Calcifying Fluid pH Research Articles

Differences in carbonate chemistry up-regulation of long-lived reef-building corals

With climate projections questioning the future survival of stony corals and their dominance as tropical reef builders, it is critical to understand the adaptive capacity of corals to ongoing climate change. Biological mediation of the carbonate chemistry of the coral calcifying fluid is a fundamental component for assessing the response of corals to global threats. The Tara Pacific expedition (2016–2018) provided an opportunity to investigate calcification patterns in extant corals throughout the Pacific Ocean. Cores from colonies of the massive Porites and Diploastrea genera were collected from different environments to assess calcification parameters of long-lived reef-building corals. At the basin scale of the Pacific Ocean, we show that both genera systematically up-regulate their calcifying fluid pH and dissolved inorganic carbon to achieve efficient skeletal precipitation. However, while Porites corals increase the aragonite saturation state of the calcifying fluid (Ωcf) at higher temperatures to enhance their calcification capacity, Diploastrea show a steady homeostatic Ωcf across the Pacific temperature gradient. Thus, the extent to which Diploastrea responds to ocean warming and/or acidification is unclear, and it deserves further attention whether this is beneficial or detrimental to future survival of this coral genus.

Impacts of Warming and Acidification on Coral Calcification Linked to Photosymbiont Loss and Deregulation of Calcifying Fluid pH

Corals are globally important calcifiers that exhibit complex responses to anthropogenic warming and acidification. Although coral calcification is supported by high seawater pH, photosynthesis by the algal symbionts of zooxanthellate corals can be promoted by elevated pCO2. To investigate the mechanisms underlying corals’ complex responses to global change, three species of tropical zooxanthellate corals (Stylophora pistillata, Pocillopora damicornis, and Seriatopora hystrix) and one species of asymbiotic cold-water coral (Desmophyllum pertusum, syn. Lophelia pertusa) were cultured under a range of ocean acidification and warming scenarios. Under control temperatures, all tropical species exhibited increased calcification rates in response to increasing pCO2. However, the tropical species’ response to increasing pCO2 flattened when they lost symbionts (i.e., bleached) under the high-temperature treatments—suggesting that the loss of symbionts neutralized the benefit of increased pCO2 on calcification rate. Notably, the cold-water species that lacks symbionts exhibited a negative calcification response to increasing pCO2, although this negative response was partially ameliorated under elevated temperature. All four species elevated their calcifying fluid pH relative to seawater pH under all pCO2 treatments, and the magnitude of this offset (Δ[H+]) increased with increasing pCO2. Furthermore, calcifying fluid pH decreased along with symbiont abundance under thermal stress for the one species in which calcifying fluid pH was measured under both temperature treatments. This observation suggests a mechanistic link between photosymbiont loss (‘bleaching’) and impairment of zooxanthellate corals’ ability to elevate calcifying fluid pH in support of calcification under heat stress. This study supports the assertion that thermally induced loss of photosymbionts impairs tropical zooxanthellate corals’ ability to cope with CO2-induced ocean acidification.

No ion is an island: Multiple ions influence boron incorporation into CaCO3

Boron isotope ratios – as measured in marine calcium carbonate – are an established tracer of past seawater and calcifying fluid pH, and thus a powerful tool for probing marine calcifier physiology and reconstructing past atmospheric CO2 levels. For such applications, understanding the inorganic baseline upon which foraminiferal vital effects or coral pH upregulation are superimposed should be an important prerequisite. Yet, investigations into boron isotope fractionation in synthetic CaCO3 polymorphs have often reported variable and even conflicting results, implying our understanding of the pathways of boron incorporation into calcium carbonate is incomplete. Here we address this topic with experimental data from synthetic calcite and aragonite precipitated across a range of pH in the presence of both Mg and Ca. We observe coherent patterns in B/Ca and Na/Ca ratios that, we suggest, point to paired substitution of Na and B into the carbonate lattice to achieve local charge balance. In addition, we confirm the results of previous studies that the boron isotope composition of inorganic aragonite precipitates closely reflects that of aqueous borate ion, but that inorganic calcites display a higher degree of scatter, and diverge from the boron isotope composition of aqueous borate ion at low pH. With reference to the simultaneous incorporation of other trace and minor elements, we put forward possible explanations for the observed variability in the concentration and isotopic composition of boron in synthetic CaCO3. In particular, we highlight the potential importance of interface electrostatics in driving variability in our own and published synthetic carbonate datasets. Importantly for palaeo-reconstruction, however, these electrostatic effects are unlikely to play as important a role during natural precipitation of biogenic carbonates.

