Centre for Agroecology, Water and Resilience (CAWR), Coventry University, Wolston Lane, Ryton-on-Dunsmore, CV8 3LG, UK.
School of Engineering, Deakin University, 75 Pigdons Road, Waurn Ponds, VIC 3220, Australia.
Anal Methods. 2024 Mar 14;16(11):1579-1592. doi: 10.1039/d3ay02197a.
Phthalates or phthalic acid esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) are ubiquitous chemicals often used as plasticisers and additives in many industrial products and are classified as both persistent organic pollutants (POPs) and new emerging pollutants (NEPs). Exposure to these chemicals, especially through inhalation, is linked to a wide range of negative health effects, including endocrine disruption. Air particulate matter (PM) with an aerodynamic diameter ≤ 2.5 μm can be enriched with PAEs and DEHA and if inhaled can cause multi-system human toxicity. Therefore, proper monitoring of PAEs and DEHA in PM is required to assess human exposure to these pollutants. In this work, we developed and validated a new and sensitive gas-chromatography high-resolution mass spectrometry (GC-HRMS) method for targeted analysis of PAEs including dimethyl phthalate (DMP), diethyl phthalate (DEP), di--butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl)adipate (DEHA), bis(2-ethylhexyl)phthalate (DEHP), di--octyl phthalate (DOP), in PM. Analytical aspects including sample preparation steps and GC-HRMS parameters, , quadrupole isolation window, to enhance method sensitivity have been assessed. The estimated limit of detection (LODs) of target PAEs and DEHA ranged from 5.5 to 17 pg μL, allowing their trace-level detection in PM. Extraction efficiencies of 78-101% were obtained for the target compounds. Low DMP and DEP extraction efficiencies from the spiked filter substrates indicated that significant losses of higher volatility PAEs can occur during the sample collection when filter-based techniques are used. This work is the first targeted method based on GC-Orbitrap MS for PAEs and DEHA in environmental samples. The validated method was successfully applied for the targeted analysis of PAEs and DEHA in PM samples from the eighth most populous city in Brazil, Curitiba. This work is the first to report DBP, DEHA, DEHP, and DOP in urban PM from Brazil. The observed concentrations of PAEs (up to 29 ng m) in PM from Curitiba may not represent the extent of pollution by these toxic compounds since the analysed samples were collected during a COVID-19 restriction when anthropogenic activities were reduced.
酞酸酯或邻苯二甲酸酯（PAE）和己二酸二（2-乙基己基）酯（DEHA）是无处不在的化学物质，通常用作许多工业产品的增塑剂和添加剂，被归类为持久性有机污染物（POPs）和新出现的污染物（NEPs）。这些化学物质的暴露，特别是通过吸入，与广泛的负面健康影响有关，包括内分泌干扰。空气颗粒物（PM），空气动力学直径≤2.5μm，可富集 PAE 和 DEHA，如果被吸入，可引起多系统人体毒性。因此，需要对 PM 中的 PAE 和 DEHA 进行适当监测，以评估人体对这些污染物的暴露情况。在这项工作中，我们开发并验证了一种新的、灵敏的气相色谱-高分辨率质谱（GC-HRMS）方法，用于靶向分析包括邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸苄丁酯（BBP）、己二酸二（2-乙基己基）酯（DEHA）、邻苯二甲酸二（2-乙基己基）酯（DEHP）、邻苯二甲酸二辛酯（DOP）在内的 PAE。评估了包括样品制备步骤和 GC-HRMS 参数在内的分析方面，例如四极杆隔离窗口，以提高方法的灵敏度。目标 PAE 和 DEHA 的估计检出限（LOD）范围为 5.5 至 17pgμL，允许对 PM 中的痕量进行检测。目标化合物的提取效率为 78-101%。从加标滤膜基质中提取的 DMP 和 DEP 提取效率较低表明，当使用基于滤膜的技术进行采样时，较高挥发性 PAE 可能会在采样过程中大量损失。这项工作是第一个基于 GC-Orbitrap MS 的环境样品中 PAE 和 DEHA 的靶向方法。该方法已成功应用于巴西第八大人口城市库里蒂巴的 PM 样品中 PAE 和 DEHA 的靶向分析。这是首次在巴西城市 PM 中报告 DBP、DEHA、DEHP 和 DOP。库里蒂巴 PM 中观察到的 PAE 浓度（高达 29ngm）可能不能代表这些有毒化合物的污染程度，因为分析的样本是在 COVID-19 限制期间采集的，当时人为活动减少。
