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陆源腐殖质类色氨酸荧光峰作为一种新的潜在示踪剂,追踪典型污染流域中的抗生素。

Terrestrial humic-like fluorescence peak of chromophoric dissolved organic matter as a new potential indicator tracing the antibiotics in typical polluted watershed.

机构信息

School of Environment, Northeast Normal University, Changchun 130024, PR China.

Key Laboratory of Wetland Ecology and Environment, Northeast Institute of Geography and Agroecology, Chinese Academic Science, Changchun 130102, PR China.

出版信息

J Environ Manage. 2018 Dec 15;228:65-76. doi: 10.1016/j.jenvman.2018.09.013. Epub 2018 Sep 11.

Abstract

Natural surface waters are threatened globally by antibiotics pollution. In this study, we analyzed antibiotics and CDOM (Chromophoric dissolved organic matter) fluorescence in different water bodies using HPLC method and Excitation Emission Matrix- Parallel factor analysis, respectively. A combination of field studies in the Yinma River Watershed were conducted in rivers, reservoirs and urban rivers, and 65 CDOM and antibiotic samples were taken in April, May, July, and August 2016. EEM-PARAFAC analysis identified two components; a humic-like (C1) component and a tryptophan-like (C2) component. The redundancy analysis (RDA) demonstrated that CDOM could explain 38.2% (two axes) of the five antibiotics in reservoirs (N = 31), and 26.0% (two axes) of those in rivers and urban water (N = 30). Furthermore, the Pearson correlation coefficient between Sulfamethoxazole and C1 in reservoir water was 0.91 (t-test, 2-tailed, p < 0.01), and that between Sulfamethoxazole and C2 was 0.68 (t-test, 2-tailed, p < 0.01). This indicated that the humic-like component of CDOM PARAFAC fluorescence could detect Sulfamethoxazole contamination levels in the homogenized reservoir waters. Our results identified Sulfamethoxazole and Quinolones (Norfloxacin, 16.5 ng L; Enrofloxacin, 0.3 ng L; Ciprofloxacin, 30.9 ng L) at mean concentrations of 369.5 ng L and 15.9 ng L, respectively, which were the higher levels in natural surface waters. The FTIR spectroscopy of the mixture of humic acid and sulfamethoxazole showed that the absorbance at 3415 cm linked to OH stretching of OH groups and at 1386 cm because of OH bending and vibration of COOH groups became weaker, indicating that COOH groups of humic acid can adsorb and react with -NH of sulfamethoxazole. The CDOM PARAFAC components can be adapted for online or in situ fluorescence measurements as an early warning of Sulfamethoxazole distribution and contamination in similar aquatic environments.

摘要

天然地表水受到全球范围内抗生素污染的威胁。本研究采用高效液相色谱法和激发发射矩阵-平行因子分析(EEM-PARAFAC)分别分析了不同水体中的抗生素和 CDOM(色溶解有机质)荧光。对阴马河流域的河流、水库和城市河流进行了实地研究,于 2016 年 4 月、5 月、7 月和 8 月采集了 65 个 CDOM 和抗生素样本。EEM-PARAFAC 分析确定了两个组分;一个腐殖质样(C1)组分和一个色氨酸样(C2)组分。冗余分析(RDA)表明,CDOM 可以解释水库中 5 种抗生素的 38.2%(两个轴)(N=31),以及河流和城市水中的 26.0%(两个轴)(N=30)。此外,水库水中磺胺甲恶唑与 C1 的 Pearson 相关系数为 0.91(双侧 t 检验,p<0.01),磺胺甲恶唑与 C2 的 Pearson 相关系数为 0.68(双侧 t 检验,p<0.01)。这表明,CDOM PARAFAC 荧光的腐殖质样组分可以检测到均质水库水中磺胺甲恶唑的污染水平。我们的研究结果表明,磺胺甲恶唑和喹诺酮类(诺氟沙星,16.5ngL;恩诺沙星,0.3ngL;环丙沙星,30.9ngL)的浓度分别为 369.5ngL 和 15.9ngL,这是天然地表水中的较高水平。腐殖酸和磺胺甲恶唑混合物的傅里叶变换红外光谱(FTIR)表明,与 OH 基团伸缩相关的 3415cm-1处的吸光度和与 COOH 基团弯曲和振动相关的 1386cm-1处的吸光度变弱,表明腐殖酸的 COOH 基团可以吸附并与磺胺甲恶唑的-NH 反应。CDOM PARAFAC 组分可用于在线或原位荧光测量,作为磺胺甲恶唑在类似水生环境中分布和污染的早期预警。

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