Spectrophotometric loop flow analyzer for high-precision measurement of seawater pH

Automated instrument for long-term measurement of seawater pH is important for documenting the changes of the marine carbonate system and the impacts of ocean acidification. An automated pH analyzer based on loop flow analysis (LFA-pH) was developed to achieve precise and accurate measurements of seawater pH. The circulating loop allows complete mixing of an indicator and seawater, constant mixing volume of two solutions, and correcting indicator perturbation for each measurement. During laboratory testing, the LFA-pH precision achieved 0.0004, and the accuracy was 0.0017 ± 0.0038 compared with the certified standard buffer at different temperatures. During the 59 day underway measurement across the mid and high latitudes, more than 2500 pH measurements were carried out. LFA-pH showed good stability with high temperature and salinity changes, and measurement results were consistent with the discrete surface seawater pH measurement data. In situ testing of two LFA-pHs was completed near the Zhongyuan pier in Qingdao. The average pH offset between the two LFA-pHs was 0.0010 ± 0.0032 (n = 788), with the accuracies of the two LFA-pHs of 0.0012 ± 0.0033 and 0.0005 ± 0.0035 compared to discrete measurements. For continuous measurement, the average power consumption is 3.6 W at a 10 min measurement frequency. Given its low power consumption, high precision, and accuracy, FLA-pH could be adapted for underway and in situ measurements of ocean acidification observations.