农药废水生物处理过程中溶解性有机物特性及荧光强度与COD的关系

doi:10.11934/j.issn.1673-4831.2017.09.009

摘要/Abstract

摘要：

采用三维荧光光谱技术对有机农药废水处理过程中溶解性有机物（DOM）的荧光光谱特性进行分析，并建立DOM荧光强度和COD的相关关系。三维荧光光谱分析表明，废水中DOM主要有可见光区富里酸（峰A）、紫外光区富里酸（峰B）和高激发波长色氨酸（峰C）3种物质。可见光区富里酸和紫外光区富里酸经气浮池、水解酸化池和厌氧流化床处理后，转化为更易被微生物降解的高激发波长色氨酸。经过接触氧化池处理后，3种DOM的荧光强度均因微生物降解而逐渐降低，其中高激发波长色氨酸比富里酸易降解。荧光指数（I_F）、生物源指数（X_BI）、紫外光区富里酸与可见光区富里酸荧光强度比值（r_B/A）和腐殖化指数（X_HI）分析表明：I_F和X_BI反映DOM来源以外源输入为主；r_B/A和X_HI反映DOM属于腐殖质特征。废水处理过程中COD和富里酸荧光强度均逐渐降低，COD从3 311.0降至169.6 mg·L^-1；可见光区富里酸荧光强度由4 065.2降低至903.1，紫外光区富里酸荧光强度由4 023.1降至178.6。研究表明，可见光区富里酸和紫外光区富里酸的荧光强度与COD均具有良好的相关性，R²分别为0.978 1和0.981 3，说明可通过三维荧光光谱技术快速监测有机农药废水处理过程中的COD。

关键词: 有机农药废水, 三维荧光光谱, 溶解性有机物, 荧光强度, COD

Abstract:

Three-dimensional fluorescence spectrum was used to investigate fluorescence spectral characteristics of dissolved organic matter (DOM) in organic pesticides wastewater under treatment, in an attempt to establish correlation between DOM fluorescence intensity and COD concentration. The analysis shows that there are three fluorescence peaks in the three-dimensional fluorescence spectrum. They are Peak A in the visible light zone reflecting the existence of fulvic acid, Peak B in the UV light zone reflecting the existence of fulvic acid and Peak C in the high excitation wavelength zone reflecting the existence of tryptophan. The fulvic acid with fluorescence in the visible light and UV light zones was degraded into more biodegradable tryptophan with fluorescence in the high excitation wavelength zone after the wastewater went through the air floatation tank, hydrolysis acidification tank and anaerobic fluidized bed. After going through the contact oxidation tank, the 3 types of DOM in the wastewater declined in fluorescence intensity as a result of biodegradation. Among the three, tryptophan degraded more quickly than fulvic acid. Of the four indices of DOM, fluorescence index (I_F) and biogenesis index (X_BI) reflect that the DOM in the wastewater comes mainly from extraneous sources, and fluorescence intensity ratio of fulvic acid in ultraviolet and visible region(r_B/A) and humification index (X_HI) reveal that the DOM has the properties of humus. With the treatment going on, both the fluorescence intensity of fulvic acid and the concentration of COD decreased with COD dropping from 3 311.0 to 169.6 mg·L^-1. The fulvic acid in the visible light zone dropped from 4 065.2 to 903.1 in fluorescence intensity, and the fulvic acid in the UV light zone did from 4 023.1 to 178.6. A good correlation between COD concentration and fluorescence intensities of the fulvic acid in the visible light and UV light zones has been discovered, with correlation coefficients being 0.978 1 and 0.981 3, respectively, which indicates that the technique of 3-D fluorescence spectrometry can be used to monitor real-time changes in COD concentration in organic pesticides wastewater under treatment.

Key words: organic pesticides wastewater, three-dimensional fluorescence spectrum, dissolved organic matter, fluorescence intensity, COD

中图分类号:

X703.1

黄健, 闫升, 张华, 王坤, 刘沛然, 全桂军, 田纪宇. 农药废水生物处理过程中溶解性有机物特性及荧光强度与COD的关系[J]. 生态与农村环境学报, 2017, 33(9): 830-835.

HUANG Jian, YAN Sheng, ZHANG Hua, WANG Kun, LIU Pei-ran, QUAN Gui-jun, TIAN Ji-yu. Characteristics and Fluorescence Intensity of DOM in Pesticides Wastewater Under Bio-Treatment and Their Relationships With Concentration of COD.[J]. Journal of Ecology and Rural Environment, 2017, 33(9): 830-835.

