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.

Global Ocean Spectrophotometric pH Assessment: Consistent Inconsistencies.

Ocean acidification (OA)-or the decrease in seawater pH resulting from ocean uptake of CO2 released by human activities-stresses ocean ecosystems and is recognized as a Climate and Sustainable Development Goal Indicator that needs to be evaluated and monitored. Monitoring OA-related pH changes requires a high level of precision and accuracy. The two most common ways to quantify seawater pH are to measure it spectrophotometrically or to calculate it from total alkalinity (TA) and dissolved inorganic carbon (DIC). However, despite decades of research, small but important inconsistencies remain between measured and calculated pH. To date, this issue has been circumvented by examining changes only in consistently measured properties. Currently, the oceanographic community is defining new observational strategies for OA and other key aspects of the ocean carbon cycle based on novel sensors and technologies that rely on validation against data records and/or synthesis products. Comparison of measured spectrophotometric pH to calculated pH from TA and DIC measured during the 2000s and 2010s eras reveals that (1) there is an evolution toward a better agreement between measured and calculated pH over time from 0.02 pH units in the 2000s to 0.01 pH units in the 2010s at pH > 7.6; (2) a disagreement greater than 0.01 pH units persists in waters with pH < 7.6, and (3) inconsistencies likely stem from variations in the spectrophotometric pH standard operating procedure (SOP). A reassessment of pH measurement and calculation SOPs and metrology is urgently needed.

Purified meta-Cresol Purple dye perturbation: How it influences spectrophotometric pH measurements.

Ocean acidification, a phenomenon of seawater pH decrease due to increasing atmospheric CO2, has a global effect on seawater chemistry, marine biology, and ecosystems. Ocean acidification is a gradual and global long-term process, the study of which demands high-quality pH data. The spectrophotometric technique is capable of generating accurate and precise pH measurements but requires adding an indicator dye that perturbs the sample original pH. While the perturbation is modest in well-buffered seawater, applications of the method in environments with lower buffer capacity such as riverine, estuarine, sea-ice meltwater and lacustrine environments are increasingly common, and uncertainties related to larger potential dye perturbations need further evaluation. In this paper, we assess the effect of purified meta-Cresol Purple (mCP) dye addition on the sample pH and how to correct for this dye perturbation. We conducted numerical simulations by incorporating mCP speciation into the MATLAB CO2SYS program to examine the changes in water sample pH caused by the dye addition and to reveal the dye perturbation mechanisms. Then, laboratory experiments were carried out to verify the simulation results. The simulations suggest that the dye perturbation on sample pH is a result of total alkalinity (TA) contributions from the indicator dye and chemical equilibrium shifts that are related to both the water sample properties (pH, TA, and salinity) and the indicator dye solution properties (pH and solvent matrix). The laboratory experiments supported the simulation results; the same dye solution can lead to different dye perturbations in water samples with different pH, TA, and salinity values. The modeled adjustments agreed well with the empirically determined adjustments for salinities > 5, but it showed greater errors for lower salinities with disagreements as large as 0.005 pH units. Adjustments are minimized when the pH and salinity of the dye are matched to the sample. When the dye is used over a wide range of salinity, we suggest that it should be prepared in deionized water to minimize the dye perturbation effect on pH in the fresher sample waters with less well-constrained perturbation adjustments. We also suggest that the dye perturbation correction should be based on double dye addition experiments performed over a wide range of pH, TA, and salinity. Otherwise, multiple volume dye addition experiments are recommended for each sample to determine the dye perturbation adjustment. We further create a MATLAB function dyeperturbation.m that calculates the expected dye perturbation. This function can be used to validate empirically-derived adjustments or in lieu of empirical adjustments if dye addition experiments are unfeasible (e.g., for historical data). This study of dye perturbation evaluation and correction will improve the accuracy of the pH data, necessary for monitoring the long-term anthropogenic-driven changes in the seawater carbonate system.

Detecting the unexpected: a research framework for ocean acidification.

The threat that ocean acidification (OA) poses to marine ecosystems is now recognized and U.S. funding agencies have designated specific funding for the study of OA. We present a research framework for studying OA that describes it as a biogeochemical event that impacts individual species and ecosystems in potentially unexpected ways. We draw upon specific lessons learned about ecosystem responses from research on acid rain, carbon dioxide enrichment in terrestrial plant communities, and nitrogen deposition. We further characterize the links between carbon chemistry changes and effects on individuals and ecosystems, and enumerate key hypotheses for testing. Finally, we quantify how U.S. research funding has been distributed among these linkages, concluding that there is an urgent need for research programs designed to anticipate how the effects of OA will reverberate throughout assemblages of species.

A mapped dataset of surface ocean acidification indicators in large marine ecosystems of the United States.

Mapped monthly data products of surface ocean acidification indicators from 1998 to 2022 on a 0.25° by 0.25° spatial grid have been developed for eleven U.S. large marine ecosystems (LMEs). The data products were constructed using observations from the Surface Ocean CO2 Atlas, co-located surface ocean properties, and two types of machine learning algorithms: Gaussian mixture models to organize LMEs into clusters of similar environmental variability and random forest regressions (RFRs) that were trained and applied within each cluster to spatiotemporally interpolate the observational data. The data products, called RFR-LMEs, have been averaged into regional timeseries to summarize the status of ocean acidification in U.S. coastal waters, showing a domain-wide carbon dioxide partial pressure increase of 1.4 ± 0.4 µatm yr-1 and pH decrease of 0.0014 ± 0.0004 yr-1. RFR-LMEs have been evaluated via comparisons to discrete shipboard data, fixed timeseries, and other mapped surface ocean carbon chemistry data products. Regionally averaged timeseries of RFR-LME indicators are provided online through the NOAA National Marine Ecosystem Status web portal.

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.

High spatial resolution global ocean metagenomes from Bio-GO-SHIP repeat hydrography transects.

Detailed descriptions of microbial communities have lagged far behind physical and chemical measurements in the marine environment. Here, we present 971 globally distributed surface ocean metagenomes collected at high spatio-temporal resolution. Our low-cost metagenomic sequencing protocol produced 3.65 terabases of data, where the median number of base pairs per sample was 3.41 billion. The median distance between sampling stations was 26 km. The metagenomic libraries described here were collected as a part of a biological initiative for the Global Ocean Ship-based Hydrographic Investigations Program, or "Bio-GO-SHIP." One of the primary aims of GO-SHIP is to produce high spatial and vertical resolution measurements of key state variables to directly quantify climate change impacts on ocean environments. By similarly collecting marine metagenomes at high spatiotemporal resolution, we expect that this dataset will help answer questions about the link between microbial communities and biogeochemical fluxes in a changing ocean.

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.

An observing system simulation for Southern Ocean carbon dioxide uptake.

The Southern Ocean is critically important to the oceanic uptake of anthropogenic CO2. Up to half of the excess CO2 currently in the ocean entered through the Southern Ocean. That uptake helps to maintain the global carbon balance and buffers transient climate change from fossil fuel emissions. However, the future evolution of the uptake is uncertain, because our understanding of the dynamics that govern the Southern Ocean CO2 uptake is incomplete. Sparse observations and incomplete model formulations limit our ability to constrain the monthly and annual uptake, interannual variability and long-term trends. Float-based sampling of ocean biogeochemistry provides an opportunity for transforming our understanding of the Southern Ocean CO2 flux. In this work, we review current estimates of the CO2 uptake in the Southern Ocean and projections of its response to climate change. We then show, via an observational system simulation experiment, that float-based sampling provides a significant opportunity for measuring the mean fluxes and monitoring the mean uptake over decadal scales.