Impact of impurities in bromocresol green indicator dye on spectrophotometric total alkalinity measurements

Abstract

Due to its accurate and precise character, spectrophotometric pH detection is a common technique applied in measurement methods for carbonate system parameters. However, impurities in the used pH indicator dyes can influence the measurements quality. During our work described here, we focused on impacts of impurities in the pH indicator dye bromocresol green (BCG) on spectrophotometric seawater total alkalinity (AT) measurements. In order to evaluate the extent of such influences, purified BCG served as a reference. First, a high-performance liquid chromatography (HPLC) purification method for BCG was developed as such a method did not exist at the time of this study. An analysis of BCG dye from four different vendors with this method revealed different types and quantities of impurities. After successful purification, AT measurements with purified and unpurified BCG were carried out using the novel autonomous analyzer CONTROS HydroFIA® TA. Long-term measurements in the laboratory revealed a direct influence of impurity types and quantities on the drift behavior of the analyzer. The purer the BCG, the smaller was the AT increase per measurement. The observed drift is generally caused by deposits in the optical pathway mainly generated by the impurities. However, the analyzers drift behavior could not be fully overcome. Furthermore, we could show that a certain impurity type in some indicator dyes changed the drift pattern from linear to nonlinear, which can impair long-term deployments of the system. Consequently, such indicators are impractical for these applications. Laboratory performance characterization experiments revealed no improvement of the measurement quality (precision and bias) by using purified BCG as long as the impurities of the unpurified dye do not exceed a quantity of 2 % (relationship of peak areas in the chromatogram). However, BCG with impurity quantities higher than 6 % provided AT values which failed fundamental quality requirements. In conclusion, to gain optimal AT measurements especially during long-term deployments, an indicator purification is not necessarily required as long as the purchased dye has a purity level of at least 98 % and is free of the named impurity type. Consequently, high-quality AT measurements do not require pure but the purest BCG that is purchasable.