The primary controls on U/Ca and minor element proxies in a cold-water coral cultured under decoupled carbonate chemistry conditions

Culture experiments are uniquely suited for uncovering the fundamental factors controlling skeletal geochemistry because it is possible to explore conditions beyond what is found in the modern ocean and to decouple parameters that co-vary in nature. We cultured juvenile individuals of a cold-water coral (Balanophyllia elegans) in a set of experiments that decoupled carbonate chemistry parameters over a wide range of pH, DIC, and [CO32−] values. Using a multi-element mixed spike isotope dilution method we then analyzed cultured skeletons for U/Ca, which has been proposed as a potential proxy for seawater pH and [CO32−], as well as Sr/Ca, and Mg/Ca.We find that U/Ca and Sr/Ca ratios in cultured B. elegans are most strongly correlated with solution DIC and not pH or [CO32−]. We also confirm previous observations that Metal/Calcium (Me/Ca) ratios follow the same correlated relationships between and among individuals across different experimental conditions. Interpretation of these robust Me/Ca patterns within the framework of a geochemical model of biomineralization allows us to identify two “rules” of skeletal growth for B. elegans. First, changes in seawater exchange rates can explain variability in B. elegans Me/Ca ratios, correlations between these ratios, and sensitivity of Me/Ca to changes in seawater carbonate chemistry. Second, our model best fits our data if we assume that calcifying fluid pH for B. elegans remains constant across widely varying experimental seawater compositions. Our study has implications for the recently developed Sr-U paleothermometer because it refines our understanding of the environmental parameters affecting this proxy. Our model further demonstrates that U/Ca is not a robust indicator of seawater pH or [CO32−]. Instead, U/Ca may record how calcifying fluid [CO32−] responds to changes in the environment or calcification dynamics, which may be useful in evaluating how corals respond to changes like ocean acidification. Measurements of U/Ca and additional Me/Ca ratios in other coral species, evaluated within a similar framework, may elucidate how those species respond to environmental change.

Porites Calcifying Fluid pH on Seasonal to Diurnal Scales

AbstractCoral resilience to ocean acidification is largely determined by the degree of physiological control corals can exert on their calcifying fluid carbonate chemistry. In this study, the boron isotopic composition (δ11B) of a Porites colony growing on a reef flat on Kiritimati Island in the equatorial central Pacific is examined to quantify the sensitivity of calcifying fluid pH (pHcf) to ambient environmental conditions. Skeletal δ11B along the growth axis of one annual growth band was determined with bulk analysis and by laser ablation (LA) MC‐ICP‐MS. Furthermore, the oxygen and carbon isotopic composition, trace element ratios, and skeletal density were quantified. Sclerochronological data were interpreted in the context of simultaneous recordings of reef flat seawater pH (pHsw), temperature, salinity, and water depth, and by measurements of these parameters on the fore‐reef. A recent model of pHcf upregulation, after optimization with seasonally resolved data, was used to simulate pHcf variability on a diurnal scale. Results showed that on a seasonal scale, Porites pHcf is upregulated compared to ambient seawater: both bulk and LA‐MC‐ICP‐MS derived δ11B resulted in a mean pHcf of 8.35 pH units. Calcifying fluid pH upregulation primarily followed variations in seawater temperatures, that is likely related to the control of temperature on calcification rate. On the reef flat, the diurnal range in pHsw was substantially higher (0.29 pH units) than on the fore‐reef (0.07 pH units). However, model results suggest that the high diurnal variability in reef flat pHsw resulted only in a limited variability in Porites pHcf.

