The effect of Ocean Acidification (OA) on marine biota is quasi-predictable at best. While perturbation studies, in the form of incubations under elevated pCO2, reveal sensitivities and responses of individual species, one missing link in the OA story results from a chronic lack of pH data specific to a given species' natural habitat. Here, we present a compilation of continuous, high-resolution time series of upper ocean pH, collected using autonomous sensors, over a variety of ecosystems ranging from polar to tropical, open-ocean to coastal, kelp forest to coral reef. These observations reveal a continuum of month-long pH variability with standard deviations from 0.004 to 0.277 and ranges spanning 0.024 to 1.430 pH units. The nature of the observed variability was also highly site-dependent, with characteristic diel, semi-diurnal, and stochastic patterns of varying amplitudes. These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100. Our data provide a first step toward crystallizing the biophysical link between environmental history of pH exposure and physiological resilience of marine organisms to fluctuations in seawater CO2. Knowledge of this spatial and temporal variation in seawater chemistry allows us to improve the design of OA experiments: we can test organisms with a priori expectations of their tolerance guardrails, based on their natural range of exposure. Such hypothesis-testing will provide a deeper understanding of the effects of OA. Both intuitively simple to understand and powerfully informative, these and similar comparative time series can help guide management efforts to identify areas of marine habitat that can serve as refugia to acidification as well as areas that are particularly vulnerable to future ocean change.

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Ocean acidification, a reduction in ocean pH due to the uptake of anthropogenic carbon dioxide (CO2) by surface waters, has recently emerged as a research theme in marine biology due to an expected deleterious effect of altered seawater chemistry on calcification. Owing to the importance of larval survival and dispersal for the maintenance of adult populations, early life history stages of calcifying marine invertebrates have been a central focus of this research. Here, we present an experimental system that unites the culturing needs of larval invertebrates with methods for careful control, monitoring, and manipulation of seawater carbonate chemistry necessary to conduct laboratory‐based studies of ocean acidification. Using a series of mass flow controllers, the system produces three unique pCO2 levels, which are bubbled into gas‐mixing reservoirs for equilibration with filtered seawater. This seawater is then delivered to larval culturing vessels providing the larvae with a continual supply of clean seawater consistent with optimal culturing methodologies. In this flow‐through system, pCO2 levels are determined at 3 points: the inflowing seawater, the gas‐mixing reservoirs, and the larval culture vessels. The delivered gas pCO2 values are adjusted to achieve the desired stable‐state relationship for each experimental pCO2 treatment. We evaluated the performance of this system in terms of 1) the stability of the parameters of the inorganic carbonate system in all experimental vessels and 2) our ability to successfully rear larvae using these methodologies. Our results indicate the suitability of this design for successful manipulation of pCO2 for ocean acidification experiments on larvae.

The Southern Ocean, a region that will be an ocean acidification hotspot in the near future, is home to a uniquely adapted fauna that includes a diversity of lightly-calcified invertebrates. We exposed the larvae of the echinoid Sterechinus neumayeri to environmental levels of CO2 in McMurdo Sound (control: 410 µatm, Ω = 1.35) and mildly elevated pCO2 levels, both near the level of the aragonite saturation horizon (510 µatm pCO2, Ω = 1.12), and to under-saturating conditions (730 µatm, Ω = 0.82). Early embryological development was normal under these conditions with the exception of the hatching process, which was slightly delayed. Appearance of the initial calcium carbonate (CaCO3) spicule nuclei among the primary mesenchyme cells of the gastrulae was synchronous between control and elevated pCO2 treatments. However, by prism (7 days after the initial appearance of the spicule nucleus), elongating arm rod spicules were already significantly shorter in the highest CO2 treatment. Unfed larvae in the 730 µatm pCO2 treatment remained significantly smaller than unfed control larvae at days 15–30, and larvae in the 510 µatm treatment were significantly smaller at day 20. At day 30, the arm lengths were more differentiated between 730 µatm and control CO2 treatments than were body lengths as components of total length. Arm length is the most plastic morphological aspect of the echinopluteus, and appears to exhibit the greatest response to high pCO2/low pH/low carbonate, even in the absence of food. Thus, while the effects of elevated pCO2 representative of near future climate scenarios are proportionally minor on these early developmental stages, the longer term effects on these long-lived invertebrates is still unknown.

