近年来,波罗的海生物群中受管制的持久性有机污染物(POP)浓度的下降速度趋于平稳,新的污染物经常被发现。有,因此,需要全面的方法来研究各种环境污染物的发生和时间趋势,包括传统的持久性有机污染物,新兴关注污染物(CEC),和新的污染物。在目前的工作中,非目标筛选(NTS)工作流程被开发和使用,据我们所知,首次使用气相色谱-高分辨率质谱(GC-HRMS)对生物群进行NTS。为了最大限度地提高污染物覆盖率,使用了电子电离(EI)和电子捕获负离子化学电离(ECNI)。EI数据使用高度自动化的工作流程进行处理,优先考虑,并初步确定具有统计上显著的时间趋势的污染物。在时间趋势分析之前,对ECNI数据进行了手动处理和审查。总之,超过300种初步确定的污染物被发现在波罗的海海利摩样本中具有显著的时间趋势,港口海豚,或者白尾海鹰。发现许多受管制化学品显著减少,正如可以预料的那样,如PCB,多氯三联苯,氯苯,Toxaphenes,滴滴涕,其他有机氯农药,以及三溴二苯醚和四溴二苯醚(BDE)。遗留持久性有机污染物的下降速度与有针对性的分析报告的数据非常吻合。观察到小多环芳烃的显着增加,七溴二苯醚,CECs,以及萜烯和相关化合物。CEC包括,其中,一种增塑剂乙酰柠檬酸三丁酯(ATBC),两种抗氧化剂2,6-双(1,1-二甲基乙基)苯酚和2,6-双(叔丁基)-4-(4-吗啉基甲基)苯酚,和两种用于聚合物生产的化合物,三甲基异氰脲酸酯和2-巯基苯并噻唑,以前从未在生物群中报道过。它们在生物群中的浓度增加表明使用和释放增加。ATBC的增加可能与它作为邻苯二甲酸二-2-乙基己酯(DEHP)替代品的使用增加有关,在过去的十年中已经被淘汰。
The rate of decline in regulated persistent organic pollutant (POP) concentrations in Baltic Sea biota has leveled off in recent years, with new contaminants frequently being discovered. There is, therefore, a need for comprehensive approaches to
study occurrence and temporal trends of a wide range of environmental contaminants, including legacy POPs, contaminants of emerging concern (CECs), and new contaminants. In the current work, non-target screening (NTS) workflows were developed and used for, to the best of our knowledge, the first time-trend directed NTS of biota using gas chromatography-high-resolution mass spectrometry (GC-HRMS). To maximize contaminant coverage, both electron ionization (EI) and electron capture negative ion chemical ionization (ECNI) were used. The EI data were treated using highly automated workflows to find, prioritize, and tentatively identify contaminants with statistically significant temporal trends. The ECNI data were manually processed and reviewed prior to time-trend analysis. Altogether, more than 300 tentatively identified contaminants were found to have significant temporal trends in samples of Baltic guillemot, harbor porpoise, or white-tailed sea eagle. Significant decreases were found for many regulated chemicals, as could be expected, such as PCBs, polychlorinated terphenyls, chlorobenzenes, toxaphenes, DDT, other organochlorine pesticides, and tri- and tetra- bromodiphenyl ethers (BDEs). The rate of decline of legacy POPs agreed well with data reported from targeted analyses. Significant increases were observed for small polycyclic aromatic hydrocarbons, heptaBDEs, CECs, and terpenes and related compounds. The CECs included, among others, one plasticizer tributyl acetylcitrate (ATBC), two antioxidants 2,6-bis(1,1-dimethylethyl)phenol and 2,6-bis(tert-butyl)-4-(4-morpholinyl-methyl)phenol, and two compounds used in polymer production, trimethyl isocyanurate and 2-mercaptobenzothiazole, which had not previously been reported in biota. Their increased concentrations in biota indicate increased use and release. The increase in ATBC may be linked to increased use of it as a substitute for di-2-ethylhexyl phthalate (DEHP), which has been phased out over the last decade.