摘要
以国际腐殖质协会腐殖酸和实验室提纯腐殖酸为研究对象,发现被H2还原前后腐殖酸的三维荧光光谱明显不同,但有共同的变化趋势:还原态腐殖酸的三维荧光光谱图的波峰荧光强度均明显低于还原前,说明腐殖酸还原过程有类似π-π*化学键断开的结构变化.对苯醌是腐殖酸氧化还原醌基官能团的代表化合物,将其还原前后与腐殖酸还原前后的荧光光谱对比,发现两组变化趋势一致,这一发现是利用荧光特性量化腐殖质氧化还原官能团的基础.利用铁氰化钾测定腐殖酸的得失电子能力,发现不同土壤提纯的腐殖酸得失电子能力有一定差别:鹰潭土壤腐殖酸和桃源土壤腐殖酸在原态下对三价铁的还原能力都较弱,分别为0.998和0.465 meq.g-1C(原态转移电子数);但还原后得电子数(还原态转移电子数减原态转移电子数)分别为3.384 meq.g-1C(鹰潭土壤腐殖酸)和1.187 meq.g-1C(桃源土壤腐殖酸).鹰潭土壤腐殖酸具有较高的得电子数,与其具有较高荧光峰值这一结果互相支持.结合得失电子能力测定,利用光学分析方法,量化官能团,预测氧化还原反应进程,使三维荧光光谱法测定土壤有机质的氧化还原性在实际应用中具有广阔的前景.
Humic substances serve as electron shuttles in the soil environment. They not only stimulate the element migration, but also accelerate containment degradation and environment remediation. In this study, a standard humic acid and two extracted humic acids from soil samples were reduced by H2, and three-dimensional excitation emission matrix fluorescence spectroscopy （3DEEM） was employed to characterize these humic acids. The results of 3DEEMs revealed the differences between native and reduced humic acids. Fluorescence peak intensity of humic acids in the reduced state was lower than those in the natural state, which can be explained by the changes of chemical structures of humic acids, such as the loss of π-π bonds. As a model compound of quinone groups in humic acids, benzoquinone reduction and 3DEEM analysis were carried out under the same conditions. It was observed that there was a decrease of fluorescence with benzoquinone reduction. Potassium ferricyanide method was used to measure the reducing capacity of native extracted humic acids, which was found to be 0. 998 and 0. 465 meq. g-1 C for Yingtan and Taoyuan soils, respectively. Electron accepting capacities of humic acids were 3. 384 and 1.187 meq-g 1 C for Yingtan and Taoyuan soils, respectively. Determination of electron accepting capacities, quantification of redox-active functional groups and prediction of redox reaction processes in soil are all important applications of 3 DEEM in the investigation of humic acid redox-activities.
出处
《环境化学》
CAS
CSCD
北大核心
2012年第12期2002-2007,共6页
Environmental Chemistry
基金
北京林业大学青年科技启动基金(BLX2011022)
国家自然科学基金(41090284)资助
