Flow-through solid-phase based optical sensor for the multisyringe flow injection trace determination of orthophosphate in waters with chemiluminescence detection

摘要

In this work, a novel flow-through solid-phase based chemiluminescence (CL) optical sensor is described for the trace determinationof orthophosphate in waters exploiting the multisyringe flow injection analysis (MSFIA) concept with multicommutation. The proposedtime-based injection flow system relies upon the in-line derivatisation of the analyte with ammonium molybdate in the presence of vanadate,and the transient immobilisation of the resulting heteropolyacid in a N-vinylpyrrolidone/divinylbenzene copolymer packed spiral shapeflow-through cell located in front of the window of a photomultiplier tube. The simultaneous injection of well-defined slugs of luminol inalkaline medium and methanol solution towards the packed reactor is afterwards performed by proper switching of the solenoid valves. Then,the light emission from the luminol oxidation by the oxidant species retained onto the sorbent material is readily detected. At the sametime, the generated molybdenum-blue compound is eluted by the minute amount of injected methanol, rendering the system prepared for anew measuring cycle. Therefore, the devised sensor enables the integration of the solid-phase CL reaction with elution and detection of theemitted light without the typical drawbacks of the molybdenum-blue based spectrophotometric procedures regarding the excess of molybdateanion, which causes high background signals due to its self-reduction. The noteworthy features of the developed CL–MSFIA system are thefeasibility to accommodate reactions with different pH requirements and the ability to determine trace levels of orthophosphate in high silicatecontent samples (Si/P ratios up to 500). Under the optimised conditions, a dynamic linear range from 5 to 50 g P l−1 for a 1.8 ml sample,repeatability better than 3.0% and a quantification limit of 4 g P l−1 were attained. The flowing stream system handles 11 analysis h−1 andhas been successfully applied to the determination of trace levels of orthophosphate in environmental samples such as mineral, ground, tapand pond waters as well as samples from a water-steam cycle of an incineration plant. The t-test comparison of the means for the developedoptical sensor and the molybdenum-blue spectrophotometric APHA/AWWA/WPCF reference method revealed that there is no evidence ofsignificant differences between the obtained results at the 95% confidence level.