Coastal eutrophication drives acidification, oxygen loss, and ecosystem change in a major oceanic upwelling system.

Global change is leading to warming, acidification, and oxygen loss in the ocean. In the Southern California Bight, an eastern boundary upwelling system, these stressors are exacerbated by the localized discharge of anthropogenically enhanced nutrients from a coastal population of 23 million people. Here, we use simulations with a high-resolution, physical-biogeochemical model to quantify the link between terrestrial and atmospheric nutrients, organic matter, and carbon inputs and biogeochemical change in the coastal waters of the Southern California Bight. The model is forced by large-scale climatic drivers and a reconstruction of local inputs via rivers, wastewater outfalls, and atmospheric deposition; it captures the fine scales of ocean circulation along the shelf; and it is validated against a large collection of physical and biogeochemical observations. Local land-based and atmospheric inputs, enhanced by anthropogenic sources, drive a 79% increase in phytoplankton biomass, a 23% increase in primary production, and a nearly 44% increase in subsurface respiration rates along the coast in summer, reshaping the biogeochemistry of the Southern California Bight. Seasonal reductions in subsurface oxygen, pH, and aragonite saturation state, by up to 50 mmol m-3, 0.09, and 0.47, respectively, rival or exceed the global open-ocean oxygen loss and acidification since the preindustrial period. The biological effects of these changes on local fisheries, proliferation of harmful algal blooms, water clarity, and submerged aquatic vegetation have yet to be fully explored.

Global variability in seawater Mg:Ca and Sr:Ca ratios in the modern ocean.

Seawater Mg:Ca and Sr:Ca ratios are biogeochemical parameters reflecting the Earth-ocean-atmosphere dynamic exchange of elements. The ratios' dependence on the environment and organisms' biology facilitates their application in marine sciences. Here, we present a measured single-laboratory dataset, combined with previous data, to test the assumption of limited seawater Mg:Ca and Sr:Ca variability across marine environments globally. High variability was found in open-ocean upwelling and polar regions, shelves/neritic and river-influenced areas, where seawater Mg:Ca and Sr:Ca ratios range from ∼4.40 to 6.40 mmol:mol and ∼6.95 to 9.80 mmol:mol, respectively. Open-ocean seawater Mg:Ca is semiconservative (∼4.90 to 5.30 mol:mol), while Sr:Ca is more variable and nonconservative (∼7.70 to 8.80 mmol:mol); both ratios are nonconservative in coastal seas. Further, the Ca, Mg, and Sr elemental fluxes are connected to large total alkalinity deviations from International Association for the Physical Sciences of the Oceans (IAPSO) standard values. Because there is significant modern seawater Mg:Ca and Sr:Ca ratios variability across marine environments we cannot absolutely assume that fossil archives using taxa-specific proxies reflect true global seawater chemistry but rather taxa- and process-specific ecosystem variations, reflecting regional conditions. This variability could reconcile secular seawater Mg:Ca and Sr:Ca ratio reconstructions using different taxa and techniques by assuming an error of 1 to 1.50 mol:mol, and 1 to 1.90 mmol:mol, respectively. The modern ratios' variability is similar to the reconstructed rise over 20 Ma (Neogene Period), nurturing the question of seminonconservative behavior of Ca, Mg, and Sr over modern Earth geological history with an overlooked environmental effect.

Pelagic calcifiers face increased mortality and habitat loss with warming and ocean acidification.

Global change is impacting the oceans in an unprecedented way, and multiple lines of evidence suggest that species distributions are changing in space and time. There is increasing evidence that multiple environmental stressors act together to constrain species habitat more than expected from warming alone. Here, we conducted a comprehensive study of how temperature and aragonite saturation state act together to limit Limacina helicina, globally distributed pteropods that are ecologically important pelagic calcifiers and an indicator species for ocean change. We co-validated three different approaches to evaluate the impact of ocean warming and acidification (OWA) on the survival and distribution of this species in the California Current Ecosystem. First, we used colocated physical, chemical, and biological data from three large-scale west coast cruises and regional time series; second, we conducted multifactorial experimental incubations to evaluate how OWA impacts pteropod survival; and third, we validated the relationships we found against global distributions of pteropods and carbonate chemistry. OWA experimental work revealed mortality increases under OWA, while regional habitat suitability indices and global distributions of L. helicina suggest that a multi-stressor framework is essential for understanding pteropod distributions. In California Current Ecosystem habitats, where pteropods are living close to their thermal maximum already, additional warming and acidification through unabated fossil fuel emissions (RCP 8.5) are expected to dramatically reduce habitat suitability.