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Although predictions suggest that ocean acidification will significantly impact polar oceans within 20-30 years, there is limited information regarding present-day pH dynamics of the Southern Ocean. Here, we present novel high-frequency observations of pH collected during spring of 2010 using SeaFET pH sensors at three locations under fast sea ice in the southern Ross Sea. During these deployments in McMurdo Sound, baseline pH ranged between 8.019-8.045, with low to moderate overall variation (0.043-0.114 units) on the scale of hours to days. The variation was predominantly in the direction of increased pH relative to baseline observations. Estimates of aragonite saturation state (V Ar ) were . 1 with no observations of subsaturation. Time series records such as these are significant to the Antarctic science community; this information can be leveraged towards framing more environmentally relevant laboratory experiments aimed at assessing the vulnerability of Antarctic species to ocean acidification. In addition, increased spatial and temporal coverage of pH datasets may reveal ecologically significant patterns. Specifically, whether such variation in natural ocean pH dynamics may drive local adaptation to pH variation or provide refugia for populations of marine calcifiers in a future, acidifying ocean.

Ocean acidification is expected to have a major effect on the marine carbonate system over the next century, particularly in high latitude seas. Less appreciated is natural environmental variation within these systems, particularly in terms of pH, and how this natural variation may inform laboratory experiments. In this study, we deployed sensor-equipped moorings at 20 m depths at three locations in McMurdo Sound, comprising deep (bottom depth>200 m: Hut Point Peninsula) and shallow environments (bottom depth ∼25 m: Cape Evans and New Harbor). Our sensors recorded high-frequency variation in pH (Hut Point and Cape Evans only), tide (Cape Evans and New Harbor), and water mass properties (temperature and salinity) during spring and early summer 2011. These collective observations showed that (1) pH differed spatially both in terms of mean pH (Cape Evans: 8.009±0.015; Hut Point: 8.020±0.007) and range of pH (Cape Evans: 0.090; Hut Point: 0.036), and (2) pH was not related to the mixing of two water masses, suggesting that the observed pH variation is likely not driven by this abiotic process. Given the large daily fluctuation in pH at Cape Evans, we developed a simple mechanistic model to explore the potential for biotic processes – in this case algal photosynthesis – to increase pH by fixing carbon from the water column. For this model, we incorporated published photosynthetic parameters for the three dominant algal functional groups found at Cape Evans (benthic fleshy red macroalgae, crustose coralline algae, and sea ice algal communities) to estimate oxygen produced/carbon fixed from the water column underneath fast sea ice and the resulting pH change. These results suggest that biotic processes may be a primary driver of pH variation observed under fast sea ice at Cape Evans and potentially at other shallow sites in McMurdo Sound.

Ocean acidification (OA) is expected to have a major impact on marine species, particularly during early life-history stages. These effects appear to be species-specific and may include reduced survival, altered morphology, and depressed metabolism. However, less information is available regarding the bioenergetics of development under elevated CO(2) conditions. We examined the biochemical and morphological responses of Strongylocentrotus purpuratus during early development under ecologically relevant levels of pCO(2) (365, 1030, and 1450 μatm) that may occur during intense upwelling events. The principal findings of this study were (1) lipid utilization rates and protein content in S. purpuratus did not vary with pCO(2); (2) larval growth was reduced at elevated pCO(2) despite similar rates of energy utilization; and (3) relationships between egg phospholipid content and larval length were found under control but not high pCO(2) conditions. These results suggest that this species may either prioritize endogenous energy toward development and physiological function at the expense of growth, or that reduced larval length may be strictly due to higher costs of growth under OA conditions. This study highlights the need to further expand our knowledge of the physiological mechanisms involved in OA response in order to better understand how present populations may respond to global environmental change.