Technical note: Continuous fluorescence-based monitoring of seawater pH in situ

Electrical conductivity (salinity), temperature and fluorescence-based measurements of pH were employed to examine diel fluctuations in seawater carbonate chemistry of surface waters in Sydney Harbour over two multiple-day periods. A proof-of-concept device employing the fluorescence-based technique provided a useful time series for pH. Alkalinity with pH and temperature were used to calculate the degree of calcite and aragonite saturation (Omega Ca and Omega Ar, respectively). Alkalinity was determined from a published alkalinity-salinity relationship. The fluctuations observed in pH over intervals of minutes to hours could be distinguished from background noise. While the stated phase angle resolution of the lifetime fluorometer translated into pH units was +/- 0.0028 pH units, the repeatability standard deviation of calculated pH was 0.007 to 0.009. Diel variability in pH, Omega Ar and Omega Ca showed a clear pattern that appeared to correlate with both salinity and temperature. Drift due to photodegradation of the fluorophore was minimized by reducing exposure to ambient light. The Omega Ca and Omega Ar fluctuated on a daily cycle. The net result of changes in pH, salinity and temperature combined to influence seawater carbonate chemistry. The fluorescence-based pH monitoring technique is simple, provides good resolution and is unaffected by moving parts or leaching of solutions over time. The use of optics is pressure insensitive, making this approach to ocean acidification monitoring well suited to deepwater applications.