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  1. Abstract

    Long-term ocean time series have proven to be the most robust approach for direct observation of climate change processes such as Ocean Acidification. The California Cooperative Oceanic Fisheries Investigations (CalCOFI) program has collected quarterly samples for seawater inorganic carbon since 1983. The longest time series is at CalCOFI line 90 station 90 from 1984–present, with a gap from 2002 to 2008. Here we present the first analysis of this 37- year time series, the oldest in the Pacific. Station 90.90 exhibits an unambiguous acidification signal in agreement with the global surface ocean (decrease in pH of −0.0015 ± 0.0001 yr−1), with a distinct seasonal cycle driven by temperature and total dissolved inorganic carbon. This provides direct evidence that the unique carbon chemistry signature (compared to other long standing time series) results in a reduced uptake rate of carbon dioxide (CO2) due to proximity to a mid-latitude eastern boundary current upwelling zone. Comparison to an independent empirical model estimate and climatology at the same location reveals regional differences not captured in the existing models.

     
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  2. null (Ed.)
    Abstract. Equimolal tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer in artificialseawater is a well characterized and commonly used standard for oceanographic pH measurements. We evaluated the stability of tris pH when stored in purportedly gas-impermeable bags across a variety of experimental conditions, including bag type and storage in air vs. seawater over300 d. Bench-top spectrophotometric pH analysis revealed that the pH of tris stored in bags decreased at a rate of 0.0058±0.0011 yr−1 (mean slope ±95 % confidence interval of slope). The upper and lower bounds of expected pH change att=365 d, calculated using the averages and confidence intervals of slope and intercept of measured pH change vs. time data, were −0.0042 and −0.0076 from initial pH. Analyses of total dissolved inorganic carbonconfirmed that a combination of CO2 infiltration and/or microbialrespiration led to the observed decrease in pH. Eliminating the change in pH of bagged tris remains a goal, yet the rate of pH change is lower than many processes of interest and demonstrates the potential of bagged tris for sensor calibration and validation of autonomous in situ pH measurements. 
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