CAJ | 학술논문

激光拉曼光谱技术是水下原位探测酸根离子浓度的强有力工具，建立一套适用于海洋环境、基于拉曼光谱技术的定量分析方法对实时了解海洋化学信息具有重要意义。本文在实验室条件下，以 SO2－4和HCO－3系列浓度水溶液及近海海域的海水为样品，532 nm 激光作为激发光源，模拟原位探测方式采用侵入式光学探头采集拉曼光谱。分别采用内定标法、多元线性回归法（MLR）、偏最小二乘法（PLS）和基于主导因素的 PLS 法对光谱数据进行定量分析。研究结果表明，采用以1640 cm－1水分子 O—H 振动谱峰为内标峰的内定标法预测待测离子浓度，预测误差均相对较大，定标曲线线性相关系数不高；采用多元线性回归法，定标曲线的线性相关系数有较大提高，在一定程度上提高了定量分析的精度；采用酸根拉曼峰强度、酸根峰面积、水峰强度、水峰面积作主导因素结合 PLS 法预测配置溶液中 SO2－4和 HCO－3浓度的定标曲线相关系数 R 2分别为0．990和0．916，对待测样30 mmol·L－1的 SO2－4预测相对误差为3．262％，对20 mmol·L－1的 HCO－3预测相对误差为5．267％。以海水中 SO2－4为分析对象时，与离子色谱法预测的28．01 mmol·L－1进行对比，以上四种定标方法的研究结果表明，主导因素结合 PLS 法优于其余三种分析方法，其均值相对误差降低为1．128％。因此，采用水的拉曼信号作为主导因素结合 PLS 法预测水溶液中的酸根离子浓度时能有效提高定量分析的精度，并可应用于现场和原位探测中的定标。
격광랍만광보기술시수하원위탐측산근리자농도적강유력공구，건립일투괄용우해양배경、기우랍만광보기술적정량분석방법대실시료해해양화학신식구유중요의의。본문재실험실조건하，이 SO2－4화HCO－3계렬농도수용액급근해해역적해수위양품，532 nm 격광작위격발광원，모의원위탐측방식채용침입식광학탐두채집랍만광보。분별채용내정표법、다원선성회귀법（MLR）、편최소이승법（PLS）화기우주도인소적 PLS 법대광보수거진행정량분석。연구결과표명，채용이1640 cm－1수분자 O—H 진동보봉위내표봉적내정표법예측대측리자농도，예측오차균상대교대，정표곡선선성상관계수불고；채용다원선성회귀법，정표곡선적선성상관계수유교대제고，재일정정도상제고료정량분석적정도；채용산근랍만봉강도、산근봉면적、수봉강도、수봉면적작주도인소결합 PLS 법예측배치용액중 SO2－4화 HCO－3농도적정표곡선상관계수 R 2분별위0．990화0．916，대대측양30 mmol·L－1적 SO2－4예측상대오차위3．262％，대20 mmol·L－1적 HCO－3예측상대오차위5．267％。이해수중 SO2－4위분석대상시，여리자색보법예측적28．01 mmol·L－1진행대비，이상사충정표방법적연구결과표명，주도인소결합 PLS 법우우기여삼충분석방법，기균치상대오차강저위1．128％。인차，채용수적랍만신호작위주도인소결합 PLS 법예측수용액중적산근리자농도시능유효제고정량분석적정도，병가응용우현장화원위탐측중적정표。
Laser Raman spectroscopy as an in situ analytical technology can enable detailed investigation of the ocean environ-ment.It is necessary to set up a quantitative analysis method based on laser Raman spectroscopy to understand the marine status in situ.In the laboratory investigations,varied concentration of HCO-3 ,SO2 -4 and coastal waters of Qingdao are taken as the samples,operating 532 nm of laser,using fiber optic probes to simulate detection mode in situ.Raman spectra are analyzed using the method of internal standard normalization,multiple linear regression(MLR),general Partial Least Squares(PLS)and PLS based on dominant factor respectively in data processing.It was found that correlation coefficients of calibration curves are not high in internal standard normalization method and predicted relative errors on the prepared samples are much high,so inter-nal standard normalization method cannot be effectively used in the quantitative analysis of HCO-3 ,SO2 -4 in the water.And with the multiple linear regression,the analysis accuracy was improved effectively.The calibration curve of PLS based on dominant factor showed that the SO2 -4 and HCO-3 of pre-made solution with correlation coefficient R 2 of 0.990 and 0.916 respectively.The 30 mmol·L-1 of SO2 -4 and 20 mmol·L-1 of HCO-3 in two target samples were determined with the relative errors lower than 3.262% and 5.267% respectively.SO2 -4 in the coastal waters as the research object was analyzed by above-mentioned methods, comparing with 28.01 mmol·L-1 by ion chromatography.It was demonstrated that PLS based on dominant factor method is su-perior to the rest of the three analysis methods,which can be used in situ calibration,with the mean relative error about 1.128%.All the results show that analysis accuracy would be improved by the PLS based on dominant factor method to predict concentration of acid radical ions.