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Stable Ca and Sr isotopes support volcanically triggered biocalcification crisis during Oceanic Anoxic Event 1a

Large igneous province (LIP) eruptions are hypothesized to trigger biocalcification crises. The Aptian nannoconid crisis, which correlates with emplacement of the Ontong Java Plateau and Oceanic Anoxic Event 1a (OAE 1a, ca. 120 Ma), represents one such example. The Ca isotope (δ44/40Ca) system offers potential to detect biocalcification fluctuations in the rock record because Ca isotope fractionation is sensitive to precipitation rate. However, other primary and secondary processes, such as input-output flux perturbations and early diagenesis, can produce similar signals. Here, we exploit emergent properties of the stable Sr isotope (δ88/86Sr) system to resolve the origin of δ44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ44/40Ca, δ88/86Sr, and 87Sr/86Sr records for Hole 866A of Ocean Drilling Program Leg 143 drilled in Resolution Guyot, mid-Pacific Ocean. The samples span ~27 m.y. from the Barremian (ca. 127 Ma) to the Albian (ca. 100 Ma). The δ44/40Ca and δ88/86Sr secular trends differ from the 87Sr/86Sr record but mimic each other. δ44/40Ca and [Sr], as well as δ44/40Ca and δ88/86Sr, strongly correlate and yield slopes predicted for kinetic control, which demonstrates that variable mass-dependent fractionation rather than end-member mixing dominated the isotopic relationship between carbonates and seawater. Positive δ44/40Ca and δ88/86Sr shifts that begin before OAE 1a and peak within the interval are consistent with reduced precipitation rates. All results combined point to a cascade of effects on rate-dependent Ca and Sr isotope fractionation, which derive from the dynamic interplay between LIP eruptions and biocalcification feedbacks.

Continue reading ‘Stable Ca and Sr isotopes support volcanically triggered biocalcification crisis during Oceanic Anoxic Event 1a’

New edition of the “OA-ICC Highlights”, July-December 2020

Continue reading ‘New edition of the “OA-ICC Highlights”, July-December 2020’

Volcanic eruptions directly triggered ocean acidification during Early Cretaceous

Around 120 million years ago, the earth experienced an extreme environmental disruption that choked oxygen from its oceans.

Known as oceanic anoxic event (OAE) 1a, the oxygen-deprived water led to a minor — but significant — mass extinction that affected the entire globe. During this age in the Early Cretaceous Period, an entire family of sea-dwelling nannoplankton virtually disappeared.

By measuring calcium and strontium isotope abundances in nannoplankton fossils, Northwestern earth scientists have concluded the eruption of the Ontong Java Plateau large igneous province (LIP) directly triggered OAE1a. Roughly the size of Alaska, the Ontong Java LIP erupted for seven million years, making it one of the largest known LIP events ever. During this time, it spewed tons of carbon dioxide (CO2) into the atmosphere, pushing Earth into a greenhouse period that acidified seawater and suffocated the oceans.

Continue reading ‘Volcanic eruptions directly triggered ocean acidification during Early Cretaceous’

Dichotomy between regulation of coral bacterial communities and calcification physiology under ocean acidification conditions

Ocean acidification (OA) threatens the growth and function of coral reef ecosystems. A key component to coral health is the microbiome, but little is known about the impact of OA on coral microbiomes. A submarine CO2 vent at Maug Island in the Northern Marianas Islands provides a natural pH gradient to investigate coral responses to long-term OA conditions. Three coral species (Pocillopora eydouxiPorites lobata, and Porites rus) were sampled from three sites where mean seawater pH is 8.04, 7.98, and 7.94. We characterized coral bacterial communities (using 16S rRNA gene sequencing) and determined pH of the extracellular calcifying fluid (ECF) (using skeletal boron isotopes) across the seawater pH gradient. Bacterial communities of both Porites species stabilized (decreases in community dispersion) with decreased seawater pH, coupled with large increases in the abundance of Endozoicomonas, an endosymbiont. P. lobata experienced a significant decrease in ECF pH near the vent, whereas P. rus experienced a trending decrease in ECF pH near the vent. By contrast, Pocillopora exhibited bacterial community destabilization (increases in community dispersion), with significant decreases in Endozoicomonas abundance, while its ECF pH remained unchanged across the pH gradient. Our study shows that OA has multiple consequences on Endozoicomonas abundance and suggests that Endozoicomonas abundance may be an indicator of coral response to OA. We reveal an interesting dichotomy between two facets of coral physiology (regulation of bacterial communities and regulation of calcification), highlighting the importance of multidisciplinary approaches to understanding coral health and function in a changing ocean.