Controls on boron isotopes in a cold-water coral and the cost of resilience to ocean acidification

Coral skeletal growth is sensitive to environmental change and may be adversely impacted by an acidifying ocean. However, physiological processes can also buffer biomineralization from external conditions, providing apparent resilience to acidification in some species. These same physiological processes affect skeletal composition and can impact paleoenvironmental proxies. Understanding the mechanisms of coral calcification is thus crucial for predicting the vulnerability of different corals to ocean acidification and for accurately interpreting coral-based climate records. Here, using boron isotope (δ11B) measurements on cultured cold-water corals, we explain fundamental features of coral calcification and its sensitivity to environmental change. Boron isotopes are one of the most widely used proxies for past seawater pH, and we observe the expected sensitivity between δ11B and pH. Surprisingly, we also discover that coral δ11B is independently sensitive to seawater dissolved inorganic carbon (DIC). We can explain this new DIC effect if we introduce boric acid diffusion across cell membranes as a new flux within a geochemical model of biomineralization. This model independently predicts the sensitivity of the δ11B-pH proxy, without being trained to these data, even though calcifying fluid pH (pHCF) is constant. Boric acid diffusion can resolve why δ11B is a useful proxy across a range of calcifiers, including foraminifera, even when calcifying fluid pH differs from seawater. Our modeling shows that δ11B cannot be interpreted unequivocally as a direct tracer of pHCF. Constant pHCF implies similar calcification rates as seawater pH decreases, which can explain the resilience of some corals to ocean acidification. However, we show that this resilience has a hidden energetic cost such that calcification becomes less efficient in an acidifying ocean.

Resilience of the temperate coral Oculina arbuscula to ocean acidification extends to the physiological level

Both juvenile and adult life stages of the temperate scleractinian coral Oculina arbuscula are resilient to the effects of moderate ocean acidification (OA) in contrast to many tropical corals in which growth and calcification rates are suppressed. Here, potential mechanisms of resilience to OA related to photosynthetic physiology and inorganic carbon processing were studied in adult O. arbuscula colonies. After exposing colonies to ambient and elevated carbon dioxide (CO2) treatments for 7 weeks, photosynthetic performance was characterized using photosynthesis versus irradiance experiments, chlorophyll fluorescence kinetics, and algal pigment content. Inorganic carbon-processing capabilities were assessed by measurement of internal and external carbonic anhydrase activity of the coral host, internal carbonic anhydrase activity of symbiotic algae, and the reliance of photosynthesis on external carbonic anhydrase. Photosynthetic physiology was unaffected by OA ruling out the possibility that resilience was mediated by increased photosynthetic energy supply. Carbonic anhydrase activities were maintained at elevated CO2 suggesting no major rearrangements of the inorganic carbon-processing machinery, but this could be a sign of resilience since tropical corals often down-regulate carbonic anhydrases at high CO2. The general lack of effect of ocean acidification on these physiological traits suggests other characteristics, such as maintenance of calcifying fluid pH and ability to acquire energy from heterotrophy, may be more important for the resilience of O. arbuscula to OA.

Linking Internal Carbonate Chemistry Regulation and Calcification in Corals Growing at a Mediterranean CO2 Vent

