Zervou Sevasti-Kiriaki, Hammoud Noura Alice, Godin Simon, Hiskia Anastasia, Szpunar Joanna, Lobinski Ryszard
Laboratory of Photo-Catalytic Processes and Environmental Chemistry, Institute of Nanoscience & Nanotechnology, National Center for Scientific Research "Demokritos", Patr. Gregoriou E & 27 Neapoleos Str, 15431 Agia Paraskevi, Athens, Greece.
Laboratory of Photo-Catalytic Processes and Environmental Chemistry, Institute of Nanoscience & Nanotechnology, National Center for Scientific Research "Demokritos", Patr. Gregoriou E & 27 Neapoleos Str, 15431 Agia Paraskevi, Athens, Greece; Université de Pau, CNRS, E2S UPPA, Institute of Analytical and Physical Chemistry for the Environment and Materials (IPREM-UMR 5254), 64000 Pau, France.
Sci Total Environ. 2023 Sep 20;892:164725. doi: 10.1016/j.scitotenv.2023.164725. Epub 2023 Jun 7.
Harmful algal blooms events have been reported worldwide and during the last decades are occurred with increasing frequency and intensity due to the climate change and the high inputs of nutrients in freshwaters from anthropogenic activities. During blooms cyanobacteria release in water their toxic secondary metabolites, known as cyanotoxins, along with other bioactive metabolites. Due to the negative impacts of these compounds on aquatic ecosystems and public health, there is an urgent need to detect and identify known and unknown cyanobacterial metabolites in surface waters. In the frame of the present study, a method based on liquid chromatography - high resolution mass spectrometry (LC-HRMS) was developed to investigate the presence of cyanometabolites in bloom samples from Lake Karaoun, Lebanon. Data analysis was performed using Compound Discoverer software with related tools and databases in combination to the CyanoMetDB mass list for detection, identification and structural elucidation of the cyanobacterial metabolites. In the course of this study, 92 cyanometabolites were annotated including 51 cyanotoxins belonging to microcystins, 15 microginins, 10 aeruginosins, 6 cyclamides, 5 anabaenopeptins, a cyanopeptolin, the dipeptides radiosumin B and dehydroradiosumin, the planktoncyclin and a mycosporine-like amino acid. Out of them, 7 new cyanobacterial metabolites, the chlorinated MC-ClYR, [epoxyAdda]MC-YR, MC-LI, aeruginosin 638, aeruginosin 588, microginin 755C and microginin 727 were discovered. Moreover, the presence of anthropogenic contaminants was recorded indicating the pollution of the lake and emphasizing the need for assessment of the co-occurrence of cyanotoxins, other cyanobacterial metabolites and other compounds hazardous to the environment. Overall, results prove the suitability of the proposed approach for the detection of cyanobacterial metabolites in environmental samples but also highlight the necessity of spectral libraries for these compounds, considering the absence of their reference standards.
有害藻华事件在全球范围内均有报道，在过去几十年中，由于气候变化以及人为活动导致淡水营养物质的大量输入，此类事件发生的频率和强度不断增加。在藻华中，蓝藻会向水中释放其有毒的次生代谢产物，即蓝藻毒素，以及其他生物活性代谢产物。由于这些化合物对水生生态系统和公众健康具有负面影响，因此迫切需要检测和识别地表水中已知和未知的蓝藻代谢产物。在本研究框架内，开发了一种基于液相色谱 - 高分辨率质谱（LC-HRMS）的方法，用于调查黎巴嫩卡拉oun湖藻华样本中蓝藻代谢产物的存在情况。使用Compound Discoverer软件结合相关工具和数据库以及CyanoMetDB质量列表进行数据分析，以检测、识别和阐明蓝藻代谢产物的结构。在本研究过程中，共注释了92种蓝藻代谢产物，其中包括51种属于微囊藻毒素的蓝藻毒素、15种微口毒素、10种铜绿肽、6种环肽、5种鱼腥藻肽、1种蓝肽、二肽放射菌素B和脱氢放射菌素、浮游环肽和1种类菌孢素氨基酸。其中，发现了7种新的蓝藻代谢产物，即氯化微囊藻毒素 - ClYR、[环氧Adda]微囊藻毒素 - YR、微囊藻毒素 - LI、铜绿肽638、铜绿肽588、微口毒素755C和微口毒素727。此外，还记录了人为污染物的存在情况，这表明该湖受到了污染，并强调需要评估蓝藻毒素、其他蓝藻代谢产物和其他对环境有害化合物的共存情况。总体而言，结果证明了所提出的方法适用于检测环境样本中的蓝藻代谢产物，但也突出了考虑到这些化合物缺乏参考标准，光谱库对于它们的必要性。
