沈阳市黑臭水体表层水DOM紫外光谱特征分析
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摘要
为识别黑臭水体中DOM组成、结构及腐殖化水平,运用UV-vis(紫外-可见吸收光谱)与多元统计相结合的方式,对沈阳市5条黑臭水体的27个表层水样中DOM的UV-vis特征及9个紫外光谱指数进行研究。研究表明:27个表层水样中DOM的UV-vis吸收系数的变异系数在30%～80%之间,轻度黑臭水体相对于重度黑臭水体的紫外吸收峰在356、487、657 nm处分别发生了1、2、2 nm的蓝移;轻度黑臭水体紫外光谱指数SUVA_(254)、S_(275～295)、S_(350～400)、A_2/A_1、A_3/A_1、A_3/A_2均高于重度黑臭水体,而E_2/E_3、E_4/E_6、E_2/E_4低于重度黑臭水体,轻度黑臭水体的腐殖化水平与腐殖化趋势高于重度黑臭水体。进一步分析得出:苯酚基(木质素和奎宁基团)决定了黑臭水体中DOM腐殖化进程,不同黑臭水体DOM的组分存在明显差异;轻度黑臭水体中DOM的腐殖化水平、芳香化程度、木质素与其他物质在腐殖化开始的比例、分子质量等均高于重度黑臭水体。多元统计与UV-vis技术对黑臭水体中DOM的组成及结构进行了定性,为黑臭水体的溯源和整治工作提供理论基础。
In order to identify the composition, structure and humification level of DOM in black and odorous water body, the ultraviolet absorption spectra and nine ultraviolet spectral indices of DOM in 27 surface water samples of five black and odorous water bodies in Shenyang city were studied by using the combination of ultraviolet-visible absorption spectroscopy and statistical analysis techniques. The results showed that the variation coefficients of DOM ultraviolet spectral absorption indices of 27 surface water samples ranged from30% to 80%, and the ultraviolet absorption peaks of mild black and odorous water bodies at 356, 487 and 657 nm showed blue shifts of 1, 2 and 2 nm, respectively. The ultraviolet spectral indices of mild black and odorous water bodies, such as SUVA_(254)、S_(275～295)、S_(350～400)、A_2/A_1、A_3/A_1、A_3/A_2, were higher than those of severe black and odorous water bodies, while E_2/E_3, E_4/E_6 and E_2/E_4 were lower than those of severe black and odorous water bodies, and the humification level and trend of mild black and odorous water bodies were higher than those of severe black and odorous water bodies. The further results showed that phenol group(lignin and quinine group)determined the humification process of DOM in black and odorous water body. There are obvious differences in DOM components among different black and odorous water bodies. The humification level, aromatization degree,ratio of lignin to other substances and molecular weight of DOM in mild black and odorous water body were higher than those in severe black and odorous water body. Multivariate statistics and UV-vis technology were used to qualitatively characterize the structure of DOM in black and odorous water body, which provided a basis for the traceability and treatment of black and odorous water body.
In order to identify the composition, structure and humification level of DOM in black and odorous water body, the ultraviolet absorption spectra and nine ultraviolet spectral indices of DOM in 27 surface water samples of five black and odorous water bodies in Shenyang city were studied by using the combination of ultraviolet-visible absorption spectroscopy and statistical analysis techniques. The results showed that the variation coefficients of DOM ultraviolet spectral absorption indices of 27 surface water samples ranged from30% to 80%, and the ultraviolet absorption peaks of mild black and odorous water bodies at 356, 487 and 657 nm showed blue shifts of 1, 2 and 2 nm, respectively. The ultraviolet spectral indices of mild black and odorous water bodies, such as SUVA_(254)、S_(275～295)、S_(350～400)、A_2/A_1、A_3/A_1、A_3/A_2, were higher than those of severe black and odorous water bodies, while E_2/E_3, E_4/E_6 and E_2/E_4 were lower than those of severe black and odorous water bodies, and the humification level and trend of mild black and odorous water bodies were higher than those of severe black and odorous water bodies. The further results showed that phenol group(lignin and quinine group)determined the humification process of DOM in black and odorous water body. There are obvious differences in DOM components among different black and odorous water bodies. The humification level, aromatization degree,ratio of lignin to other substances and molecular weight of DOM in mild black and odorous water body were higher than those in severe black and odorous water body. Multivariate statistics and UV-vis technology were used to qualitatively characterize the structure of DOM in black and odorous water body, which provided a basis for the traceability and treatment of black and odorous water body.
引文
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[14]MARKAGER S S.Tracing the production and degradation of autochthonous fractions of dissolved organic matter by fluores‐cence analysis[J].Limnology and Oceanography,2005,50(5):1415-1426.
[15]YAN M,DRYER D,KORSHIN G V,et al.In situ study of binding of copper by fulvic acid:Comparison of differential absor‐bance data and model predictions[J].Water Research,2013,47(2):588-596.
[16]ZHU Y Z,SONG Y H,YU H B,et al.Characterization of dissolved organic matter in Dongjianghu Lake by UV-visible ab‐sorption spectroscopy with multivariate analysis[J].Environmental Monitoring&Assessment,2017,189(9):443.
[17]NISHIJIMA W,KIM W H,SHOTO E,et al.The performance of an ozonation-biological activated carbon process under long term operation[J].Water Science&Technology,1998,38(38):163-169.
[18]岳兰秀,吴丰昌,刘丛强,等.红枫湖和百花湖天然溶解有机质的分子荧光特征与分子量分布的关系[J].科学通报,2005,50(24):2774-2780.