Continue reading ‘Dichotomy between regulation of coral bacterial communities and calcification physiology under ocean acidification conditions’

Autonomous in situ calibration of ion‐sensitive field effect transistor pH sensors

Ion‐sensitive field effect transistor‐based pH sensors have been shown to perform well in high frequency and long‐term ocean sampling regimes. The Honeywell Durafet is widely used due to its stability, fast response, and characterization over a large range of oceanic conditions. However, potentiometric pH monitoring is inherently complicated by the fact that the sensors require careful calibration. Offsets in calibration coefficients have been observed when comparing laboratory to field‐based calibrations and prior work has led to the recommendation that an in situ calibration be performed based on comparison to discrete samples. Here, we describe our work toward a self‐calibration apparatus integrated into a SeapHOx pH, dissolved oxygen, and CTD sensor package. This Self‐Calibrating SeapHOx is capable of autonomously recording calibration values from a high quality, traceable, primary reference standard: equimolar tris buffer. The Self‐Calibrating SeapHOx’s functionality was demonstrated in a 6‐d test in a seawater tank at Scripps Institution of Oceanography (La Jolla, California, U.S.A.) and was successfully deployed for 2 weeks on a shallow, coral reef flat (Lizard Island, Australia). During the latter deployment, the tris‐based self‐calibration using 15 on‐board samples exhibited superior reproducibility to the standard spectrophotometric pH‐based calibration using > 100 discrete samples. Standard deviations of calibration pH using tris ranged from 0.002 to 0.005 whereas they ranged from 0.006 to 0.009 for the standard spectrophotometric pH‐based method; the two independent calibration methods resulted in a mean pH difference of 0.008. We anticipate that the Self‐Calibrating SeapHOx will be capable of autonomously providing climate quality pH data, directly linked to a primary seawater pH standard, and with improvements over standard calibration techniques.

Continue reading ‘Autonomous in situ calibration of ion‐sensitive field effect transistor pH sensors’

A Polar outlook: potential interactions of micro- and nano-plastic with other anthropogenic stressors


  • MP/NP at the poles should be addressed with chemical and climate stressors.
  • MP/NP and anthropogenic stress interactions may vary seasonally and locally.
  • MP/NP research should focus on polar species enduring high anthropogenic stress.


Polar marine ecosystems may have higher sensitivity than other ecosystems to plastic pollution due to recurrent physical and biological features; presence of ice and high UV radiation, slow growth rates and weak genetic differentiation of resident biota, accumulation of persistent organic pollutants and heavy metals, and fast rates of warming and global ocean acidification. Here, we discuss potential sources of and exposure to micro- and nano-plastic in polar marine ecosystems and potential mixture effects of micro- and nano-plastic coupled with chemical and climate related stressors. We address the anthropogenic contaminants likely to be ‘high risk’ for interactions in Arctic and Antarctic waters for reasons such as accumulation under sea-ice, a known sink for plastic particulates. Consequently, we address the potential for localised plastic-chemical interactions and possible seasonal fluctuations in interactions associated with freeze-thaw events. The risks for keystone polar species are also considered, incorporating the behavioural and physiological traits of biota and addressing potential ‘hotspot’ areas. Finally, we discuss a possible direction for future research.

Continue reading ‘A Polar outlook: potential interactions of micro- and nano-plastic with other anthropogenic stressors’

Ocean acidification alters properties of the exoskeleton in adult tanner crabs, Chionoecetes bairdi

Ocean acidification can affect the ability of calcifying organisms to build and maintain mineralized tissue. In decapod crustaceans, the exoskeleton is a multilayered structure composed of chitin, protein, and mineral, predominately magnesian calcite or amorphous calcium carbonate (ACC). We investigated the effects of acidification on the exoskeleton of mature (post-terminal-molt) female southern Tanner crabs, Chionoecetes bairdi. Crabs were exposed to one of three pH levels—8.1, 7.8, or 7.5—for two years. Reduced pH led to a suite of body-region-specific effects on the exoskeleton. Microhardness of the claw was 38% lower in crabs at pH 7.5 compared with those at pH 8.1, but carapace microhardness was unaffected by pH. In contrast, reduced pH altered elemental content in the carapace (reduced calcium, increased magnesium), but not the claw. Diminished structural integrity and thinning of the exoskeleton was observed at reduced pH in both body regions; internal erosion of the carapace was present in most crabs at pH 7.5, and the claws of these crabs showed substantial external erosion, with tooth-like denticles nearly or completely worn away. Using infrared spectroscopy, we observed a shift in the phase of calcium carbonate present in the carapace of pH-7.5 crabs: a mix of ACC and calcite was found in the carapace of crabs at pH 8.1, whereas the bulk of calcium carbonate had transformed to calcite in pH-7.5 crabs. With limited capacity for repair, the exoskeleton of long-lived crabs that undergo a terminal molt, such as Cbairdi, may be especially susceptible to ocean acidification.

Continue reading ‘Ocean acidification alters properties of the exoskeleton in adult tanner crabs, Chionoecetes bairdi’

Projections of algae, eelgrass, and zooplankton ecological interactions in the inner Salish Sea – for future climate, and altered oceanic states


  • Harmonized simulation of DO, pH, and Y2095 climate change impacts in the Salish Sea
  • A 52-fold increase in exposure and near-bed pelagic species to hypoxic waters in Y2095
  • Ocean acidification projections for Y2095 indicate ≈ 20 −114% increase in water column (ΩA) <1)
  • Primary productivity propagation to zooplankton projected for Y2095 with ≈ 13%−25% increases.
  • Eelgrass sensitive to stressors and potential for loss of eelgrass biomass in the future.