Corals exert a strong biological control over their calcification processes, but there is a lack of knowledge on their capability of long-term acclimatization to ocean acidification. We used a dual geochemical proxy approach to estimate the calcifying fluid pH (pHcf) and carbonate chemistry of a Mediterranean coral (Balanophyllia europaea) naturally growing along a pH gradient (range: pHTS 8.07-7.74). The pHcf derived from skeletal boron isotopic composition (11B) was 0.3-0.6 units above seawater values and homogeneous along the gradient (mean  sem: Site 1 = 8.39  0.03, Site 2 = 8.34  0.03, Site 3 = 8.34  0.02). Also carbonate ion concentration derived from B/Ca was homogeneous (mean  sem (µmol kg-1): Site 1 = 579  34, Site 2 = 541  27, Site 3 = 568  30) regardless of seawater pH. Furthermore, gross calcification rate (GCR, mass of CaCO3 deposited on the skeletal unit area per unit of time), estimated by a “bio-inorganic model” (IpHRAC), was homogeneous with decreasing pH. The homogeneous GCR, internal pH and carbonate chemistry confirm that the features of the ‘building blocks’ – the fundamental structural components - produced by the biomineralization process were substantially unaffected by increased acidification. Furthermore, the pH up-regulation observed in this study could potentially explain the previous hypothesis that less ‘building blocks’ are produced with increasing acidification ultimately leading to increased skeletal porosity and to reduced net calcification rate obtained by including the total volume of the pore space. In fact, assuming that the available energy at the three sites is the same, this energy at the low pH sites could be partitioned among fewer calicoblastic cells that consume more energy given the larger difference between external and internal pH compared to the control, leading to the production of less building blocks (i.e., formation of pores inside the skeleton structure, determining increased porosity). However, we cannot exclude that also dissolution may play a role in increasing porosity. Thus, the ability of scleractinian corals to maintain elevated pHcf relative to ambient seawater might not always be sufficient to counteract declines in net calcification under ocean acidification scenarios.

The influence of seawater calcium ions on coral calcification mechanisms: Constraints from boron and carbon isotopes and B/Ca ratios in Pocillopora damicornis

In order to better understand the response of coral calcification to changes in seawater chemistry, fragments of the coral Pocillopora damicornis were grown in seawater with varying [Ca2+]. Using a combined trace element (B/Ca) and stable isotope (δ11B, δ13C) approach, this paper explores the effect of seawater calcium concentrations ([Ca2+]SW) on coral calcification mechanisms and describes the manipulation of the extracellular calcifying fluid (ECF) pH (pHECF), saturation state (ΩECF) and dissolved inorganic carbon (DIC) speciation of the ECF. In these experiments, increases in [Ca2+]SW did not significantly influence calcification rates but caused the skeletal B/Ca ratio to significantly increase. To explain these results we propose a mechanism by which [CO32−]ECF is influenced by [Ca2+]SW. This mechanism suggests that the pHECF will be lowest in our highest [Ca2+] treatment and using this relationship we can place constraints on the pHECF. The difference in pHECF in our treatments is supported in part by a slight, but insignificant decrease in skeletal δ11B and δ13C values. We propose a novel dual-proxy approach to estimate pHECF, where calcification occurs at a pHECF > 9. This work emphasizes the importance of multi-element proxy approaches in understanding pH up-regulation and CO32− concentrations during calcification of corals.

Seawater temperature and buffering capacity modulate coral calcifying pH

Scleractinian corals promote the precipitation of their carbonate skeleton by elevating the pH and dissolved inorganic carbon (DIC) concentration of their calcifying fluid above that of seawater. The fact corals actively regulate their calcifying fluid chemistry implies the potential for acclimation to ocean acidification. However, the extent to which corals can adjust their regulation mechanism in the face of decreasing ocean pH has not been rigorously tested. Here I present a numerical model simulating pH and DIC up-regulation by corals, and use it to determine the relative importance of physiological regulation versus seawater conditions in controlling coral calcifying fluid chemistry. I show that external seawater temperature and buffering capacity exert the first-order control on the extent of pH elevation in the calcifying fluid and explain most of the observed inter- and intra-species variability. Conversely, physiological regulation, represented by the interplay between enzymatic proton pumping, carbon influx and the exchange of calcifying fluid with external seawater, contributes to some variability but remain relatively constant as seawater conditions change. The model quantitatively reproduces variations of calcifying fluid pH in natural Porites colonies, and predicts an average 0.16 unit decrease in Porites calcifying fluid pH, i.e., ~43% increase in H+ concentration, by the end of this century as a combined result of projected ocean warming and acidification, highlighting the susceptibility of coral calcification to future changes in ocean conditions. In addition, my findings support the development of coral-based seawater pH proxies, but suggest the influences of physicochemical and biological factors other than seawater pH must be considered.