[19]BARRETO S R G,NOZAKI J,BARRETO W J.Origin of dissolved organic carbon studied by UV‐vis spectroscopy[J].CleanSoil Air Water,2010,31(6):513-518.
[20]陶澍,崔军,张朝生.水生腐殖酸的可见-紫外光谱特征[J].地理学报,1990,45(4):484-489.
[21]HELMS J R,STUBBINS A,RITCHIE J D,et al.Absorption spectral slopes and slope ratios as indicators of molecular weight,source,and photobleaching of chromophoric dissolved organic matter[J].Limnology&Oceanography,2008,53(3):955-969.
[22]CHEN Y,SENESI N,SCHNITZER M.Information provided on humic substances by E4/E6ratios[J].Soil Science Society of America Journal,1977,41(2):352-358.
[23]ALBRECHT R,LE P J,TERROM G,et al.Comparison between UV spectroscopy and Nirs to assess humification process during sewage sludge and green wastes co-composting[J].Bioresource Technology,2011,102(6):4495-4500.
[2]沈烁,王育来,杨长明,等.南淝河不同排口表层沉积物DOM光谱特征[J].中国环境科学,2014,34(9):2351-2361.
[3]杨楠,于会彬,宋永会,等.应用多元统计研究城市河流沉积物孔隙水中DOM紫外光谱特征[J].环境科学学报,2014,34(7):1751-1757.
[4]李璐璐,江韬,卢松,等.利用紫外-可见吸收光谱估算三峡库区消落带水体、土壤和沉积物溶解性有机质(DOM)浓度[J].环境科学,2014,35(9):3408-3416.
[5]赵越,魏雨泉,李洋,等.不同物料堆肥腐熟程度的紫外-可见光谱特性表征[J].光谱学与光谱分析,2015,35(4):961-965.
[6]王齐磊,江韬,赵铮,等.三峡库区典型农业小流域土壤溶解性有机质的紫外-可见及荧光特征[J].环境科学,2015,36(3):879-887.
[7]吕纯剑,高红杰,李晓洁,等.沈阳市黑臭水体溶解性有机物组分及其光学特征[J].环境工程学报,2019,13(3):559-568.
[8]张甲申,曹军.土壤水溶性有机物的紫外光谱特征及地域分异[J].土壤学报,2003,40(1):118-122.
[9]李丹,何小松,高如泰,等.紫外-可见光谱研究堆肥水溶性有机物不同组分演化特征[J].中国环境科学,2016,36(11):3412-3421.
[10]李会杰.腐殖酸和富里酸的提取与表征研究[D].武汉:华中科技大学,2012.
[11]GUO X J,YUAN D H,JIANG J Y,et al.Detection of dissolved organic matter in saline-alkali soils using synchronous fluo‐rescence spectroscopy and principal component analysis[J].Spectrochim Acta Part A:Molecular and Biomolecular Spectros‐copy,2013,104(3):280-286.
[12]YU H B,SONG Y H,PAN H W,et al.Synchronous fluorescence spectroscopy combined with two-dimensional correlation and principle component analysis to characterize dissolved organic matter in an urban river[J].Environmental Monitoring&Assessment,2016,188(10):579.
[13]DRYER D J,KORSHIN G V,FABBRICINO M.In situ examination of the protonation behavior of fulvic acids using differen‐tial absorbance spectroscopy[J].Environmental Science&Technology,2008,42(17):6644-6649.
[14]MARKAGER S S.Tracing the production and degradation of autochthonous fractions of dissolved organic matter by fluores‐cence analysis[J].Limnology and Oceanography,2005,50(5):1415-1426.
[15]YAN M,DRYER D,KORSHIN G V,et al.In situ study of binding of copper by fulvic acid:Comparison of differential absor‐bance data and model predictions[J].Water Research,2013,47(2):588-596.
[16]ZHU Y Z,SONG Y H,YU H B,et al.Characterization of dissolved organic matter in Dongjianghu Lake by UV-visible ab‐sorption spectroscopy with multivariate analysis[J].Environmental Monitoring&Assessment,2017,189(9):443.
[17]NISHIJIMA W,KIM W H,SHOTO E,et al.The performance of an ozonation-biological activated carbon process under long term operation[J].Water Science&Technology,1998,38(38):163-169.
[18]岳兰秀,吴丰昌,刘丛强,等.红枫湖和百花湖天然溶解有机质的分子荧光特征与分子量分布的关系[J].科学通报,2005,50(24):2774-2780.
[19]BARRETO S R G,NOZAKI J,BARRETO W J.Origin of dissolved organic carbon studied by UV‐vis spectroscopy[J].CleanSoil Air Water,2010,31(6):513-518.
[20]陶澍,崔军,张朝生.水生腐殖酸的可见-紫外光谱特征[J].地理学报,1990,45(4):484-489.
[21]HELMS J R,STUBBINS A,RITCHIE J D,et al.Absorption spectral slopes and slope ratios as indicators of molecular weight,source,and photobleaching of chromophoric dissolved organic matter[J].Limnology&Oceanography,2008,53(3):955-969.
[22]CHEN Y,SENESI N,SCHNITZER M.Information provided on humic substances by E4/E6ratios[J].Soil Science Society of America Journal,1977,41(2):352-358.
[23]ALBRECHT R,LE P J,TERROM G,et al.Comparison between UV spectroscopy and Nirs to assess humification process during sewage sludge and green wastes co-composting[J].Bioresource Technology,2011,102(6):4495-4500.
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