Explore the vast range of titles available.

Streams, rivers, lakes, and other inland waters are important agents in the coupling of biogeochemical cycles between continents, atmosphere, and oceans. The depiction of these roles in global-scale assessments of carbon (C) and other bioactive elements remains limited, yet recent findings suggest that C discharged to the oceans is only a fraction of that entering rivers from terrestrial ecosystems via soil respiration, leaching, chemical weathering, and physical erosion. Most of this C influx is returned to the atmosphere from inland waters as carbon dioxide (CO 2 ) or buried in sedimentary deposits within impoundments, lakes, floodplains, and other wetlands. Carbon and mineral cycles are coupled by both erosion-–deposition processes and chemical weathering, with the latter producing dissolved inorganic C and carbonate buffering capacity that strongly modulate downstream pH, biological production of calcium-carbonate shells, and CO 2 outgassing in rivers, estuaries, and coastal zones. Human activities substantially affect all of these processes.

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 CO 2 ( p CO 2 ) 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. Anthropogenic CO 2 is acidifying the ocean, but knowledge of the carbonate properties underlying these dynamics in coastal oceans is lacking. Here, the authors reveal spatial distribution patterns and variability in carbonate chemistry along North America’s coasts.

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 CO 2 -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.

Predicting the pace of acidification in the California Current System (CCS), a productive upwelling system that borders the west coast of North America, is complex because the anthropogenic contribution is intertwined with other natural sources. A central question is whether acidification in the CCS will follow the pace of increasing atmospheric CO 2 , or if climate effects and other biogeochemical processes will either amplify or attenuate acidification. Here, we apply the boron isotope pH proxy to cold-water orange cup corals to establish a historic level of acidification in the CCS and the Salish Sea, an associated marginal sea. Through a combination of complementary modeling and geochemical approaches, we show that the CCS and Salish Sea have experienced amplified acidification over the industrial era, driven by the interaction between anthropogenic CO 2 and a thermodynamic buffering effect. From this foundation, we project future acidification in the CCS under elevated CO 2 emissions. The projected change in p CO 2 over the 21 st century will continue to outpace atmospheric CO 2 , posing challenges to marine ecosystems of biological, cultural, and economic importance. Boron isotopes in cold-water corals reveal that acidification in the California Current and Salish Sea has outpaced atmospheric CO 2 over the industrial era, posing a threat to ecosystems of ecological, cultural and economic value.

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.

The California Current System (CCS) is expected to experience the ecological impacts of ocean acidification (OA) earlier than most other ocean regions because coastal upwelling brings old, CO2‐rich water relatively close to the surface ocean. Historical inorganic carbon measurements are scarce, so the progression of OA in the CCS is unknown. We used a multiple linear regression approach to generate empirical models using oxygen (O2), temperature (T), salinity (S), and sigma theta (σθ) as proxy variables to reconstruct pH, carbonate saturation states, carbonate ion concentration ([CO32−]), dissolved inorganic carbon (DIC) concentration, and total alkalinity (TA) in the southern CCS. The calibration data included high‐quality measurements of carbon, oxygen, and other hydrographic variables, collected during a cruise from British Columbia to Baja California in May–June 2007. All resulting empirical relationships were robust, withr2values >0.92 and low root mean square errors. Estimated and measured carbon chemistry matched very well for independent data sets from the CalCOFI and IMECOCAL programs. Reconstructed CCS pH and saturation states for 2005–2011 reveal a pronounced seasonal cycle and inter‐annual variability in the upper water column. Deeper in the water column, conditions are stable throughout the annual cycle, with perennially low pH and saturation states. Over sub‐decadal time scales, these empirical models provide a valuable tool for reconstructing carbonate chemistry related to ocean acidification where direct observations are limited. However, progressive increases in anthropogenic CO2 content of southern CCS water masses must be carefully addressed to apply the models over longer time scales. Key Points Carbonate system parameters can be robustly estimated using proxy variables Large seasonal and inter‐annual variability in the California Current System Eddy formation and upwelling bring undersaturated water near the surface