Natural Analogues in pH Variability and Predictability across the Coastal Pacific Estuaries: Extrapolation of the Increased Oyster Dissolution under Increased pH Amplitude and Low Predictability Related to Ocean Acidification.

Coastal-estuarine habitats are rapidly changing due to global climate change, with impacts influenced by the variability of carbonate chemistry conditions. However, our understanding of the responses of ecologically and economically important calcifiers to pH variability and temporal variation is limited, particularly with respect to shell-building processes. We investigated the mechanisms driving biomineralogical and physiological responses in juveniles of introduced (Pacific; Crassostrea gigas) and native (Olympia; Ostrea lurida) oysters under flow-through experimental conditions over a six-week period that simulate current and future conditions: static control and low pH (8.0 and 7.7); low pH with fluctuating (24-h) amplitude (7.7 ± 0.2 and 7.7 ± 0.5); and high-frequency (12-h) fluctuating (8.0 ± 0.2) treatment. The oysters showed physiological tolerance in vital processes, including calcification, respiration, clearance, and survival. However, shell dissolution significantly increased with larger amplitudes of pH variability compared to static pH conditions, attributable to the longer cumulative exposure to lower pH conditions, with the dissolution threshold of pH 7.7 with 0.2 amplitude. Moreover, the high-frequency treatment triggered significantly greater dissolution, likely because of the oyster's inability to respond to the unpredictable frequency of variations. The experimental findings were extrapolated to provide context for conditions existing in several Pacific coastal estuaries, with time series analyses demonstrating unique signatures of pH predictability and variability in these habitats, indicating potentially benefiting effects on fitness in these habitats. These implications are crucial for evaluating the suitability of coastal habitats for aquaculture, adaptation, and carbon dioxide removal strategies.

Spectrophotometric Determination of Carbonate Ion Concentrations: Elimination of Instrument-Dependent Offsets and Calculation of In Situ Saturation States.

This work describes an improved algorithm for spectrophotometric determinations of seawater carbonate ion concentrations ([CO32-]spec) derived from observations of ultraviolet absorbance spectra in lead-enriched seawater. Quality-control assessments of [CO32-]spec data obtained on two NOAA research cruises (2012 and 2016) revealed a substantial intercruise difference in average Δ[CO32-] (the difference between a sample's [CO32-]spec value and the corresponding [CO32-] value calculated from paired measurements of pH and dissolved inorganic carbon). Follow-up investigation determined that this discordance was due to the use of two different spectrophotometers, even though both had been properly calibrated. Here we present an essential methodological refinement to correct [CO32-]spec absorbance data for small but significant instrumental differences. After applying the correction (which, notably, is not necessary for pH determinations from sulfonephthalein dye absorbances) to the shipboard absorbance data, we fit the combined-cruise data set to produce empirically updated parameters for use in processing future (and historical) [CO32-]spec absorbance measurements. With the new procedure, the average Δ[CO32-] offset between the two aforementioned cruises was reduced from 3.7 µmol kg-1 to 0.7 µmol kg-1, which is well within the standard deviation of the measurements (1.9 µmol kg-1). We also introduce an empirical model to calculate in situ carbonate ion concentrations from [CO32-]spec. We demonstrate that these in situ values can be used to determine calcium carbonate saturation states that are in good agreement with those determined by more laborious and expensive conventional methods.

Predictable patterns within the kelp forest can indirectly create temporary refugia from ocean acidification.

