CHEMOSPHERE
·
2024
·
IF 8.1
Bin Li,Jianghong Shi,Xueling Xiang,Mengtao Zhang,Hui Ge,Shuhan Sun
Bromophenols has been proven to synthesize hydroxylated polybrominated diphenyl ethers (OH-PBDEs), which may pose additional environmental and health risks in the process of bioremediation. In this study, the removal of 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP) and the biosynthetic of OH-PBDEs by Prorocentrum donghaiense were explored. The removal efficiencies of 2,4-DBP and 2,4,6-TBP ranged from 32.71% to 76.89% and 31.15%–78.12%, respectively. Low concentrations of 2,4-DBP stimulated algal growth , while high concentrations were inhibitory. Furthermore, exposure to 10.00 mg L −1 2,4-DBP resulted in the detection of 2′-hydroxy-2,3′,4,5′-tetrabromodiphenyl ether (2′–OH–BDE-68) within P . donghaiense . In contrast, increasing concentrations of 2,4,6-TBP considerably inhibited P . donghaiense growth, with 4′-hydroxy-2,3′,4,5′,6-pentabromodiphenyl ether (4′–OH–BDE-121) detected within P. donghaiense under 5.00 mg L −1 2,4,6-TBP. Metabolomic analysis further revealed that the synthesized OH-PBDEs exhibited higher toxicity than their precursors and identified the oxidative coupling as a key biosynthetic mechanism. These findings confirm the capacity of P. donghaiense to remove bromophenols and biosynthesize OH-PBDEs from bromophenols, offering valuable insights into formulating algal bioremediation to mitigate bromophenol contamination.
研究领域:
环境科学
·
海洋生物学
·
毒理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICAL CHEMISTRY
·
2026
·
IF 7.3
Bairong Fu,Dongqin Tan,Jing Jin,Lei Tong,Longxing Wang,Yihou Peng,Ningbo Geng,Lidong Wu,Huilian Ma,Yuwen Ni,Jiping Chen
The fragmentation behavior of isomeric hydroxylated polybrominated diphenyl ethers (OH-PBDEs) remains poorly elucidated, although LC-MS/MS is essential for their analysis. This study systematically characterizes their fragmentation behavior by LC-ESI-MS2, elucidating relationships between product ions, structural features, and instrument detection limits. Results demonstrated congener-specific variability in the signal intensity of [M–H]−, particularly among isomers. Fragmentation behavior is highly dependent on the hydroxyl location on the diphenyl ether scaffold, as well as the bromine substituent pattern. Three distinct mechanisms are identified: (1) Br abstraction via free radical-mediated rearrangement cleavage in meta-hydroxylated PBDEs, (2) preferential formation of the [Br]− ion via γ-elimination in ortho-hydroxylated PBDEs, and (3) characteristic formation of bromobenzoquinone anions via multistep fragmentation mechanisms in para-hydroxylated PBDEs. Furthermore, the ortho-effect, particularly pronounced in 2′–OH substituted congeners, significantly alters the fragmentation pathways. While the elucidated fragmentation pathways provided structural insights, the inherent weak signals challenged detection. A sensitivity-enhancing precolumn derivatization protocol with dansulfonyl chloride was introduced to solve the problem. The MS2 fragmentation of these derivatives was conveniently dominated by the cleavage of the C–S bond within the dansyl group, yielding abundant diagnostic ions that greatly aided in structural confirmation. As predicted, the derivatization strategy achieved a remarkable up to 15-fold improvement in the sensitivity. This investigation advances the understanding of OH-PBDE fragmentation, establishes an identification framework using specific patterns and diagnostic ions, and demonstrates a practical derivatization approach for enhanced sensitivity, elucidating structure-fragmentation relationships in brominated aromatics and providing methodological guidance for future analysis.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
WATER RESEARCH
·
2024
·
IF 11.4
Jie Chen,Peizeng Yang,Jing Chen,Bin Gao,Junhe Lu
This study investigated the expediated transformation of halophenols in the presence of nitrite (NO 2 − ) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO 2 − and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO 2 − underwent protonation to generate reactive nitrous acid (HNO 2 ) and nitrosonium ions (NO + ) that facilitate the nitration and oxidation of halophenols. When 10 μМ halophenol was treated by freezing in the presence of 5 μМ NO 2 − , the total yields of nitrated products reached 2.4 μМ and 1.4 μМ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO + drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.
研究领域:
环境化学
·
低温环境化学
·
水处理
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）