Future projections based on the IPCC high emissions scenario RCP8.5 have previously shown that the Pacific Northwest coastal waters will be subjected to altered ocean states in the upwelled shelf waters, resulting in higher primary productivity and increased regions of hypoxia and acidification in the inner estuarine waters such as the Salish Sea. However, corresponding effects on the lower trophic levels and submerged aquatic vegetation have not yet been quantified. Supported by new synoptic field data, explicit coupled simulation of algae, zooplankton, and eelgrass biomass was accomplished for the first time in the Salish Sea. We re-applied the improved model to evaluate future ecological response and examined potential algal species shift, but with the effects of zooplankton production, metabolism, and predation-prey interactions included. We also evaluated the role of eelgrass with respect to potential for improvements to dissolved oxygen and pH levels and as a mitigation measure against hypoxia and ocean acidification. The results re-confirm the possibility that there could be a substantial area-days increase (≈52-fold) in exposure of benthic and near-bed pelagic species to hypoxic waters in 2095. The projections for ocean acidification similarly indicate ≈ 20 -114% increase in exposure to lower pH corrosive waters with aragonite saturation state ΩA <1. Importantly, projected increase in primary productivity was shown to propagate to higher trophic levels, with ≈ 13% and 25% increases in micro and mesozooplankton biomass levels. However, the preliminary results also point to sensitivity of the eelgrass model to environmental stressor and potential loss eelgrass biomass in the future.

Continue reading ‘Projections of algae, eelgrass, and zooplankton ecological interactions in the inner Salish Sea – for future climate, and altered oceanic states’

Abundances and morphotypes of the coccolithophore Emiliania huxleyi in southern Patagonia compared to neighboring oceans and northern-hemisphere fjords

Coccolithophores are potentially affected by ongoing ocean acidification, where rising CO2 lowers seawater pH and calcite saturation state (Ωcal). Southern Patagonian fjords and channels provide natural laboratories for studying these issues due to high variability in physical and chemical conditions. We surveyed coccolithophore assemblages in Patagonian fjords during late-spring 2015 and early-spring 2017. Surface Ωcal exhibited large variations driven mostly by freshwater inputs. High Ωcal conditions (max. 3.6) occurred in the Archipelago Madre de Dios. Ωcal ranged from 2.0–2.6 in the western Strait of Magellan, 1.5–2.2 in the Inner Channel, and was sub-saturating (0.5) in Skyring Sound. Emiliania huxleyi was the only coccolithophore widely distributed in Patagonian fjords (> 96 % of total coccolitophores), only disappearing in the Skyring Sound, a semi-closed mesohaline system. Correspondence analysis associated higher E. huxleyi biomasses with lower diatom biomasses. The highest E. huxleyi abundances in Patagonia were in the lower range of those reported in Norwegian fjords. Predominant morphotypes were distinct from those previously documented in nearby oceans but similar to those of Norwegian fjords. Moderate-calcified forms of E. huxleyi A morphotype were uniformly distributed throughout Patagonia fjords. The exceptional R/hyper-calcified coccoliths, associated with low Ωcal values in Chilean and Peruvian coastal upwellings, were a minor component associated with high Ωcal levels in Patagonia. Outlying mean index (OMI) niche analysis suggested that pH/Ωcal conditions explained most variation in the realized niches of E. huxleyi morphotypes. The moderate-calcified A morphotype exhibited the widest niche-breadth (generalist), while the R/hyper-calcified morphotype exhibited a more restricted realized niche (specialist). Nevertheless, when considering an expanded sampling domain, including nearby Southeast Pacific coastal and offshore waters, even the R/hyper-calcified morphotype exhibited a higher niche breadth than other closely phylogenetically-related coccolithophore species. The occurrence of E. huxleyi in naturally low pH/Ωcal environments indicates that its ecological response is plastic and capable of adaptation.

Continue reading ‘Abundances and morphotypes of the coccolithophore Emiliania huxleyi in southern Patagonia compared to neighboring oceans and northern-hemisphere fjords’

Seacarbx – seacarb extension for deep-time carbonate system calculations

seacarbx is a seacarb extension written in R, which enables to use seacarb (Gattuso et al., 2019) for deep-time carbonate system calculations or for culturing studies carried out in seawater with modified [Mg2+] and [Ca2+]. For this, the functions carbK0K1K2KsKwKbKspa, and Kspc were modfied to account for the effect of seawater [Mg2+] and [Ca2+] on the dissociation constants of carbonic and boric acid. In addition to the modified functions, seacarbx contains MyAMI that are tabulated parameters defining the temperature and salinity dependencies of the conditional equilibrium constants for [Mg2+] and [Ca2+] in the range 1–60 mM (from Hain et al., 2015, 2018), as well as a function for bilinear interpolation

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Ocean acidification in the IPCC AR5 WG II

OUP book