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In this research, a simple, sensitive chemiluminescence (CL) method for the determination of humic acid (HA) in water samples was first developed based on the redox reaction between humic acid and cerium(IV) in the acidic condition. Different with the former redox CL reaction which occurred in alkaline solution, no enhancers were needed and neither precipitation nor a second contamination would occur in the present CL system. Comparing with other spectrometric methods, we find that the proposed analysis system had better applicability and accuracy. Under the optimal experiment conditions, the CL peak height was linear with the concentration of HA in the range of 0.03 to 10.0 microg mL(-1). The detection limit is 0.01 microg mL(-1) (S/N = 3), and the relative standard deviation was 2.3% for 0.5 microg mL(-1) HA solution with eleven repeated measurements. The present CL method was successfully applied to the determination of HA in tap water, spring water and river water samples with good recovery from 90.0 to 110.0%. A possible CL mechanism was proposed based on the results of UV and fluorescence spectrometry and the CL spectrum of HA. It was speculated that the semi-quinone radicals in the excited state were the emitters.

Sensitive Monitoring of Humic Acid in Various Aquatic Environments with Acidic Cerium Chemiluminescence Detection