Marine carbon dioxide (CO2) system data has been collected from December 2014 to June 2018 in the northern Salish Sea (NSS; British Columbia, Canada) and consisted of continuous measurements at two sites as well as spatially- and seasonally-distributed discrete seawater samples. The array of CO2 observing activities included high-resolution CO2 partial pressure (pCO2) and pHT (total scale) measurements made at the Hakai Institute’s Quadra Island Field Station (QIFS) and from an Environment Canada weather buoy, respectively, as well as discrete seawater measurements of pCO2 and total dissolved inorganic carbon (TCO2) obtained during a number of field campaigns. A relationship between NSS alkalinity and salinity was developed with the discrete datasets and used with the continuous measurements to highly resolve the marine CO2 system. Collectively, these datasets provided insights into the seasonality in this historically under-sampled region and detail the area’s tendency for aragonite saturation state () to be at non-corrosive levels (i.e. > 1) only in the upper water column during spring and summer months. This depth zone and time period of reprieve can be periodically interrupted by strong northwesterly winds that drive short-lived (~1 week) episodes of high-pCO2, low-pH, and low- conditions throughout the region. Interannual variability in summertime conditions was evident and linked to reduced northwesterly winds and increased stratification. Anthropogenic CO2 in NSS surface water was estimated using data from 2017 combined with the global atmospheric CO2 forcing for the period 1765 to 2100, and projected a mean value of 49 ± 5 µmol kg-1 for 2018. The estimated trend in anthropogenic CO2 was further used to assess the evolution of and pHT levels in NSS surface water, and revealed that wintertime corrosive conditions were likely absent pre-1900. The percent of the year spent above = 1 has dropped from ~98% in 1900 to ~60% by 2018. Over the coming decades, winter pHT and spring and summer are projected to decline to conditions below identified biological thresholds for select vulnerable species.

Evidence of ocean acidification (OA) throughout the global ocean has galvanized some coastal communities to evaluate carbonate chemistry variations closer to home. An impediment to doing this effectively is that, often, only one carbonate system parameter is measured at a time, while two are required to fully constrain the inorganic carbon chemistry of seawater. In order to leverage the abundant singlecaibonate-parameter datasets in Washington State for more rigorous OA research, we have characterized an empirical relationship between total alkalinity (TA) and salinity (TA = 47.7 × S + 647; lσ = ±17 μmol kg⁻¹) for regional surface waters (≤25 m) that is robust in the salinity range from 20 to 35 for all seasons. The relationship was evaluated using 5 years of 3-h contemporaneous observations of salinity, carbon dioxide partial pressure (pCO₂), and pH from a surface mooring on the outer coast of Washington. In situ pCO₂ observations and salinity-based estimates of TA were used to calculate pH for comparison with in situ pH measurements. On average, the calculated pH values were 0.02 units lower than the measured pH values across multiple pH sensor deployments and showed extremely high fidelity in tracking the measured high-frequency pH variations. Our results indicate that the TA-salinity relationship will be a useful tool for expanding single-carbonate-parameter datasets in Washington State and quality controlling dual pCO₂-pH time senes.

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).

Dungeness crab ( Metacarcinus magister ) have significant socioeconomic value, but are threatened by ocean acidification (OA) and other environmental stressors that are driven by climate change. Despite evidence that adult harvests are sensitive to the abundance of larval populations, relatively little is known about how Dungeness megalopae will respond to these stressors. Here we evaluate the ability to use micro-computed tomography (μCT) to detect variations in megalope exoskeleton density and how these measurements reflect environmental variables and calcification mechanisms. We use a combination of field data, culture experiments, and model simulations to suggest resolvable differences in density are best explained by minimum pH at the time zoeae molt into megalopae. We suggest that this occurs because more energy must be expended on active ion pumping to reach a given degree of calcite supersaturation at lower pH. Energy availability may also be reduced due to its diversion to other coping mechanisms. Alternate models based on minimum temperature at the time of the zoea-megalope molt are nearly as strong and complicate the ability to conclusively disentangle pH and temperature influences. Despite this, our results suggest that carryover effects between life stages and short-lived extreme events may be particularly important controls on exoskeleton integrity. μCT-based estimates of exoskeleton density are a promising tool for evaluating the health of Dungeness crab populations that will likely provide more nuanced information than presence-absence observations, but future in situ field sampling and culture experiments are needed to refine and validate our results.