Precision and accuracy of spectrophotometric pH measurements at environmental conditions in the Baltic Sea

The increasing uptake of anthropogenic CO2 by the oceans has raised an interest in precise and accurate pH measurement in order to assess the impact on the marine CO2-system. Spectrophotometric pH measurements were refined during the last decade yielding a precision and accuracy that cannot be achieved with the conventional potentiometric method. However, until now the method was only tested in oceanic systems with a relative stable and high salinity and a small pH range. This paper describes the first application of such a pH measurement system at conditions in the Baltic Sea which is characterized by a wide salinity and pH range. The performance of the spectrophotometric system at pH values as low as 7.0 (total scale) and salinities between 0 and 35 was examined using TRIS-buffer solutions, certified reference materials, and tests of consistency with measurements of other parameters of the marine CO2 system. Using m-cresol purple as indicator dye and a spectrophotometric measurement system designed at Scripps Institution of Oceanography (B. Carter, A. Dickson), a precision better than +/- 0.001 and an accuracy between +/- 0.01 and +/- 0.02 was achieved within the observed and salinity ranges in the Baltic Sea. The influence of the indicator dye on the pH of the sample was determined theoretically and is presented as a pH correction term for the different alkalinity regimes in the Baltic Sea. Because of the encouraging tests, the ease of operation and the fact that the measurements refer to the internationally accepted total pH scale, it is recommended to use the spectrophotometric method also for pH monitoring and trend detection in the Baltic Sea. (C) 2014 Elsevier Ltd. All rights reserved.