Greg Pelletier

Ocean alkalinity enhancement (OAE), one of the marine carbon dioxide removal strategies, is gaining recognition in its ability to mitigate climate change and ocean acidification (OA). OAE is based on adding alkalinity to open-ocean and coastal marine systems through a variety of different approaches, which raises carbonate chemistry parameters (such as pH, total alkalinity, aragonite saturation state), and enhances the uptake of carbon dioxide (CO2) from the atmosphere. There are large uncertainties in both short- and long-term outcomes related to potential environmental impacts, which would ultimately have an influence on the social license and success of OAE as a climate strategy. This paper represents a synthesis effort, leveraging on the OA studies and published data, observed patterns and generalizable responses. Our assessment framework was developed to predict the sensitivity of marine calcifiers to OAE by using data originating from OA studies. The synthesis was done using raw experimental OA data based on 68 collected studies, covering 84 unique species and capturing the responses of eleven biological groups (calcifying algae, corals, dinoflagellates, mollusks, gastropods, pteropods, coccolithophores, annelids, crustacean, echinoderms, and foraminifera), using regression analyses to predict biological responses to NaOH or Na2CO3 addition and their respective thresholds. Predicted responses were categorized into six different categories (linear positive and negative, threshold positive and negative, parabolic and neutral) to delineate responses per species. The results show that 34.4% of responses are predicted to be positive (N=33), 26.0% negative (N=25), and 39.2% (N=38) neutral upon alkalinity addition. For the negatively impacted species, biological thresholds, which were based on 50% reduction of calcification rate, were in the range of 50 to 500 µmol/kg NaOH addition. Thus, we emphasize the importance of including much lower additions of alkalinity in experimental trials to realistically evaluate in situ biological responses. The primary goal of the research was to provide an assessment of biological rates and thresholds predicted under NaOH/Na2CO3 addition that can serve as a tool for delineating OAE risks, guiding and prioritizing future OAE biological research and regional OAE monitoring efforts and communicate the risks with stakeholders. This is important given the fact that at least some of the current OAE approaches do not always assure safe biological space. With 60% of responses being non-neutral, a precautionary approach for OAE implementation is warranted, identifying the conditions where potential negative ecological outcomes could happen, which is key for scaling up and avoiding ecological risks.

Ocean acidification (OA) is projected to have profound impacts on marine ecosystems and resources, especially in estuarine habitats. Here, we describe biological risks under current levels of exposure to anthropogenic OA in the Salish Sea, an estuarine system that already experiences inherently low pH and aragonite saturation state (Ω_ar) conditions. We used the Pacific Northwest National Laboratory and Washington State Department of Ecology Salish Sea biogeochemical model (SSM) informed by a selection of OA-related biological thresholds of ecologically and economically important calcifiers, pteropods, and Dungeness crabs. The SSM was implemented to assess current exposure and associated risk due to reduced Ω_ar and pH conditions with respect to the magnitude, duration, and severity of exposure below the biological thresholds in the Salish Sea in comparison to the pre-industrial era. We further investigated the individual effects of atmospheric CO₂ uptake and nutrient-driven eutrophication on changes in chemical exposure since pre-industrial times. Our model predicts average decreases in Ω_ar and pH since pre-industrial times of about 0.11 and 0.06, respectively, in the top 100 m of the water column of the Salish Sea. These decreases predispose pelagic calcifiers to increased duration, intensity, and severity of exposure. For pteropods, present-day exposure is below the thresholds related to sublethal effects across the entire Salish Sea basin, while mortality threshold exposure occurs on a spatially limited basis. The greatest risk for larval Dungeness crabs is associated with spatially limited exposures to low calcite saturation state in the South Sound in the springtime, triggering an increase in internal dissolution. The main anthropogenic driver behind the predicted impacts is atmospheric CO₂ uptake, while nutrient-driven eutrophication plays only a marginal role over spatially and temporally limited scales. Reduction of CO₂ emissions can help sustain biological species vital for ecosystem functions and society.