参考文献

[1] 徐璟,王红武.有机磷农药废水处理方法研究进展[J].安徽农业科学,2015,43(1):93-94,97.[XU Jing,WANG Hong-wu.Research Progress of Treatment Technologies for Organophosphorus Pesticide Wastewater[J].Journal of Anhui Agricultural Sciences,2015,43(1):93-94,97.]
[2] 李继,刘勇,崔康平,等.颗粒活性炭厌氧生物流化床处理有机农药废水[J].环境科学与技术,2010(增刊1):357-359.[LI Ji,LIU Yong,CUI Kang-ping,et al.Granular Activated Carbon Anaerobic Fluidized Bed for Treatment of Organic Pesticides Wastewater[J].Environmental Science and Technology,2010(Suppl. 1):357-359.]
[3] 陈敬,朱乐辉,刘小虎.某生产甲基磺草酮农药厂废水处理工程实例[J].工业水处理,2016,36(5):99-102.[CHEN Jing,ZHU Le-hui,LIU Xiao-hu.Case Study on the Wastewater Treatment in a Pesticide Plant Producing Mesotrione[J].Industrial Water Treatment,2016,36(5):99-102.]
[4] 叶蓓蓉,姚日生,边侠玲.农药生产废水处理技术与研究进展[J].工业用水与废水,2009,40(4):23-26.[YE Bei-rong,YAO Ri-sheng,BIAN Xia-ling.Treatment Technologies of Wastewater From Pesticide Production and Research Progress Thereof[J].Industrial Water & Wastewater,2009,40(4):23-26.]
[5] 张华,王宽,黄显怀,等.间歇曝气实现上覆水脱氮及氨氮荧光法表征[J].中国环境科学,2015,35(11):3275-3281.[ZHANG Hua,WANG Kuan,HUANG Xian-huai,et al.Nitrogen Removal in Overlying Water by Intermittent Aeration and Ammonia Indirect Measurement by Fluorescence Method[J].China Environmental Science,2015,35(11):3275-3281.]
[6] ZHANG Y L,YIN Y,FENG L Q,et al.Characterizing Chromophoric Dissolved Organic Matter in Lake Tianmuhu and Its Catchment Basin Using Excitation-Emission Matrix Fluorescence and Parallel Factor Analysis[J].Water Research,2011,45(16):5110-5122.
[7] 黄健,凌玲,张华,等.ASBR处理食品废水中DOM转化过程的荧光光谱[J].中国环境科学,2016,36(6):1746-1751.[HUANG Jian,LING Ling,ZHANG Hua,et al.Fluorescence Spectra of Dissolved Organic Matter in Food Wastewater Treatment by ASBR Process[J].China Environmental Science,2016,36(6):1746-1751.]
[8] 周璟玲,席宏波,周岳溪,等.石化废水处理过程中荧光有机物变化特征及去除效果[J].光谱学与光谱分析,2014,34(3):704-708.[ZHOU Jing-ling,XI Hong-bo,ZHOU Yue-xi,et al.Variation Characteristics and Removal Rate of Fluorescence Organic Matter in the Petrochemical Wastewater Treatment Process[J].Spectroscopy and Spectral Analysis,2014,34(3):704-708.]
[9] 黄健,王萌,宋箭,等.高碳氮废水处理中有机物的荧光光谱特征分析[J].中国给水排水,2015,31(3):28-31.[HUANG Jian,WANG Meng,SONG Jian,et al.Analysis of Fluorescent Properties of Organic Matter in High Carbon-Nitrogen Wastewater[J].China Water & Wastewater,2015,31(3):28-31.]
[10] 刘学利,姚昕,董杰,等.东平湖可溶性有机物的荧光特征及环境意义[J].生态与农村环境学报,2016,32(6):933-939.[LIU Xue-li,YAO Xin,DONG Jie,et al.Fluorescence Features of Chromophoric Dissolved Organic Matter in Dongping Lake and Their Environmental Significance[J].Journal of Ecology and Rural Environment,2016,32(6):933-939.]
[11] 李淑娟,葛利云,邓欢欢.复合垂直流人工湿地净化过程中DOM的三维荧光光谱分析[J].光谱学与光谱分析,2015,35(4):946-950.[LI Shu-juan,GE Li-yun,DENG Huan-huan.Excitation-Emission Matrix Fluorescence Spectra Characteristics of DOM in Integrated Vertical Flow Constructed Wetland for Treating Eutrophic Water[J].Spectroscopy and Spectral Analysis,2015,35(4):946-950.]
