Schweizer Sina, Halder Kristin, Schäfer Annika, Hauns Jakob, Marsili Letizia, Mazzariol Sandro, Fossi Maria Cristina, Muñoz-Arnanz Juan, Jiménez Begoña, Vetter Walter
Institute of Food Chemistry, Department of Food Chemistry (170b), University of Hohenheim, 70599 Stuttgart, Germany.
European Union Reference Laboratory (EURL) for Halogenated POPs in Feed and Food, 79114 Freiburg, Germany.
Environ Health (Wash). 2024 Feb 19;2(4):233-242. doi: 10.1021/envhealth.3c00182. eCollection 2024 Apr 19.
Halogenated natural products (HNPs) are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known. Therefore, several persistent and bioaccumulative HNP groups, together with man-made polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), were quantified in the blubber of nine sperm whales () stranded on the coast of the Mediterranean Sea in Italy. The naturally occurring polybrominated hexahydroxanthene derivatives (PBHDs; sum of TetraBHD and TriBHD) were the most prominent substance class with up to 77,000 ng/g blubber. The mean PBHD content (35,800 ng/g blubber) even exceeded the one of PCBs (28,400 ng/g blubber), although the region is known to be highly contaminated with man-made contaminants. Based on mean values, Q1 ∼ PBDEs > MeO-BDEs ∼ 2,2'-diMeO-BB 80 and several other HNPs followed with decreasing amounts. All blubber samples contained an abundant compound whose molecular formula (CHBrO) was verified using high-resolution mass spectrometry. The only plausible matching isomer was (2,4',9,9')-2,7-dibromo-4'-bromomethyl-1,1-dimethyl-2,3,4,4',9,9'-9,9'-hexahydro-1-xanthen-9-ol (OH-TriBHD), a hydroxylated secondary metabolite previously detected together with TriBHD and TetraBHD in a sponge known to be a natural producer of PBHDs. The estimated mean amount of the presumed OH-TriBHD was 3000 ng/g blubber, which is unexpectedly high for hydroxylated compounds in the lipids of marine mammals.
卤化天然产物（HNPs）被认为是新出现的污染物，其在环境中的分布和归宿尚不完全清楚。因此，对搁浅在意大利地中海沿岸的9头抹香鲸的鲸脂中几种持久性和生物累积性HNP组，以及人造多氯联苯（PCBs）和多溴二苯醚（PBDEs）进行了定量分析。天然存在的多溴化六氢氧杂蒽衍生物（PBHDs；四溴化六氢氧杂蒽和三溴化六氢氧杂蒽的总和）是最主要的物质类别，鲸脂中含量高达77,000 ng/g。尽管已知该地区受到人造污染物的高度污染，但PBHD的平均含量（35,800 ng/g鲸脂）甚至超过了多氯联苯（28,400 ng/g鲸脂）。基于平均值，Q1 ∼ 多溴二苯醚 > 甲氧基多溴二苯醚 ∼ 2,2'-二甲基氧基联苯 80，其他几种卤化天然产物含量依次递减。所有鲸脂样品都含有一种丰富的化合物，其分子式（CHBrO）通过高分辨率质谱法得到验证。唯一合理的匹配异构体是（2,4',9,9'）-2,7-二溴-4'-溴甲基-1,1-二甲基-2,3,4,4',9,9'-9,9'-六氢-1-氧杂蒽-9-醇（OH-三溴化六氢氧杂蒽），这是一种羟基化次生代谢产物，之前在一种已知为PBHD天然生产者的海绵中与三溴化六氢氧杂蒽和四溴化六氢氧杂蒽一起被检测到。假定的OH-三溴化六氢氧杂蒽的估计平均含量为3000 ng/g鲸脂，这对于海洋哺乳动物脂质中的羟基化化合物来说出乎意料地高。