Fingerprinting ocean acidification (OA) in US West Coast waters is extremely challenging due to the large magnitude of natural carbonate chemistry variations common to these regions. Additionally, quantifying a change requires information about the initial conditions, which is not readily available in most coastal systems. In an effort to address this issue, we have collated high-quality publicly available data to characterize the modern seasonal carbonate chemistry variability in marine surface waters of the US Pacific Northwest. Underway ship data from version 4 of the Surface Ocean CO₂ Atlas, discrete observations from various sampling platforms, and sustained measurements from regional moorings were incorporated to provide ∼ 100 000 inorganic carbon observations from which modern seasonal cycles were estimated. Underway ship and discrete observations were merged and gridded to a 0.1° × 0.1° scale. Eight unique regions were identified and seasonal cycles from grid cells within each region were averaged. Data from nine surface moorings were also compiled and used to develop robust estimates of mean seasonal cycles for comparison with the eight regions. This manuscript describes our methodology and the resulting mean seasonal cycles for multiple OA metrics in an effort to provide a large-scale environmental context for ongoing research, adaptation, and management efforts throughout the US Pacific Northwest. Major findings include the identification of unique chemical characteristics across the study domain. There is a clear increase in the ratio of dissolved inorganic carbon (DIC) to total alkalinity (TA) and in the seasonal cycle amplitude of carbonate system parameters when moving from the open ocean North Pacific into the Salish Sea. Due to the logarithmic nature of the pH scale (pH = −log₁₀[H⁺], where [H⁺] is the hydrogen ion concentration), lower annual mean pH values (associated with elevated DIC : TA ratios) coupled with larger magnitude seasonal pH cycles results in seasonal [H⁺] ranges that are ∼ 27 times larger in Hood Canal than in the neighboring North Pacific open ocean. Organisms living in the Salish Sea are thus exposed to much larger seasonal acidity changes than those living in nearby open ocean waters. Additionally, our findings suggest that lower buffering capacities in the Salish Sea make these waters less efficient at absorbing anthropogenic carbon than open ocean waters at the same latitude. All data used in this analysis are publically available at the following websites: Surface Ocean CO₂ Atlas version 4 coastal data, https://doi.pangaea.de/10.1594/PANGAEA.866856 (Bakker et al., 2016a); National Oceanic and Atmospheric Administration (NOAA) West Coast Ocean Acidification cruise data, https://doi.org/10.3334/CDIAC/otg.CLIVAR_NACP_West_Coast_Cruise_2007 (Feely and Sabine, 2013); https://doi.org/10.7289/V5JQ0XZ1 (Feely et al., 2015b); https://data.nodc.noaa.gov/cgi-bin/iso?id=gov.noaa.nodc:0157445 (Feely et al., 2016a); https://doi.org/10.7289/V5C53HXP (Feely et al., 2015a); University of Washington (UW) and Washington Ocean Acidification Center cruise data, https://doi.org/10.5281/zenodo.1184657 (Fassbender et al., 2018); Washington State Department of Ecology seaplane data, https://doi.org/10.5281/zenodo.1184657 (Fassbender et al., 2018); NOAA Moored Autonomous pCO₂ (MAPCO2) buoy data, https://doi.org/10.3334/CDIAC/OTG.TSM_LAPUSH_125W_48N (Sutton et al., 2012); https://doi.org/10.3334/CDIAC/OTG.TSM_WA_125W_47N (Sutton et al., 2013); https://doi.org/10.3334/CDIAC/OTG.TSM_DABOB_122W_478N (Sutton et al., 2014a); https://doi.org/10.3334/CDIAC/OTG.TSM_TWANOH_123W_47N (Sutton et al., 2016a); UW Oceanic Remote Chemical/Optical Analyzer buoy data, https://doi.org/10.5281/zenodo.1184657 (Fassbender et al., 2018); NOAA Pacific Coast Ocean Observing System cruise data, https://doi.org/10.5281/zenodo.1184657 (Fassbender et al., 2018).

Increasing levels of nutrients, persistent hypoxia, harmful algal blooms, and increased frequency of fish kills are degrading the ecological health of the Salish Sea. An improved version of a diagnostic hydrodynamic and biogeochemical model (nutrients, phytoplankton, carbon, dissolved oxygen, and pH) of the Salish Sea has been developed with the ability to simulate characteristic circulation and water quality features. Sensitivity tests were conducted to assess the responsiveness of the system to land‐based (rivers and wastewater sources) nutrient loading. The influence of Fraser River on the magnitude of estuarine exchange with the Pacific Ocean and nearshore habitat was examined given that it contributes nearly half of the total freshwater discharged to the Salish Sea. A large region of hypoxia in Hood Canal that extends over 30–40 km during its peak was reproduced and attributed primarily to the existence of a two‐layer classic fjord‐type circulation and a nearly stagnant deep bottom layer that occupies nearly 60% of the water column. Nitrate mass in the euphotic zone from land‐based and oceanic sources is depleted to near‐zero limiting levels during summer. Under such conditions, the Salish Sea is responsive to changes in nutrient loads entering the euphotic zone directly. A hypothetical scenario involving the elimination of land‐based nutrient sources results in notable water‐quality improvement, featuring a reduction in algal biomass (≈5.4%), reduction in sediment oxygen demand (≈17.1%), and significant reduction in hypoxic area (≈39%) and exposure in area‐days to bottom layer hypoxia (≈62%) within the Salish Sea.

