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Attribution of the ocean acidification (OA) signal in estuarine carbonate system observations is necessary for quantifying the impacts of global anthropogenic CO 2 emissions on water quality, and informing managers of the efficacy of potential mitigation options. We present an analysis of observational data to characterize dynamics and drivers of seasonal carbonate system variability in two seagrass habitats of Puget Sound, WA, USA, and estimate how carbon accumulations due to anthropogenic CO 2 emissions C anth interact with these drivers of carbonate chemistry to determine seasonally resolved rates of acidification in these habitats. Three independent simulations of C anth accumulation from 1765 to 2100 were run using two previously published methods and one novel method for C anth estimation. Our results revealed persistent seasonal differences in the magnitude of carbonate system responses to anthropogenic CO 2 emissions caused by seasonal metabolic changes to the buffering capacity of estuarine waters. The seasonal variability of pH T and p CO 2 is increased (while that of Ω aragonite is decreased) and acidification rates are accelerated when compared with open-ocean estimates, highlighting how feedbacks between local metabolism and C anth can control the susceptibility of estuarine habitats to OA impacts. The changes in seasonal variability can shorten the timeline to exceedance of established physiological thresholds for endemic organisms and existing Washington State water quality criteria for pH. We highlight how C anth estimation uncertainties manifest in shallow coastal waters and limit our ability to predict impacts to coastal organisms and ecosystems from anthropogenic CO 2 emissions.

The impacts of ocean acidification (OA) on coastal water quality have been subject to intensive research in the past decade, but how emissions-driven OA combines with human modifications of coastal river inputs to affect estuarine acidification dynamics is less well understood. This study presents a methodology for quantifying the synergistic water quality impacts of OA and riverine acidification on biologically-relevant timescales through a case study from a small, temperate estuary influenced by coastal upwelling and watershed development. We characterized the dynamics and drivers of carbonate chemistry in Tillamook Bay, OR (USA), along with its coastal ocean and riverine end-members, through a series of synoptic samplings and continuous water quality monitoring from July 2017 to July 2018. Synoptic river sampling showed acidification and increased CO 2 content in areas with higher proportions of watershed anthropogenic land use. We propagated the impacts of 1). the observed riverine acidification, and 2). modeled OA changes to incoming coastal ocean waters across the full estuarine salinity spectrum and quantified changes in estuarine carbonate chemistry at a 15-minute temporal resolution. The largest magnitude of acidification (-1.4 pH ⊤ units) was found in oligo- and mesohaline portions of the estuary due to the poor buffering characteristics of these waters, and was primarily driven by acidified riverine inputs. Despite this, emissions-driven OA is responsible for over 94% of anthropogenic carbon loading to Tillamook Bay and the dominant driver of acidification across most of the estuary due to its large tidal prism and relatively small river discharges. This dominance of ocean-sourced anthropogenic carbon challenges the efficacy of local management actions to ameliorate estuarine acidification impacts. Despite the relatively large acidification effects experienced in Tillamook Bay (-0.16 to -0.23 p H ⊤ units) as compared with typical open ocean change (approximately -0.1 pH ⊤ units), observations of estuarine pH ⊤ would meet existing state standards for pH ⊤ . Our analytical framework addresses pressing needs for water quality assessment and coastal resilience strategies to differentiate the impacts of anthropogenic acidification from natural variability in dynamic estuarine systems., Competing Interests: Conflict of interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

The role of rising atmospheric CO 2 in modulating estuarine carbonate system dynamics remains poorly characterized, likely due to myriad processes driving the complex chemistry in these habitats. We reconstructed the full carbonate system of an estuarine seagrass habitat for a summer period of 2.5 months utilizing a combination of time-series observations and mechanistic modeling, and quantified the roles of aerobic metabolism, mixing, and gas exchange in the observed dynamics. The anthropogenic CO 2 burden in the habitat was estimated for the years 1765-2100 to quantify changes in observed high-frequency carbonate chemistry dynamics. The addition of anthropogenic CO 2 alters the thermodynamic buffer factors (e.g., the Revelle factor) of the carbonate system, decreasing the seagrass habitat's ability to buffer natural carbonate system fluctuations. As a result, the most harmful carbonate system indices for many estuarine organisms [minimum pH T , minimum Ω arag , and maximum pCO 2(s.w.) ] change up to 1.8×, 2.3×, and 1.5× more rapidly than the medians for each parameter, respectively. In this system, the relative benefits of the seagrass habitat in locally mitigating ocean acidification increase with the higher atmospheric CO 2 levels predicted toward 2100. Presently, however, these mitigating effects are mixed due to intense diel cycling of CO 2 driven by aerobic metabolism. This study provides estimates of how high-frequency pH T , Ω arag , and pCO 2(s.w.) dynamics are altered by rising atmospheric CO 2 in an estuarine habitat, and highlights nonlinear responses of coastal carbonate parameters to ocean acidification relevant for water quality management., Competing Interests: The authors declare no conflict of interest.

Ocean acidification (OA) is altering the chemistry of the world's oceans at rates unparalleled in the past roughly 1 million years. Understanding the impacts of this rapid change in baseline carbonate chemistry on marine organisms needs a precise, mechanistic understanding of physiological responses to carbonate chemistry. Recent experimental work has shown shell development and growth in some bivalve larvae, have direct sensitivities to calcium carbonate saturation state that is not modulated through organismal acid-base chemistry. To understand different modes of action of OA on bivalve larvae, we experimentally tested how pH, PCO2, and saturation state independently affect shell growth and development, respiration rate, and initiation of feeding in Mytilus californianus embryos and larvae. We found, as documented in other bivalve larvae, that shell development and growth were affected by aragonite saturation state, and not by pH or PCO2. Respiration rate was elevated under very low pH (~7.4) with no change between pH of ~ 8.3 to ~7.8. Initiation of feeding appeared to be most sensitive to PCO2, and possibly minor response to pH under elevated PCO2. Although different components of physiology responded to different carbonate system variables, the inability to normally develop a shell due to lower saturation state precludes pH or PCO2 effects later in the life history. However, saturation state effects during early shell development will carry-over to later stages, where pH or PCO2 effects can compound OA effects on bivalve larvae. Our findings suggest OA may be a multi-stressor unto itself. Shell development and growth of the native mussel, M. californianus, was indistinguishable from the Mediterranean mussel, Mytilus galloprovincialis, collected from the southern U.S. Pacific coast, an area not subjected to seasonal upwelling. The concordance in responses suggests a fundamental OA bottleneck during development of the first shell material affected only by saturation state.

The absorption of atmospheric carbon dioxide (CO2) into the ocean lowers the pH of the waters. This so-called ocean acidification could have important consequences for marine ecosystems. To better understand the extent of this ocean acidification in coastal waters, we conducted hydrographic surveys along the continental shelf of western North America from central Canada to northern Mexico. We observed seawater that is undersaturated with respect to aragonite upwelling onto large portions of the continental shelf, reaching depths of approximately 40 to 120 meters along most transect lines and all the way to the surface on one transect off northern California. Although seasonal upwelling of the undersaturated waters onto the shelf is a natural phenomenon in this region, the ocean uptake of anthropogenic CO2 has increased the areal extent of the affected area.

The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide.