溶解无机碳的拉曼光谱定量分析可行性研究

海水溶解无机碳(DIC)的平均浓度约为2.05mmol/L,其中HCO3-占93%, CO32-为6%,CO2和H2CO3共1%.HCO3-的拉曼散射活性太弱,而其他成分的浓度又过低,使得海水中DIC组分不能产生明显的拉曼散射强度,目前还未见有关溶解无机碳拉曼光谱定量分析的报道.为突破这一局限,本研究探索了一种碱化辅助的拉曼定量分析方法,以海水DIC中拉曼活性最低、占比例最大的HCO3-为研究对象进行了可行性实验研究.通过碱化处理(100mL样品中添加NaOH试剂15mg)将HCO3-转化为拉曼活性更强的CO32-,有效提高了拉曼光谱系统对HCO3-的检出限(<3mmol/L).定量分析使用内标定法,选取水在~1635cm-1附近的O—H弯曲振动谱带作为标定物.实验结果显示,该方法对与海水中浓度相当的低浓度HCO3-溶液的定量分析具有良好的精度(相对误差<6.5%).

Feasibility investigation of quantitative analysis of dissolved inorganic carbon by Raman spectrometry

The mean concentration of dissolved inorganic carbon(DIC) in seawater is about 2.05mmol/L. Approximately 93% of DIC is HCO3-, 6% is CO32-, and only 1% is CO2 and H2CO3. Since Raman activity of HCO3- is weak and the concentration of other species is low, it is impossible for DIC in seawater to generate Raman scattering that is intense enough to be detected. There is no report on quantitative analysis of DIC in seawater using Laser Raman Spectrometry so far. In order to break through the limitation, a Raman spectroscopy quantitative analysis method assisted with sample alkalization was proposed. HCO3- was treated as study object because it takes the largest share and the Raman activity of it was the weakest among all DIC species. The solution was alkalized to convert HCO3- into CO32- which was more Raman active. OH bending band of water was treated as the internal standard for its stability. The Raman spectroscopy analysis detecting limit of HCO3- was increased, and the quantitative analysis result showed good accuracy (relative error<6.5%).