be used for the simultaneous determination of 27 OPEs in marine sediments. |
| Key words: organophosphate esters (OPEs) high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) ultrasonic extraction solid phase extraction sediment |