Kelps are recognized for providing many ecosystem services in coastal areas and considered in ocean acidification (OA) mitigation. However, assessing OA modification requires an understanding of the multiple parameters involved in carbonate chemistry, especially in highly dynamic systems. We studied the effects of sugar kelp (Saccharina latissima) on an experimental farm at the north end of Hood Canal, Washington-a low retentive coastal system. In this field mesocosm study, two oyster species (Magallana gigas, Ostrea lurida) were exposed at locations in the mid, edge, and outside the kelp array. The Hood Head Sugar Kelp Farm Model outputs were used to identify dominating factors in spatial and temporal kelp dynamics, while wavelet spectrum analyses helped in understanding predictability patterns. This was linked to the measured biological responses (dissolution, growth, isotopes) of the exposed organisms. Positioned in an area of high (sub)-diel tidal fluxes with low retention potential, there were no measurable alterations of the seawater pH at the study site, demonstrating that the kelp array could not induce a direct mitigating effect against OA. However, beneficial responses in calcifiers were still observed, which are linked to two causes: increased pH predictability and improved provisioning through kelp-derived particulate organic resource utilization and as such, kelp improved habitat suitability and indirectly created refugia against OA. This study can serve as an analogue for many coastal bay habitats where prevailing physical forcing drives chemical changes. Future macrophyte studies that investigate OA mitigating effects should focus also on the importance of predictability patterns, which can additionally improve the conditions for marine calcifiers and ecosystem services vulnerable to or compromised by OA, including aquaculture sustainability.

Widespread and increasing near-bottom hypoxia in the coastal ocean off the United States Pacific Northwest.

The 2021 summer upwelling season off the United States Pacific Northwest coast was unusually strong leading to widespread near-bottom, low-oxygen waters. During summer 2021, an unprecedented number of ship- and underwater glider-based measurements of dissolved oxygen were made in this region. Near-bottom hypoxia, that is dissolved oxygen less than 61 µmol kg-1 and harmful to marine animals, was observed over nearly half of the continental shelf inshore of the 200-m isobath, covering 15,500 square kilometers. A mid-shelf ribbon with near-bottom, dissolved oxygen less than 50 µmol kg-1 extended for 450 km off north-central Oregon and Washington. Spatial patterns in near-bottom oxygen are related to the continental shelf width and other features of the region. Maps of near-bottom oxygen since 1950 show a consistent trend toward lower oxygen levels over time. The fraction of near-bottom water inshore of the 200-m isobath that is hypoxic on average during the summer upwelling season increases over time from nearly absent (2%) in 1950-1980, to 24% in 2009-2018, compared with 56% during the anomalously strong upwelling conditions in 2021. Widespread and increasing near-bottom hypoxia is consistent with increased upwelling-favorable wind forcing under climate change.

Spectrophotometric measurement of calcium carbonate saturation states in seawater.

Measurements of ocean pH and carbonate ion concentrations in the North Pacific and Arctic Oceans were used to determine calcium carbonate saturation states (Ω(CaCO(3))) from spectrophotometric methods alone. Total carbonate ion concentrations, [CO(3)(2-)](T), were for the first time at sea directly measured using Pb(II) UV absorbance spectra. The basis of the method is given by the following: [formula see text] where (CO(3))ß(1) is the PbCO(3)(0) formation constant, e(i) are molar absorptivity ratios, and R = (250)A/(234)A (ratio of absorbances measured at 250 and 234 nm). On the basis of shipboard and laboratory Pb(II) data and complementary carbon-system measurements, the experimental parameters were determined to be (25 °C) the following: [formula see text]. The resulting mean difference between the shipboard spectrophotometric and conventional determinations of [CO(3)(2-)](T) was ±2.03 µmol kg(-1). The shipboard analytical precision of the Pb(II) method was ∼1.71 µmol kg(-1) (2.28%). Spectrophotometric [CO(3)(2-)](T) and pH(T) were then combined to calculate Ω(CaCO(3)). For the case of aragonite, 95% of the spectrophotometric aragonite saturation states (Ω(Aspec)) were within ±0.06 of the conventionally calculated values (Ω(Acalc)) when 0.5 ≤ Ω(A) ≤ 2.0. When Ω(A) > 2.0, 95% of the Ω(Aspec) values were within ±0.18 of Ω(Acalc). Our shipboard experience indicates that spectrophotometric determinations of [CO(3)(2-)](T) and Ω(CaCO(3)) are straightforward, fast, and precise. The method yields high-quality measurements of two important, rapidly changing aspects of ocean chemistry and offers capabilities suitable for long-term automated in situ monitoring.

Climate change drives rapid decadal acidification in the Arctic Ocean from 1994 to 2020.

