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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng    2012, Vol. 6 Issue (6) : 784-796     https://doi.org/10.1007/s11783-012-0436-5
RESEARCH ARTICLE |
Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions
Shuang XUE1,2, Qingliang ZHAO3, Liangliang WEI3, Xiujuan HUI1,2(), Xiping MA1,2, Yingzi LIN4
1. School of Environmental Science, Liaoning University, Shenyang 110036, China; 2. Key Laboratory of Water Environment Biomonitoring and Ecological Security Liaoning Province, Shenyang 110036, China; 3. School of Municipal & Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China; 4. Key Laboratory of Songliao Aquatic Environment, Ministry of Education, Jilin Architectural and Civil Engineering Institute, Changchun 130118, China
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Abstract

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ0.5 value for HPO–A, increased λ0.5 values for HPO–N, TPI–A and HPI, and a consistent λ0.5 value for TPI–N.

Keywords granular activated carbon adsorption      dissolved organic matter      fractionation      fluorescence     
Corresponding Authors: HUI Xiujuan,Email:shuangxue_777@163.com   
Issue Date: 01 December 2012
 Cite this article:   
Shuang XUE,Qingliang ZHAO,Liangliang WEI, et al. Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions[J]. Front Envir Sci Eng, 2012, 6(6): 784-796.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-012-0436-5
http://journal.hep.com.cn/fese/EN/Y2012/V6/I6/784
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Shuang XUE
Qingliang ZHAO
Liangliang WEI
Xiujuan HUI
Xiping MA
Yingzi LIN
parametersvalueparametervalue
pH8.1Br-(μg·L-1)<20 a)
TOC (mg·L-1)17.3Ammonia (mg N·L-1)5.3
DOC (mg·L-1)13.7Nitrate (mg N·L-1)13.9
UV–254 (m-1)18.7Alkalinity (mg CaCO3·L-1)105.8
Tab.1  Characteristics of the NWTP secondary effluent
Fig.1  XAD fractionation of DOM before and after GACA. The two pie diagrams indicate the distributions of five DOM fractions in the water samples
Fig.2  EEM spectra of DOM fractions before and after GACA
DOM fractionΦI+ II, n ( × 10-7)/(AU·nm2·mg·L-1)ΦIII, n ( × 10-7)/(AU·nm2·mg·L-1)ΦIV, n ( × 10-7)/(AU·nm2·mg·L-1)ΦV, n ( × 10-7)/((AU·nm2·mg·L-1)ΦT, n ( × 10-7)/(AU·nm2·mg·L-1)PI+ II, n/%PIII, n/%PIV, n/%PV, n/%
before GACA
HPO–A20.040.417.521.299.120411821
HPO–N10.318.87.77.544.323421717
TPI–A13.735.113.619.682.017431724
TPI–N20.424.712.69.767.330371914
HPI2.212.16.47.728.48432327
after GACA
HPO–A16.138.113.820.788.718431623
HPO–N17.719.711.26.955.432362012
TPI–A13.116.810.18.048.027352117
TPI–N24.529.917.714.186.228352116
HPI1.97.94.44.919.110412325
Tab.2  , and values for DOM fractions before and after GACA
Fig.3  Total (a), total (b), total (c), total (d) and total (e) value for DOM fractions before and after GACA
HPO–A, HPO–N, TPI–A, TPI–N and HPI accounted for 37%, 10%, 20%, 19% and 14% of fluorescence in the NWTP secondary effluent (Fig. 4). With the high value, HPO–A, TPI–A and TPI–N contributed more to fluorescence than they contributed to DOC, and this was contrary to HPO–N and HPI. The contribution of HPO–A, TPI–A and HPI to fluorescence decreased after GACA, due to preferential removal of fluorescent materials in these three fractions during GACA. In contrast, the contribution of HPO–N and TPI–N increased. As a result, TPI–N became the major contributor and was responsible for 33% of the fluorescence after GACA. HPO–A ranked second, constituting 30% of the fluorescence after GACA. HPO–N, TPI–A and HPI were relatively unimportant, corresponding to 13%, 13% and 11% of the fluorescence after GACA.
Fig.4  Contributions DOM fractions to fluorescence before and after GACA
Fig.5  synchronous spectra of DOM fractions with ? = 18 nm (a) and with ? = 66 nm (b) before and after GACA
Fig.6  Fluorescence emission spectra of DOM fractions at = 370 nm before and after GACA
Fig.7  in the normalized fluorescence emission spectra of DOM fractions before and after GACA
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