一种适用于浊水的海水化学需氧量紫外-可见光谱测量补偿方法

A Turbidity Compensation Method for Seawater COD Measurement Using UV-Visible Spectroscopy

  • 摘要: 紫外-可见光谱法作为一种简便快捷、无污染的测量方法,近年来被广泛应用于海洋水体化学需氧量(Chemical Oxygen Demand, COD)的原位测量,但其测量精度会受到海水复杂组分干扰产生显著偏差。为提高紫外-可见光谱水质传感器在实际海水环境中测量的准确性,本文提出了一种改进的COD原位测量补偿方法,该方法通过实验室配制水样,分析水体浊度对于COD质量浓度测量的影响规律,指出通过建立COD标准曲线斜率与浊度的二次多项式经验拟合关系,可以实现基于紫外可见光谱法COD质量浓度原位测量动态补偿。采用浊度为0~200 NTU、COD质量浓度为1~75 mg/L的实验室配制混合水样进行测量精度验证,结果表明,应用本文浊度补偿方法后,COD质量浓度测量均方根误差(RMSE)为0.82 mg/L,低COD质量浓度与高COD质量浓度混合水样的决定系数分别为0.996 4与0.997 8。实地采集海水养殖场的浊度范围为6.91~107.05 NTU、COD质量浓度范围为0.96~9.15 mg/L的水样进一步测量验证,结果表明,COD测量的相对误差范围为−4.27%~6.64%,RMSE为0.25 mg/L,决定系数为0.993 9。相较于未经补偿、直接减除法及峰高补偿法,本文方法测量误差均显著减少。本文改进方法可以有效提高浊水COD质量浓度的测量精度,在海洋COD原位测量仪器的开发方面具有应用潜力。

     

    Abstract: Ultraviolet-Visible (UV-Vis) spectroscopy is widely used in in-situ seawater chemical oxygen demand (COD) measurement owing to its simplicity, rapidity, and pollution-free advantages. However, it is susceptible to interference from complex water components in coastal turbid water, which can result in a significant decrease in COD measurement accuracy. To improve the accuracy of COD measurement using UV-Vis spectroscopy in turbid water, an improved compensation method for COD in-situ measurement is proposed. The influence of turbidity on COD measurement is firstly analyzed using lab-prepared solutions with varying concentrations of marine sediments, it is found that a dynamic compensation method can be built based on the relationship between slopes of COD concentrations versus absorption at 254 nm and turbidity which can be well modeled by a least-squares fitting, and an accurate in-situ COD measurement in turbid coastal water can be achieved. Using mixed water samples with turbidity (0-200 NTU) and COD concentrations (1-75 mg/L) prepared in laboratory, it is demonstrated that the results derived by the compensation method have a root mean square error (RMSE) of 0.82 mg/L, and the determination coefficients (R2) are 0.9964 and 0.9978 for low and high COD concentrations, respectively. By collecting field samples with turbidity (6.91-107.05 NTU) and COD concentrations (0.96-9.15 mg/L) in a costal aquaculture farm, the COD measurements by this study has a relative error range of −4.27% to 6.64%, the RMSE of 0.25 mg/L, and the R2 of 0.9939. Compared to uncompensated, direct subtraction compensation, and method for compensating peak height reduction, the proposed method in this study significantly reduces measurement error and effectively improves the accuracy of in-situ COD measurement in turbid water, and has the potential to be applied in the development of in-situ instruments for COD measurements.

     

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