The Arctic Ocean has experienced rapid warming and sea ice loss in recent decades, becoming the first open-ocean basin to experience widespread aragonite undersaturation [saturation state of aragonite (Ωarag) < 1]. However, its trend toward long-term ocean acidification and the underlying mechanisms remain undocumented. Here, we report rapid acidification there, with rates three to four times higher than in other ocean basins, and attribute it to changing sea ice coverage on a decadal time scale. Sea ice melt exposes seawater to the atmosphere and promotes rapid uptake of atmospheric carbon dioxide, lowering its alkalinity and buffer capacity and thus leading to sharp declines in pH and Ωarag. We predict a further decrease in pH, particularly at higher latitudes where sea ice retreat is active, whereas Arctic warming may counteract decreases in Ωarag in the future.

Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms.

Today's surface ocean is saturated with respect to calcium carbonate, but increasing atmospheric carbon dioxide concentrations are reducing ocean pH and carbonate ion concentrations, and thus the level of calcium carbonate saturation. Experimental evidence suggests that if these trends continue, key marine organisms--such as corals and some plankton--will have difficulty maintaining their external calcium carbonate skeletons. Here we use 13 models of the ocean-carbon cycle to assess calcium carbonate saturation under the IS92a 'business-as-usual' scenario for future emissions of anthropogenic carbon dioxide. In our projections, Southern Ocean surface waters will begin to become undersaturated with respect to aragonite, a metastable form of calcium carbonate, by the year 2050. By 2100, this undersaturation could extend throughout the entire Southern Ocean and into the subarctic Pacific Ocean. When live pteropods were exposed to our predicted level of undersaturation during a two-day shipboard experiment, their aragonite shells showed notable dissolution. Our findings indicate that conditions detrimental to high-latitude ecosystems could develop within decades, not centuries as suggested previously.

Pteropods make thinner shells in the upwelling region of the California Current Ecosystem.

Shelled pteropods are widely regarded as bioindicators for ocean acidification, because their fragile aragonite shells are susceptible to increasing ocean acidity. While short-term incubations have demonstrated that pteropod calcification is negatively impacted by ocean acidification, we know little about net calcification in response to varying ocean conditions in natural populations. Here, we examine in situ calcification of Limacina helicina pteropods collected from the California Current Ecosystem, a coastal upwelling system with strong spatial gradients in ocean carbonate chemistry, dissolved oxygen and temperature. Depth-averaged pH ranged from 8.03 in warmer offshore waters to 7.77 in cold CO2-rich waters nearshore. Based on high-resolution micro-CT technology, we showed that shell thickness declined by ~ 37% along the upwelling gradient from offshore to nearshore water. Dissolution marks covered only ~ 2% of the shell surface area and were not associated with the observed variation in shell thickness. We thus infer that pteropods make thinner shells where upwelling brings more acidified and colder waters to the surface. Probably the thinner shells do not result from enhanced dissolution, but are due to a decline in calcification. Reduced calcification of pteropods is likely to have major ecological and biogeochemical implications for the cycling of calcium carbonate in the oceans.

Severe biological effects under present-day estuarine acidification in the seasonally variable Salish Sea.

Estuaries are recognized as one of the habitats most vulnerable to coastal ocean acidification due to seasonal extremes and prolonged duration of acidified conditions. This is combined with co-occurring environmental stressors such as increased temperature and low dissolved oxygen. Despite this, evidence of biological impacts of ocean acidification in estuarine habitats is largely lacking. By combining physical, biogeochemical, and biological time-series observations over relevant seasonal-to-interannual time scales, this study is the first to describe both the spatial and temporal variation of biological response in the pteropod Limacina helicina to estuarine acidification in association with other stressors. Using clustering and principal component analyses, sampling sites were grouped according to their distribution of physical and biogeochemical variables over space and time. This identified the most exposed habitats and time intervals corresponding to the most severe negative biological impacts across three seasons and three years. We developed a cumulative stress index as a means of integrating spatial-temporal OA variation over the organismal life history. Our findings show that over the 2014-2016 study period, the severity of low aragonite saturation state combined with the duration of exposure contributed to overall cumulative stress and resulted in severe shell dissolution. Seasonally-variable estuaries such as the Salish Sea (Washington, U.S.A.) predispose sensitive organisms to more severe acidified conditions than those of coastal and open-ocean habitats, yet the sensitive organisms persist. We suggest potential environmental factors and compensatory mechanisms that allow pelagic calcifiers to inhabit less favorable habitats and partially offset associated stressors, for instance through food supply, increased temperature, and adaptation of their life history. The novel metric of cumulative stress developed here can be applied to other estuarine environments with similar physical and chemical dynamics, providing a new tool for monitoring biological response in estuaries under pressure from accelerating global change.