Fingerprinting ocean acidification (OA) in U.S. West Coast waters is extremely challenging due to the large magnitude of natural carbonate chemistry variations common to these regions. Additionally, quantifying a change requires information about the initial conditions, which is not readily available in most coastal systems. In an effort to address this issue, we have collated high-quality, publicly-available data to characterize the modern seasonal carbonate chemistry variability in marine surface waters of the Pacific Northwest. Underway ship data from Version 4 of the Surface Ocean CO2 Atlas, discrete observations from various sampling platforms, and sustained measurements from regional moorings were incorporated to provide ~ 100,000 inorganic carbon observations from which modern seasonal cycles were estimated. Underway ship and discrete observations were merged and gridded to a 0.1° × 0.1° scale. Eight unique regions were identified and seasonal cycles from grid cells within each region were averaged. Data from nine surface moorings were also compiled and used to develop robust estimates of mean seasonal cycles for comparison with the eight regions. This manuscript describes our methodology and the resulting mean seasonal cycles for multiple OA metrics in an effort to provide large-scale, environmental context for ongoing research, adaptation, and management efforts throughout the Pacific Northwest. Major findings include the identification of unique chemical characteristics across the study domain. There is a clear increase in the ratio of dissolved inorganic carbon (DIC) to total alkalinity (TA) and in the seasonal cycle amplitude of carbonate system parameters when moving from the open ocean North Pacific into the Salish Sea. Due to the logarithmic nature of the pH scale (pH = −log10[H⁺], where [H⁺] is the hydrogen ion concentration), lower annual mean pH values (associated with elevated DIC : TA) coupled with larger magnitude seasonal pH cycles results in seasonal [H⁺] ranges that are ~ 27 times larger in Hood Canal than in the neighboring North Pacific open ocean. Organisms living in the Salish Sea are thus exposed to much larger seasonal acidity changes than those living in nearby open ocean waters. Additionally, our findings suggest that lower buffering capacities in the Salish Sea make these waters less efficient at absorbing anthropogenic carbon than open ocean waters at the same latitude. All data used in this analysis are publically available at the following websites: • Surface Ocean CO2 Atlas Version 4 coastal data, doi:10.1594/PANGAEA.866856; • National Oceanic and Atmospheric Administration (NOAA) West Coast Ocean Acidification cruise data, doi:10.3334/CDIAC/otg.CLIVAR_NACP_West_Coast_Cruise_2007; doi:10.3334/CDIAC/OTG.COAST_WCOA2011; doi:10.3334/CDIAC/OTG.COAST_WCOA2012; doi:10.7289/V5C53HXP; • University of Washington (UW) and Washington Ocean Acidification Center cruise data, doi:10.5281/zenodo.1184657; • Washington State Department of Ecology seaplane data, 10.5281/zenodo.1184657; • NOAA Moored Autonomous pCO₂ (MAPCO2) Buoy data, doi:10.3334/CDIAC/OTG.TSM_LAPUSH_125W_48N; doi:10.3334/CDIAC/OTG.TSM_WA_125W_47N; doi:10.3334/CDIAC/OTG.TSM_DABOB_122W_478N; doi:10.3334/CDIAC/OTG.TSM_TWANOH_123W_47N; • UW Oceanic Remote Chemical/Optical Analyzer Buoy data, doi:10.5281/zenodo.1184657; • NOAA Pacific Coast Ocean Observing System cruise data, doi:10.5281/zenodo.1184657.

While ocean acidification was first investigated as a global phenomenon, coastal acidification has received significant attention in recent years, as its impacts have been felt by different socio-economic sectors (e.g., high mortality of shellfish larvae in aquaculture farms). As a region that connects land and ocean, the Salish Sea (consisting of Puget Sound and the Straits of Juan de Fuca and Georgia) receives inputs from many different sources (rivers, wastewater treatment plants, industrial waste treatment facilities, etc.), making these coastal waters vulnerable to acidification. Moreover, the lowering of pH in the Northeast Pacific Ocean also affects the Salish Sea, as more acidic waters get transported into the bottom waters of the straits and estuaries. Here, we use a numerical ocean model of the Salish Sea to improve our understanding of the carbonate system in Puget Sound; in particular, we studied the sensitivity of carbonate variables (e.g., dissolved inorganic carbon, total alkalinity, pH, saturation state of aragonite) to ocean and freshwater inputs. The model is an updated version of our FVCOM-ICM framework, with new carbonate-system and sediment modules. Sensitivity experiments altering concentrations at the open boundaries and freshwater sources indicate that not only ocean conditions entering the Strait of Juan de Fuca, but also the dilution of carbonate variables by freshwater sources, are key drivers of the carbonate system in Puget Sound.

A pilot study of sampling, using monthly marine flights over spatially distributed stations, was conducted with the aim to characterize the carbonate system in Puget Sound over a full year-long period. Surface waters of Puget Sound were found to be under-saturated with respect to aragonite during October–March, and super-saturated during April–September. Highest pCO2 and lowest pH occurred during the corrosive October–March period. Lowest pCO2 and highest pH occurred during the super-saturated April–September period. The monthly variations in pCO2, pH, and aragonite saturation state closely followed the variations in monthly average chlorophyll a. Super-saturated conditions during April–September are likely strongly influenced by photosynthetic uptake of CO2 during the phytoplankton growing season. The relationship between phytoplankton production, the carbonate system, and aragonite saturation state suggests that long-term trends in eutrophication processes may contribute to trends in ocean acidification in Puget Sound.