Estimating Total Alkalinity in the Washington State Coastal Zone: Complexities and Surprising Utility for Ocean Acidification Research
Evidence of ocean acidification (OA) throughout the global ocean has galvanized some coastal communities to evaluate carbonate chemistry variations closer to home. An impediment to doing this effectively is that, often, only one carbonate system parameter is measured at a time, while two are required to fully constrain the inorganic carbon chemistry of seawater. In order to leverage the abundant single-carbonate-parameter datasets in Washington State for more rigorous OA research, we have characterized an empirical relationship between total alkalinity (TA) and salinity (TA = 47.7 × S + 647; 1σ = ±17 μmol kg−1) for regional surface waters (≤25 m) that is robust in the salinity range from 20 to 35 for all seasons. The relationship was evaluated using 5 years of 3-h contemporaneous observations of salinity, carbon dioxide partial pressure (pCO2), and pH from a surface mooring on the outer coast of Washington. In situ pCO2 observations and salinity-based estimates of TA were used to calculate pH for comparison with in situ pH measurements. On average, the calculated pH values were 0.02 units lower than the measured pH values across multiple pH sensor deployments and showed extremely high fidelity in tracking the measured high-frequency pH variations. Our results indicate that the TA-salinity relationship will be a useful tool for expanding single-carbonate-parameter datasets in Washington State and quality controlling dual pCO2-pH time series.
KeywordsTotal alkalinity Carbonate chemistry Washington state Seawater pH
We thank the crew and science parties on all cruises that contributed to this work, which represent University of Washington (UW) Puget Sound Regional Synthesis Model (PRISM) program, Northwest Association of Regional Ocean Observing Systems (NANOOS), and Washington Ocean Acidification Center (WOAC) cruises focused on Washington waters, as well as NOAA’s West Coast Ocean Acidification cruises and NOAA Fisheries-led PacOOS cruises focused on the outer coast. We are grateful to Beth Curry for her efforts in compiling and quality controlling the UW cruise data. The moored time series observations benefited from the technical expertise of John Mickett, Sylvia Musielewicz, and Randy Bott. Funding for cruise and mooring observations used in this paper came from the NOAA Ocean Acidification Program, NOAA Global Carbon Cycle Program, NOAA Climate Observation Division in the Climate Program Office, NOAA Fisheries, US Integrated Ocean Observing System (IOOS) through NANOOS, Washington State funded WOAC, and UW PRISM Program. The authors were supported by the Postdocs Applying Climate Expertise (PACE) Fellowship Program, partially funded by the NOAA Climate Program Office and administered by the UCAR Visiting Scientist Programs; NOAA Pacific Marine Environmental Laboratory; WOAC and NANOOS via US IOOS. This manuscript benefitted from the input of three anonymous reviewers and is PMEL contribution number 4473.
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