辽河下游CDOM吸收与荧光特性的季节变化研究

有色溶解有机物(CDOM)是一类广泛分布于水体中的溶解有机物(DOM),是水环境中最大的溶解有机碳贮库.辽河是中国七大河流之一,年径流量为14.8亿m3,因此对于辽河CDOM的研究对辽河有机碳通量的估算具有重要意义.基于吸收光谱和荧光光谱分析了不同季节辽河下游河流中CDOM的光学特性.通过分析CDOM的吸收光谱及斜率(S)得到春季水样CDOM在355 nm的吸收系数aCDOM(355)]低于秋季和冬季;秋季CDOM的分子量要小于冬季和春季,而春季CDOM的分子量大于秋、冬季.通过对比分析3期荧光强度及各荧光峰(类腐殖酸荧光峰,峰A、峰C;类蛋白质荧光峰,峰B、峰T),发现辽河下游水体CDOM的荧光特性表现明显的季节性,而且都表现出较强的类蛋白质荧光峰(峰B和峰T).春季的两个类腐殖质荧光之间以及秋、冬季两个类蛋白质荧光之间均存在很强的相关性(R2>0.9),说明来源或性质相同.春季CDOM的两个类蛋白质荧光峰的相关性较差(R2=0.21),反映了其组分的复杂性和来源的多样性;春季水体显现出较强的类腐殖酸荧光峰,说明外源输入是春季水体CDOM中类腐殖酸成分的主要来源.另外,本研究将aCDOM(355)和Fn(355)进行分析发现冬季两者相关性最好(R2=0.75),秋季次之(R2=0.48),冬季结果较不理想(R2=0.01).通过荧光峰值与CDOM浓度之间的相关分析可以得到荧光峰B是秋、冬季CDOM荧光的主要控制发光基团(R=0.66;R=0.89),而春季CDOM的类腐殖酸荧光(峰A和峰C)表现比较突出(R=0.74;R=0.82).

Seasonal Variation in the Absorption and Fluorescence Characteristics of CDOM in Downstream of Liaohe River

Chromophoric dissolved organic matter (CDOM), which is an important part of dissolved organic matter (DOM), is considered as the largest storage of dissolved organic carbon in the aquatic environment. Liaohe River is the seventh largest river in China with annual runoff of 1.48 billion m³. As a result, studying on CDOM of Liaohe River is very important in estimating the organic carbon flux into sea. Seasonal optical characteristics of CDOM in the downstream of Liaohe River were investigated using absorbance spectroscopy and fluorescence excitation-emission matrices (EEMs). CDOM absorption coefficient at 355 nm a_CDOM(355)] in spring was lower than that in autumn and winter while low molecular weight substances were found in autumn and high molecular weight substances in spring based on the absorption coefficient and absorption slope (S) of CDOM. Samples in different seasons all exhibited fairly strong protein-like fluorophore (fluorophore B and fluorophore T) in the EEMs but the values showed apparent temporal variations. Based on the analysis of the relationships between different fluorophores, strong correlations (R²>0.9) were observed between fluorophore A and C in spring, fluorophore B and T in autumn and winter, which illustrated that they had similar CDOM original sources. However, a weak relationship (R²=0.21) was found between fluorophore B and T in spring, demonstrating the complexity and diversity of CDOM sources. Starting from autumn to winter and the subsequent spring, humic-like fluorophores exhibited enhanced fluorescent intensity, which could be ascribed to exogenous input. Furthermore, linear relationship between aCDOM(355) and F_n(355) in different seasons was examined in the study, and the strongest relationship was obtained in winter (R²=0.75), followed by autumn (R²=0.48) and spring (R²=0.01). This study indicated that fluorophore B in autumn and winter (R=0.66; R=0.89) as well as humic-like fluorophores (A and C, R=0.74; R=0.82) in spring were the main contributors to the CDOM optical characteristics.