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1.00~75.00 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、直接减除法及现有同类型方法,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 was proposed. The influence of turbidity on COD measurement was 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 modelled 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 (1.00-75.00 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 existing similar methods, 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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