Dept. of Environmental Chemistry, IDAEA-CSIC, C/Jordi Girona 18-26, 08034, Barcelona, Spain.
Dept. of Environmental Chemistry, IDAEA-CSIC, C/Jordi Girona 18-26, 08034, Barcelona, Spain.
J Chromatogr A. 2018 Apr 6;1544:33-40. doi: 10.1016/j.chroma.2018.02.027. Epub 2018 Feb 21.
Insect repellents (IRs) are a group of organic chemicals whose function is to prevent the ability of insects of landing in a surface. These compounds have been found in the environment and may pose a risk to non-target organisms. In this study, an on-line solid phase extraction - high performance liquid chromatography-tandem mass spectrometry multiresidue method was developed using an atmospheric photoionization source (SPE-HPLC-(APPI)-MS/MS). The use of the APPI as an alternative ionization technique to electrospray (ESI) and atmospheric pressure chemical ionization (APCI) allowed expanding the range of analytical techniques suitable for the analysis of IRs, so far relied in gas chromatography. High sensitivity and precision was reached with method limits of quantification between 0.2 and 4.6 ng l and interday and intraday precision equal or below 15%. The validated method was applied to the study of surface water samples from three European river basins with different flow regime (Adige River in Italy, Sava River in the Balkans, and Evrotas River in Greece). The results showed that two IRs (DEET and Bayrepel) were ubiquitous in the Sava and Evrotas basins, reaching concentrations as high as 105 μg l of Bayrepel in the Sava River, and 5 μg l of DEET in the Evrotas River. Densely populated areas and effluent waste waters are pointed out as the responsible for this pollution. In the alpine river Adige, only three samples showed low levels of IRs (6.01-37.8 ng l). The concentrations measured were used to perform an environmental risk assessment based on the hazard quotients (HQs) estimation approach by using the chronic and acute eco-toxicity data available. The results revealed that despite the high frequency and eventually high concentrations of these IRs determined in the three basins, only few sites were at risk, with 1 < HQs < 3.3.
驱虫剂（IRs）是一组有机化合物，其功能是防止昆虫在表面着陆的能力。这些化合物已在环境中发现，可能对非目标生物构成风险。在这项研究中，使用大气压光解源（SPE-HPLC-（APPI）-MS/MS）开发了一种在线固相萃取-高效液相色谱-串联质谱多残留方法。使用 APPI 作为替代电喷雾（ESI）和大气压化学电离（APCI）的电离技术，扩展了适用于 IRs 分析的分析技术范围，迄今为止，这些技术一直依赖于气相色谱。该方法达到了 0.2 至 4.6 ng l 之间的方法检出限，日内和日间精密度均在 15%以下，具有高灵敏度和精度。验证后的方法应用于三个具有不同流态的欧洲河流流域（意大利的阿迪杰河、巴尔干的萨瓦河和希腊的埃夫罗塔斯河）的地表水样品研究。结果表明，两种 IRs（DEET 和 Bayrepel）在萨瓦河和埃夫罗塔斯河流域普遍存在，Bayrepel 的浓度高达萨瓦河 105 μg l，埃夫罗塔斯河 5 μg l 的 DEET。人口稠密地区和废水排放是造成这种污染的原因。在高山河流阿迪杰河，只有三个样品显示出低水平的 IRs（6.01-37.8 ng l）。使用现有慢性和急性生态毒性数据，根据危害系数（HQs）估算方法进行环境风险评估，使用所测浓度。结果表明，尽管在这三个流域中确定了这些 IRs 的高频率和最终高浓度，但只有少数几个地点存在风险，1 < HQs < 3.3。
