差分吸收光谱-高斯拟合法研究富里酸质子化

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摘要利用紫外-可见吸收光谱差分法结合高斯多峰拟合法研究了土壤富里酸在水溶液中的质子化特性.在pH 3.0~11.0范围内，富里酸差分吸收光谱在235，320，280，360nm处出现特征波峰，并拟合得到6类高斯峰（R²>0.983）：A0（211.19nm）、A1[（238.62±1.13）nm]、A2[（274.78±1.50）nm]，A3[（308.31±3.74）nm]，A4[（353.72±3.67）nm]，A5[（419.44±1.64）nm]和A6[（389.82±2.57）nm].高斯峰A1~A6位置和宽度变化程度分别为3.18~10.50nm（σ=1.13~3.74nm）和3.36~19.08nm（σ=1.33~9.54nm）.高斯峰A1、A2、A5和A6位置受pH值影响的变化程度（3.18~5.50nm）小于高斯峰A3和A4位置变化程度（10.50~10.13nm）；高斯峰A1和A2宽度受pH值影响的变化程度（3.36~8.49nm）小于高斯峰A3~A6宽度变化程度（10.86~19.08nm）.高斯峰A1~A3分别与酚羟基、羧基和酚羟基发色团有关；高斯峰A4~A6与分子构型构象的变化有关，受分子电荷转移和发色团相互作用的影响.差分吸收光谱的特征波峰的差分吸光度△A（235）、△A（280）、△A（320）和△A（360）与pH值均存在显著性正相关关系（R²=0.855~0.995）.ln△A（360）可用来反映高斯峰A4随pH值的变化情况（R²=0.938）.结果表明，差分吸收光谱法可用于研究水体中痕量富里酸质子化特性，为探究溶解性有机质与环境污染物之间的结合机理提供依据.

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	宋凡浩
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	喻文强
	雷啟焘
	白英臣

关键词 ：富里酸, 质子化, 差分吸收光谱, 高斯峰

Abstract：The protonation properties of soil fulvic acid in aquatic systems were investigated using multi-peaks Gaussian fitting method based on UV-Vis differential absorption spectra. At the pH range of 3.0~11.0, the characteristic peaks were located at 235nm, 320nm, 280nm and 360nm in differential absorption spectra of SFA. Six Gaussian peaks were fitted from the differential absorption spectra of SFA (R²>0.983):A0 (211.19nm), A1[(238.62±1.13) nm], A2[(274.78±1.50) nm], A3[(308.31±3.74) nm], A4[(353.72±3.67) nm], A5[(419.44±1.64) nm] and A6[(389.82±2.57) nm]. The changes of the locations and widths of the Gaussian peaks A1~A6 ranged 3.18~10.50nm (σ=1.13~3.74nm) and 3.36~19.08nm (σ=1.33~9.54nm), respectively. The location changes of Gaussian peaks A1, A2, A5 and A6 (3.18~5.50nm), which were induced by the changes of pH, were less than that of Gaussian peaks A3 and A4 (10.50~10.13nm). Moreover, the width changes of Gaussian peaks A1and A2 (3.36~8.49nm), which were induced by the changes of pH, were less than that of Gaussian peaks A3~A6 (10.86~19.08nm). Gaussian peaks A1~A3were related to phenolic, carboxyl and phenolic chromophores, respectively. Gaussian peaks A4~A6 were associated with the changes in molecular conformation and affected by molecular charge transfer and internal reactions between chromophores. The differential absorbance of characteristic peaks, △A(235), △A(280), △A(320) and △A(360), in differential absorption spectra had significantly positive relationship with pH (R²=0.855~0.995). The ln△A(360) in the study could be used to reflect the changes in Gaussian peak A4 with the changes of pH (R²=0.938). The results showed that differential absorption spectroscopy could be applied to investigate the protonation properties of trace fulvic acid in aquatic systems, which provided basis for exploring of the interaction mechanisms between dissolved organic matters and environmental contaminants.

Key words： fulvic acid protonation differential absorption spectra Gaussian peak

收稿日期: 2017-05-29

X703.1

基金资助:国家自然科学基金资助项目（41521003，41630645，41173084，41573130）；北京市自然科学基金资助项目（8162044）

通讯作者: 白英臣,研究员,baiyc@craes.org.cn E-mail: baiyc@craes.org.cn

作者简介: 宋凡浩(1991-),男,山东济南人,中国环境科学研究院硕士研究生,主要从事污染物环境行为及风险评估的研究.发表文章6篇.

引用本文:

宋凡浩, 吴丰昌, 冯伟莹, 王国静, 陈曲, 喻文强, 雷啟焘, 白英臣. 差分吸收光谱-高斯拟合法研究富里酸质子化[J]. 中国环境科学, 2017, 37(12): 4571-4577. SONG Fan-hao, WU Feng-chang, FENG Wei-ying, WANG Guo-jing, CHEN Qu, YU Wen-qiang, LEI Qi-tao, BAI Ying-chen. Study on protonation of fulvic acid using differential absorption spectroscopy coupled with Gaussian fitting method. CHINA ENVIRONMENTAL SCIENCECE, 2017, 37(12): 4571-4577.

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