Journal of Tropical Oceanography >
Dynamic analysis of particle-adsorbed oxylipins in typical coastal diatoms and their application in bloom monitoring*
Copy editor: LIN Qiang
Received date: 2024-10-12
Revised date: 2024-11-13
Online published: 2024-11-13
Supported by
Guangdong Basic and Applied Basic Research Foundation(2022B1515120030)
Guangdong Basic and Applied Basic Research Foundation(2022A1515010588)
Guangdong Basic and Applied Basic Research Foundation(2024A1515010938)
National Natural Science Foundation of China(42276162)
National Natural Science Foundation of China(42276130)
National Natural Science Foundation of China(41706181)
Diatom oxylipins, as key infochemicals, play a significant role in driving biological interactions during coastal diatom blooms and may influence biogeochemical cycles throughout the bloom's life cycle. Oxylipins exist in three forms in water, with particle-adsorbed oxylipins in the phycosphere reaching micromolar concentrations, making them particularly impactful in ecological contexts. In this study, we focused on polyunsaturated aldehydes (PUAs), a crucial class of oxylipins, and developed a method for rapidly quantifying particle-adsorbed PUAs during diatom growth. The method involves measuring diatom particle volumes through settling and centrifugation, and simulating the natural processes of settling and sedimentation. We observed that particle volumes varied between 12%~49%. To avoid the production of new PUAs, we optimized a derivatization process using 5% sulfuric acid-dissolved 2, 4-dinitrophenylhydrazine (DNPH), replacing the traditional neutral buffer. Using ultra-high-performance liquid chromatography (UHPLC) paired with multiple reaction monitoring (MRM) in tandem mass spectrometry, we were able to achieve rapid separation and accurate quantification of PUAs within just 5 minutes. This method was applied to monitor the growth stages of three typical red tide diatom strains in the laboratory, preliminarily exploring dynamic patterns in particle-adsorbed and related PUAs throughout the diatom growth process. Our results revealed that the particle-adsorbed PUAs concentrations in all three strains reached micromolar levels, ranging from 0.4~69 μmol·L-1. Notably, Skeletonema costatum exhibited similar trends between particle-adsorbed and particulate PUAs, with concentrations staying at a low level in the exponential phase before rising significantly during the stationary phase. In contrast, Thalassiosira rotula showed a decline in particle-adsorbed PUAs concentrations during the stationary phase compared to the exponential phase. Additionally, the composition of particle-adsorbed PUAs varied, with S. costatum being dominated by heptadienal in the exponential phase. This study provides important insights for the in situ monitoring application of diatom oxylipins during blooms and their potential ecological and biogeochemical impacts.
YANG Yang , WU Zhengchao , CHENG Yuanyue , WU Meilin , LI Qian . Dynamic analysis of particle-adsorbed oxylipins in typical coastal diatoms and their application in bloom monitoring*[J]. Journal of Tropical Oceanography, 2025 , 44(3) : 179 -187 . DOI: 10.11978/2024190
表1 苯甲醛(内标)、多不饱和醛及其衍生物在UHPLC-MS/MS负离子化模式下的MRM参数Tab. 1 MRM parameters of benzaldehyde (internal standard), PUAs and their derivatives under the negative ionization mode in UHPLC-MS/MS |
化合物 | 简写 | 醛类化学结构(衍生前) | 衍生物母离子 (一级质谱MS1) | 衍生物碎片离子对 (二级质谱MS2) | 锥孔电压/V | 碰撞能/V |
---|---|---|---|---|---|---|
苯甲醛(内标) | Ben | ![]() | 284.8 | 162.9 | 80 | 15 |
238.0 | 80 | 15 | ||||
庚二烯醛 | C7 | ![]() | 288.9 | 162.9 | 80 | 15 |
229.9 | 80 | 15 | ||||
241.9 | 80 | 15 | ||||
辛二烯醛 | C8 | ![]() | 302.8 | 162.9 | 80 | 15 |
229.9 | 80 | 15 | ||||
255.9 | 80 | 15 | ||||
葵二烯醛 | C10 | ![]() | 330.9 | 162.9 | 80 | 15 |
229.9 | 80 | 15 | ||||
284.9 | 80 | 15 |
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