Temperature coefficient of seawater pH as a function of temperature, pH, DIC and salinity
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Abstract: pH is a measure of the hydrogen ion activity in a solution, which is a function of temperature. Under normal seawater conditions, it is well constrained. Nowadays, with an increasing interest in complex environments (e.g., sea ice), a better understanding of the temperature change on pH under extreme conditions is needed. The objective of this paper was to investigate the temperature coefficient of the seawater pH (∆pH/∆T) over a wide range of temperature, pH, dissolved inorganic carbon (DIC) and salinity by a method of continuous pH measurement with the temperature change, and to verify the application of CO2SYS for pH conversion under extreme conditions (on the National Bureau of Standards (NBS) scale and the total proton scale). Both experimental results and CO2SYS calculations showed that ∆pH/∆T was slightly affected by temperature over the range of 0°C to 40°C and by pH (at 25°C) from 7.8 to 8.5. However, when pH was out of this range, ∆pH/∆T varied greatly with pH value. According to the experimental results, changes in DIC from 1 mmol/kg to 5 mmol/kg and salinity from 20 to 105 had no significant effect on ∆pH/∆T. CO2SYS calculations showed a slight increase in ∆pH/∆T with DIC on both the NBS scale and the total proton scale; and underestimated ∆pH/∆T at high salinity (i.e., beyond the oceanographic range) on the NBS scale. Nevertheless, CO2SYS is still suitable for pH conversion even under extreme conditions by simply setting the input values of DIC and salinity in CO2SYS within the oceanographic range (e.g., DIC=2 mmol/kg and S=35).
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Key words:
- temperature coefficient /
- pH measurement /
- CO2SYS /
- sea ice /
- ocean acidification
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Figure 1. Temperature coefficient of seawater pH (∆pH/∆T) at every 5°C span from temperature 0°C to 40°C and at the experimental condition of salinity=35, DIC concentration=2 mmol/kg and pH=8.0 (25°C): experimental results are labelled by red dots; lines are derived from CO2SYS calculation based on the NBS scale (blue) and the total proton scale (green), respectively.
Figure 2. Temperature coefficient of seawater pH (∆pH/∆T) at different pH (25°C) from 7.5 to 10.0 and at the experimental condition of S=35, DIC concentration=2 mmol/kg: experimental results are labelled by red dots; lines are derived from CO2SYS calculation based on the NBS scale (blue) and the total proton scale (green), respectively. The uncertainty in ∆pH/∆T for each experimental data point is within ±0.000 2°C−1.
Figure 3. Temperature coefficient of seawater pH (∆pH/∆T) at different DIC concentrations from 1 mmol/kg to 5 mmol/kg and at the experimental condition of S=35, pH=8.0 (25oC): experimental results (orange), results derived from CO2SYS calculation based on the NBS scale (blue) and the total proton scale (green), respectively.
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