Natural and Anthropogenic Drivers of Acidification in Large Estuaries.

Oceanic uptake of anthropogenic carbon dioxide (CO2) from the atmosphere has changed ocean biogeochemistry and threatened the health of organisms through a process known as ocean acidification (OA). Such large-scale changes affect ecosystem functions and can have impacts on societal uses, fisheries resources, and economies. In many large estuaries, anthropogenic CO2-induced acidification is enhanced by strong stratification, long water residence times, eutrophication, and a weak acid-base buffer capacity. In this article, we review how a variety of processes influence aquatic acid-base properties in estuarine waters, including coastal upwelling, river-ocean mixing, air-water gas exchange, biological production and subsequent aerobic and anaerobic respiration, calcium carbonate (CaCO3) dissolution, and benthic inputs. We emphasize the spatial and temporal dynamics of partial pressure of CO2 (pCO2), pH, and calcium carbonate mineral saturation states. Examples from three large estuaries-Chesapeake Bay, the Salish Sea, and Prince William Sound-are used to illustrate how natural and anthropogenic processes and climate change may manifest differently across estuaries, as well as the biological implications of OA on coastal calcifiers.

Exoskeleton dissolution with mechanoreceptor damage in larval Dungeness crab related to severity of present-day ocean acidification vertical gradients.

Ocean acidification (OA) along the US West Coast is intensifying faster than observed in the global ocean. This is particularly true in nearshore regions (<200 m) that experience a lower buffering capacity while at the same time providing important habitats for ecologically and economically significant species. While the literature on the effects of OA from laboratory experiments is voluminous, there is little understanding of present-day OA in-situ effects on marine life. Dungeness crab (Metacarcinus magister) is perennially one of the most valuable commercial and recreational fisheries. We focused on establishing OA-related vulnerability of larval crustacean based on mineralogical and elemental carapace to external and internal carapace dissolution by using a combination of different methods ranging from scanning electron microscopy, energy dispersive X-ray spectroscopy, elemental mapping and X-ray diffraction. By integrating carapace features with the chemical observations and biogeochemical model hindcast, we identify the occurrence of external carapace dissolution related to the steepest Ω calcite gradients (∆Ωcal,60) in the water column. Dissolution features are observed across the carapace, pereopods (legs), and around the calcified areas surrounding neuritic canals of mechanoreceptors. The carapace dissolution is the most extensive in the coastal habitats under prolonged (1-month) long exposure, as demonstrated by the use of the model hindcast. Such dissolution has a potential to destabilize mechanoreceptors with important sensory and behavioral functions, a pathway of sensitivity to OA. Carapace dissolution is negatively related to crab larval width, demonstrating a basis for energetic trade-offs. Using a retrospective prediction from a regression models, we estimate an 8.3% increase in external carapace dissolution over the last two decades and identified a set of affected OA-related sublethal pathways to inform future risk assessment studies of Dungeness crabs.

Controls on surface water carbonate chemistry along North American ocean margins.

Syntheses of carbonate chemistry spatial patterns are important for predicting ocean acidification impacts, but are lacking in coastal oceans. Here, we show that along the North American Atlantic and Gulf coasts the meridional distributions of dissolved inorganic carbon (DIC) and carbonate mineral saturation state (Ω) are controlled by partial equilibrium with the atmosphere resulting in relatively low DIC and high Ω in warm southern waters and the opposite in cold northern waters. However, pH and the partial pressure of CO2 (pCO2) do not exhibit a simple spatial pattern and are controlled by local physical and net biological processes which impede equilibrium with the atmosphere. Along the Pacific coast, upwelling brings subsurface waters with low Ω and pH to the surface where net biological production works to raise their values. Different temperature sensitivities of carbonate properties and different timescales of influencing processes lead to contrasting property distributions within and among margins.

Surface ocean pH and buffer capacity: past, present and future.

