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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.

 

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. 

Seasonal oxygen structure and utilization in the Sargasso Sea are characterized using nine profiling floats with oxygen 2021 sensors (years 2005–2008), deployed in an Eighteen Degree Water (EDW) experiment (CLIMODE). During autumn‐winter when the mixed layer is deepening, oxygen increases from the surface to the base of the EDW at 400 m. During spring‐summer, oxygen decreases except between the seasonal pycnocline and compensation depth, creating the seasonal shallow oxygen maximum layer (SOMax) with oxygen production of 0.04 μmol kg⁻¹·day⁻¹. In the underlying seasonal oxygen minimum (SOMin), the oxygen utilization rate (OUR) is 0.10 μmol kg⁻¹·day⁻¹, decreasing with depth to 0.04 μmol kg⁻¹·day⁻¹in the EDW. Remineralization in May to August is double that of August to November. The Sargasso Sea is a net carbon producer; estimated annual export production from the top 100–250 m is 2.9 mol C m⁻²and from the top 400 m is 4.2 mol C m⁻². Below the EDW, oxygen decreases seasonally at the same time as in the EDW, indicating remineralization down to 700 m. However, on isopycnals in this deeper layer, oxygen increases during May to September, likely due to lateral advection from nonlocal surface outcrops. Summer shoaling of these isopycnals creates this paradox. The complex vertical oxygen structure in the upper 200 m enables important vertical diffusive flux that modifies the OUR calculated from oxygen change. Ignoring mixing underestimates maximum remineralization by 19% and underestimates maximum net production by 88%. However, vertical mixing is negligible in the deeper layers, so the associated total integrated remineralization error is 5%–9%.

 

Aerosols impact climate, human health, and the chemistry of the atmosphere, and aerosol pH plays a major role in the physicochemical properties of the aerosol. However, there remains uncertainty as to whether aerosols are acidic, neutral, or basic. In this research, we show that the pH of freshly emitted (nascent) sea spray aerosols is significantly lower than that of sea water (approximately four pH units, with pH being a log scale value) and that smaller aerosol particles below 1 μm in diameter have pH values that are even lower. These measurements of nascent sea spray aerosol pH, performed in a unique ocean−atmosphere facility, provide convincing data to show that acidification occurs “across the interface” within minutes, when aerosols formed from ocean surface waters become airborne. We also show there is a correlation between aerosol acidity and dissolved carbon dioxide but no correlation with marine biology within the seawater. We discuss the mechanisms and contributing factors to this acidity and its implications on atmospheric chemistry. 

Marine aerosols strongly influence climate through their interactions with solar radiation and clouds. However, significant questions remain regarding the influences of biological activity and seawater chemistry on the flux, chemical composition, and climate-relevant properties of marine aerosols and gases. Wave channels, a traditional tool of physical oceanography, have been adapted for large-scale ocean-atmosphere mesocosm experiments in the laboratory. These experiments enable the study of aerosols under controlled conditions which isolate the marine system from atmospheric anthropogenic and terrestrial influences. Here, we present an overview of the 2019 Sea Spray Chemistry and Particle Evolution (SeaSCAPE) study, which was conducted in an 11 800 L wave channel which was modified to facilitate atmospheric measurements. The SeaSCAPE campaign sought to determine the influence of biological activity in seawater on the production of primary sea spray aerosols, volatile organic compounds (VOCs), and secondary marine aerosols. Notably, the SeaSCAPE experiment also focused on understanding how photooxidative aging processes transform the composition of marine aerosols. In addition to a broad range of aerosol, gas, and seawater measurements, we present key results which highlight the experimental capabilities during the campaign, including the phytoplankton bloom dynamics, VOC production, and the effects of photochemical aging on aerosol production, morphology, and chemical composition. Additionally, we discuss the modifications made to the wave channel to improve aerosol production and reduce background contamination, as well as subsequent characterization experiments. The SeaSCAPE experiment provides unique insight into the connections between marine biology, atmospheric chemistry, and climate-relevant aerosol properties, and demonstrates how an ocean-atmosphere-interaction facility can be used to isolate and study reactions in the marine atmosphere in the laboratory under more controlled conditions.