A new, highly sensitive chemiluminescence method for the determination of sub-ppb quantities of phosphorus in water is described. The method is based on sorption preconcentration of phosphorus as a yellow vanadomolybdophosphoric heteropoly acid (HPA) in the presence or absence of a cationic surfactant on a paper filter, followed by direct chemiluminescence detection of the phosphorus concentrate via reaction with an alkaline luminol solution. The molar ratio of cationic surfactant to HPA in the ion associate sorbed on the filter is 4:1. The detection limits for phosphorus are 0.02 microgram of P L-1 in the presence of surfactant and 0.1 microgram of P L-1 in the absence of surfactant for a sample volume of 150 mL. The calibration plot is linear from 0.06 to 1.7 micrograms of P L-1 in the presence of a surfactant, and the time required for analysis is 25 min. In the absence of surfactant, the selectivities against Si4+ and As5+ are 5 and 40 times greater than those for the standard colorimetric method based on the formation of the blue molybdophosphoric HPA. Applications of the method to the analyses of river water, seawater, and the turbine vapor condensate from a coal-fired power plant are described. It is demonstrated that the sensitivity advantage of the chemiluminescence technique can be combined with the magnesium-induced coprecipitation (MAGIC) method for a more selective measurement of soluble reactive phosphorus.
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