When these procedures are followed carefully, the uncertainty of a potentiometric measurement of seawater pH expressed total hydrogen ion conentration can be less than 0. The problem is that this approach was not implemented routinely until the s Dickson, a,b; Dickson et al. Whether measured on a ship or back in a shore-based laboratory, pH results have to be corrected back to the in situ temperature at which the samples were originally collected to provide an estimate of the in situ pH.
Unfortunately, much of the supporting metadata records of the measurement temperature, the in situ temperature and the mathematical formula for conversion of the data from one temperature to the other was not given to NCEI along with the data files Boyer et al. Hence, in many cases, we are not certain what pH value is being reported measured versus in situ. We suspect that a significant fraction of the historical pH values were reported at laboratory temperature and were never corrected back to the in situ temperature.
In many cases, the measurement temperature was not reported as part of the metadata package, making later temperature correction impossible Boyer et al. The lack of information as to whether the pH values were reported as measured versus in situ , and the lack of documentation on measurement temperature will lead to large pH uncertainties in the earlier database. In response to many of these concerns, the international ocean carbon community began a systematic process in the early s to develop rigorous and well-documented procedures for analyzing and reporting pH and carbon system parameter data.
Andrew Dickson of Scripps Institution of Oceanography was supported to make and distribute Reference Materials RMs that could be used by the international carbon community to check the quality of their measurements. We formed international data analysis teams like Surface Ocean Carbon ATlas , Carina , and Pacifica that carefully checked the data to identify mistakes and systematic biases.
The carbon data that were evaluated and synthesized were maintained as a database separate from the original data set so that if errors were identified at a later date we could revise the synthesized data set without affecting the original data. This period was characterized by the establishment of global ocean carbon hydrographic surveys and long-term time series stations that yielded high-quality measurements at highly-resolved temporal and spatial scales.
As the greatly improved spectrophotometric pH methods were refined in the early s, there was renewed interest in making high-quality pH measurements. The scientific community had greater trust in these measurements because the measurements could be compared to and validated against the independent measurements of total carbon, pCO 2 and total alkalinity from these large community evaluated data sets compiled as previously described.
Finally, starting with the WOCE-JGOFS era, we were able to collect high-quality data using standard protocols and validated with reference materials with enough temporal and spatial resolution that would allow us to determine scientifically defensible mean annual oceanic surface water trends. The resulting data from to the present have been published in many peer-reviewed scientific articles and assessments, culminating in the recent assessment published in the recent IPCC AR5 Working Group 1 Report Chapter 3 see Rhein et al. It was motivated, in part, by e-mail requests for observational pH data by Michael G.
Wallace and others over the years. Bates, N. Astor, M.
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