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RESEARCH ARTICLE

Using fluorescence quenching combined with two-dimensional correlation fluorescence spectroscopy to characterise the binding-site heterogeneity of dissolved organic matter with copper and mercury in lake sediments

Xu-jing Guo A E , Yun-zhen Li B , Yan-hong Feng C and Dong-hai Yuan D
+ Author Affiliations
- Author Affiliations

A College of Resources and Environment, Chengdu University of Information Technology, No. 24 Block 1, Xuefu Road, Chengdu 610225, China. 

B Sichuan Academy of Environmental Sciences Sichuan, No. 18 Sec 4, Renmin South Road, Chengdu 610041, China.

C Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of China, 8 Jiangwangmiao Street, Nanjing 210042, China.

D Beijing Engineering Research Center of Sustainable Urban Water System Construction and Risk Control, Beijing University of Civil Engineering and Architecture, No. 1 Zhanlanguan Road, Xicheng District, Beijing 100044, China.

E Corresponding author. Email: gxj530520@126.com

Environmental Chemistry 14(2) 91-98 https://doi.org/10.1071/EN16135
Submitted: 28 July 2016  Accepted: 31 October 2016   Published: 21 November 2016

Environmental context. Dissolved organic matter (DOM) plays an important role in influencing the migration and ultimate fate of metals. Different sources of pollution resulted in changes in the structure of sediment DOM in Lake Wuliangsuhai. We investigate the binding properties of DOM with CuII and HgII using fluorescence quenching combined with two-dimensional correlation spectroscopy (2D-COS) in order to demonstrate the influence of different sources of DOM on metals.

Abstract. Dissolved organic matter (DOM) was collected from three sampling sites (L1, L2 and L3) in Lake Wuliangsuhai. L1 received upstream industrial wastewater and domestic sewage. L2 had suffered from agricultural non-point source pollution. L3 was situated in the lake outlet area. The complexation of DOM with CuII and HgII was investigated based on fluorescence quenching of the synchronous fluorescence spectra on the addition of CuII and on two-dimensional correlation spectroscopy (2D-COS). The synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of CuII and HgII binding sites, which was not readily detected using only the synchronous fluorescence spectra. CuII and HgII complexation was stronger at shorter wavelengths than at longer wavelengths. Moreover, fluorescence quenching also occurred intensely in the fulvic-like regions (363 nm for DOM-Cu in L2 and 365 nm for DOM-Hg in L1). The logarithms of the stability constants (log KM) ranged from 4.42 to 6.23, from 4.75 to 4.86, and from 4.80 to 5.73 for DOM-Cu in L1, L2 and L3, respectively, depending on the wavelength. DOM at the longer wavelengths exhibited a higher log KM than that at the shorter wavelengths, and the f values in the protein-like region were clearly high. These results suggest that the influence of the structural and chemical properties of DOM on CuII binding may differ for DOM from different sources. The combined approach of fluorescence quenching and 2D-COS could be applied as a tool for evaluating the metal binding site heterogeneity of DOM.


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