黄河干流宁蒙段溶解性有机物组分特征及其与金属离子的相关性

Characterization of Dissolved Organic Matter Fractions in the Ning-Meng Section of the Yellow River and Relationship with Metal Ions

溶解性有机物(dissolved organic matter,DOM)是天然水体的重要组成部分,由于化学极性及所含的官能团不同,其在水体中的化学行为也不同.本研究以黄河干流宁蒙段为研究对象,于2015年4月采集了下河沿至头道拐沿程7个断面的水样,采用XAD系列树脂将DOM分为疏水性酸(hydrophobic acid,HOA)、疏水性碱(hydrophobic base,HOB)、弱疏水性酸(weak hydrophobic acid,WHOA)和亲水性物质(hydrophilic matter,HYI)这4个组分,探讨了DOM组分含量、荧光峰值及其与Pb、Zn、Cu、Cr、As这5种金属离子之间的相关性.结果表明,黄河宁蒙段DOM总量由下河沿至头道拐沿程逐渐增加.各断面DOM腐殖化程度较低,以亲水性的蛋白质类小分子物质(HYI)为主,疏水性酸(HOA)次之,这与黄河沿岸排污导致内源作用增强有关.三维荧光光谱中类腐殖质和类蛋白质荧光峰型显著,且类腐殖质峰沿程逐渐增强,进一步证实了内源污水输入的影响.SPSS相关性分析结果表明,DOM与5种金属离子呈现出不同程度的相关性,其中与Cu离子显著相关;4种组分中HYI与Cu离子的相关性最强,说明二者在迁移转化过程中存在显著相互作用.进一步研究发现,芳香蛋白类物质荧光峰强度随Cu离子浓度的升高而降低,这可能是Cu与亲水性组分中的芳香类蛋白质发生络合产生荧光淬灭效应,从而导致荧光强度降低.

Dissolved organic matter（DOM） is an important element of natural aquatic systems. Due to differences in their hydrophobic/hydrophilic properties and various functional groups,chemical appearances of DOM fractions also vary. In this study,seven natural waters,extending from Xiaheyan to Toudaoguai along the Ning-Meng section of the Yellow river,were sampled in April 2015. Four DOM fractions were obtained by pumping through XAD-4 and XAD-8 resins,i. e.,hydrophobic acid（HOA）,hydrophobic base（HOB）,weak hydrophobic acid（WHOA）,and hydrophilic matter（HYI）. Based on detection by three-dimensional excitationemission matrix fluorescence（EEM） and correlation analysis,relationships with five metal ions（Pb,Zn,Cu,Cr,As） were analyzed. Results show that DOC gradually increased along an upstream to downstream continuum in the Ning-Meng section. HYI（small molecular proteins） was the main DOM fraction present,followed by HOA,suggesting enhanced microbial-sourced impact from industrial sewage discharges. The significant peaks of humic-like（A,C） and protein-like compounds（T1） in the EEM chart further highlight the effect of endogenous pollution caused by wastewater. Furthermore,SPSS fitting results indicate that DOM is correlated with all five metal ions,especially with Cu. In terms of the four DOM fractions,HYI showed the strongest correlation with Cu,illustrating the significant relationship between HYI and Cu during the migration and transformation process. Moreover,the fluorescence intensity of protein-like compounds decreased with increasing Cu concentration,possibly due to fluorescence quenching caused by complexation between Cu and proteins in HYI.