The ocean's chemistry is changing due to the uptake of anthropogenic carbon dioxide (CO2). This phenomenon, commonly referred to as "Ocean Acidification", is endangering coral reefs and the broader marine ecosystems. In this study, we combine a recent observational seawater CO2 data product, i.e., the 6th version of the Surface Ocean CO2 Atlas (1991-2018, ~23 million observations), with temporal trends at individual locations of the global ocean from a robust Earth System Model to provide a high-resolution regionally varying view of global surface ocean pH and the Revelle Factor. The climatology extends from the pre-Industrial era (1750 C.E.) to the end of this century under historical atmospheric CO2 concentrations (pre-2005) and the Representative Concentrations Pathways (post-2005) of the Intergovernmental Panel on Climate Change (IPCC)'s 5th Assessment Report. By linking the modeled pH trends to the observed modern pH distribution, the climatology benefits from recent improvements in both model design and observational data coverage, and is likely to provide improved regional OA trajectories than the model output could alone, therefore, will help guide the regional OA adaptation strategies. We show that air-sea CO2 disequilibrium is the dominant mode of spatial variability for surface pH, and discuss why pH and calcium carbonate mineral saturation states, two important metrics for OA, show contrasting spatial variability.

The oceanic sink for anthropogenic CO2 from 1994 to 2007.

We quantify the oceanic sink for anthropogenic carbon dioxide (CO2) over the period 1994 to 2007 by using observations from the global repeat hydrography program and contrasting them to observations from the 1990s. Using a linear regression-based method, we find a global increase in the anthropogenic CO2 inventory of 34 ± 4 petagrams of carbon (Pg C) between 1994 and 2007. This is equivalent to an average uptake rate of 2.6 ± 0.3 Pg C year-1 and represents 31 ± 4% of the global anthropogenic CO2 emissions over this period. Although this global ocean sink estimate is consistent with the expectation of the ocean uptake having increased in proportion to the rise in atmospheric CO2, substantial regional differences in storage rate are found, likely owing to climate variability-driven changes in ocean circulation.

Progressive Infantile Scoliosis Managed With Osteopathic Manipulative Treatment.

Infantile idiopathic scoliosis is a compensatory result of cranial and sacral intraosseous dysfunction associated with asymmetric developmental deformation of the occiput, leading to dysfunction of the sphenobasilar synchondrosis. A female infant with progressive infantile idiopathic scoliosis diagnosed at age 12 months (46.9° left scoliotic curve) initially received standard orthopedic care, including casting. The patient presented for osteopathic evaluation at age 14 months, at which time her scoliotic curve was 52°. The patient wore a Risser cast extending from T1-L5 at her first osteopathic manipulative treatment (OMT) visit, which included osteopathic cranial manipulative medicine. Her parents chose to have the cast removed at age 17 months, with a 23° curve remaining. For approximately 12 months, OMT was the only continued, consistent treatment, which occurred once per month. By 28 months of age, radiographs measured 0° of scoliosis. This case demonstrates that OMT can dramatically improve infantile idiopathic scoliosis and prevent its progression.

Experiments with Seasonal Forecasts of ocean conditions for the Northern region of the California Current upwelling system.

Resource managers at the state, federal, and tribal levels make decisions on a weekly to quarterly basis, and fishers operate on a similar timeframe. To determine the potential of a support tool for these efforts, a seasonal forecast system is experimented with here. JISAO's Seasonal Coastal Ocean Prediction of the Ecosystem (J-SCOPE) features dynamical downscaling of regional ocean conditions in Washington and Oregon waters using a combination of a high-resolution regional model with biogeochemistry and forecasts from NOAA's Climate Forecast System (CFS). Model performance and predictability were examined for sea surface temperature (SST), bottom temperature, bottom oxygen, pH, and aragonite saturation state through model hindcasts, reforecast, and forecast comparisons with observations. Results indicate J-SCOPE forecasts have measurable skill on seasonal timescales. Experiments suggest that seasonal forecasting of ocean conditions important for fisheries is possible with the right combination of components. Those components include regional predictability on seasonal timescales of the physical environment from a large-scale model, a high-resolution regional model with biogeochemistry that simulates seasonal conditions in hindcasts, a relationship with local stakeholders, and a real-time observational network. Multiple efforts and approaches in different regions would advance knowledge to provide additional tools to fishers and other stakeholders.

Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.