[12] 何莉,吉芳英,来铭笙,等.径流污染对城市污水处理过程的DOM荧光特性影响研究[J].光谱学与光谱分析,2015,35(3):663-667.[HE Li,JI Fang-ying,LAI Ming-sheng,et al.The Influence of Runoff Pollution to DOM Features in an Urban Wastewater Treatment Plant[J].Spectroscopy and Spectral Analysis,2015,35(3):663-667.]
[13] 郝瑞霞,曹可心,邓亦文.三维荧光光谱法表征污水中溶解性有机污染物[J].分析试验室,2007,26(10):41-44.[HAO Rui-xia,CAO Ke-xin,DENG Yi-wen.Characterization of Dissolved Organic Pollutants in Wastewater by Three-Dimensional Fluorescent Spectroscopy[J].Chinese Journal of Analysis Laboratory,2007,26(10):41-44.]
[14] ANDY B.Fluorescence Properties of Some Farm Wastes:Implications for Water Quality Monitoring[J].Water Research,2002,36(1):189-195.
[15] YAMASHITA Y,TANOUE E.Chemical Characterization of Protein-Like Fluorophores in DOM in Relation to Aromatic Amino Acids[J].Marine Chemistry,2003,82(3/4):255-271.
[16] 何磊,王志伟,吴志超.餐饮废水MBR处理过程中DOM的三维荧光光谱分析[J].中国环境科学,2011,31(2):225-232.[HE Lei,WANG Zhi-wei,WU Zhi-chao.Excitation-Emission Matrix Fluorescence Spectra Analysis of Dissolved Organic Matter in MBR Used for Restaurant Wastewater Treatment[J].China Environmental Science,2011,31(2):225-232.]
[17] OHNO T.Fluorescence Inner-Filtering Correction for Determining the Humification Index of Dissolved Organic Matter[J].Environmental Science & Technology,2002,36(4):742-746.
[18] COBLE P G.Characterization of Marine and Terrestrial DOM in Seawater Using Excitation-Emission Matrix Spectroscopy[J].Marine Chemistry,1996,51(4):325-346.
[19] WILSON H F,XENOPOULOS M A.Effects of Agricultural Land Use on the Composition of Fluvial Dissolved Organic Matter[J].Nature Geoscience,2009,2:37-41.
[20] WICKLAND K P,NEFF J C,AIKEN G R.Dissolved Organic Carbon in Alaskan Boreal Forest:Sources,Chemical Characteristics,and Biodegradability[J].Ecosystems,2007,10(8):1323-1340.
[21] HUGUET A,VACHER L,RELEXANS S,et al.Properties of Fluo-rescent Dissolved Organic Matter in the Gironde Estuary[J].Organic Geochemistry,2009,40(6):706-719.
[22] 傅平青,刘丛强,吴丰昌.溶解有机质的三维荧光光谱特征研究[J].光谱学与光谱分析,2005,25(12):2024-2028.[FU Ping-qing,LIU Cong-qiang,WU Feng-chang.Three-Dimensional Excitation Emission Matrix Fluorescence Spectroscopic Characterization of Dissolved Organic Matter[J].Spectroscopy and Spectral Analysis,2005,25(12):2024-2028.]
[23] 高洁,江韬,李璐璐,等.三峡库区消落带土壤中溶解性有机质(DOM)吸收及荧光光谱特征[J].环境科学,2015,36(1):151-162.[GAO Jie,JIANG Tao,LI Lu-lu,et al.Ultraviolet-Visible (UV-Vis) and Fluorescence Spectral Characteristics of Dissolved Organic Matter (DOM) in Soils of Water-Level Fluctuation Zones of the Three Gorges Reservoir Region[J].Environmental Science,2015,36(1):151-162.]
[24] 傅平青,刘丛强,尹祚莹,等.腐殖酸三维荧光光谱特性研究[J].地球化学,2004,33(3):301-308.[FU Ping-qing,LIU Cong-qiang,YIN Zuo-ying,et al.Characterization of Humic Acid by Three-Dimensional Excitation Emission Matrix Fluorescence Spectroscopy[J].Geochimica,2004,33(3):301-308.]