Boron isotope systematics of cultured brachiopods: Response to acidification, vital effects and implications for palaeo-pH reconstruction

CO2-induced ocean acidification and associated decrease of seawater carbonate saturation state contributed to multiple environmental crises in Earth’s history, and currently poses a major threat for marine calcifying organisms. Owing to their high abundance and good preservation in the Phanerozoic geological record, brachiopods present an advantageous taxon of marine calcifiers for palaeo-proxy applications as well as studies on biological mechanism to cope with environmental change. To investigate the geochemical and physiological responses of brachiopods to prolonged low-pH conditions we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years. Our experiments demonstrate that brachiopods form their calcite shells under strong biological control, which enables them to survive and grow under low-pH conditions and even in seawater strongly undersaturated with respect to calcite (pH = 7.35, Ωcal = 0.6). Using boron isotope (δ11B) systematics including MC-ICP-MS as well as SIMS analyses, validated against in vivo microelectrode measurements, we show that this resilience is achieved by strict regulation of the calcifying fluid pH between the epithelial mantle and the shell. We provide a culture-based δ11B−pH calibration, which as a result of the internal pH regulatory mechanisms deviates from the inorganic borate ion to pH relationship, but confirms a clear yet subtle pH dependency for brachiopods. At a micro-scale level, the incorporation of 11B appears to be principally driven by a physiological gradient across the shell, where the δ11B values of the innermost calcite record the internal calcifying fluid pH while the composition of the outermost layers is also influenced by seawater pH. These findings are of consequence to studies on biomineralisation processes, physiological adaptations as well as past climate reconstructions.

Coral calcifying fluid aragonite saturation states derived from Raman spectroscopy

Abstract. Quantifying the saturation state of aragonite (ΩAr) within the calcifying fluid of corals is critical for understanding their biomineralization process and sensitivity to environmental changes including ocean acidification. Recent advances in microscopy, microprobes, and isotope geochemistry enable the determination of calcifying fluid pH and [CO32−], but direct quantification of ΩAr (where ΩAr = [CO32−][Ca2+]∕Ksp) has proved elusive. Here we test a new technique for deriving ΩAr based on Raman spectroscopy. First, we analysed abiogenic aragonite crystals precipitated under a range of ΩAr from 10 to 34, and we found a strong dependence of Raman peak width on ΩAr with no significant effects of other factors including pH, Mg∕Ca partitioning, and temperature. Validation of our Raman technique for corals is difficult because there are presently no direct measurements of calcifying fluid ΩAr available for comparison. However, Raman analysis of the international coral standard JCp-1 produced ΩAr of 12.3 ± 0.3, which we demonstrate is consistent with published skeletal Mg∕Ca, Sr∕Ca, B∕Ca, δ11B, and δ44Ca data. Raman measurements are rapid ( ≤ 1 s), high-resolution ( ≤ 1 µm), precise (derived ΩAr ± 1 to 2 per spectrum depending on instrument configuration), accurate ( ±2 if ΩAr < 20), and require minimal sample preparation, making the technique well suited for testing the sensitivity of coral calcifying fluid ΩAr to ocean acidification and warming using samples from natural and laboratory settings. To demonstrate this, we also show a high-resolution time series of ΩAr over multiple years of growth in a Porites skeleton from the Great Barrier Reef, and we evaluate the response of ΩAr in juvenile Acropora cultured under elevated CO2 and temperature.

Decoupling between the response of coral calcifying fluid pH and calcification to ocean acidification

Evaluating the factors responsible for differing species-specific sensitivities to declining seawater pH is central to understanding the mechanisms via which ocean acidification (OA) affects coral calcification. We report here the results of an experiment comparing the responses of the coral Acropora yongei and Pocillopora damicornis to differing pH levels (8.09, 7.81, and 7.63) over an 8-week period. Calcification of A. youngei was reduced by 35% at pH 7.63, while calcification of P. damicornis was unaffected. The pH in the calcifying fluid (pHcf) was determined using δ11B systematics, and for both species pHcf declined slightly with seawater pH, with the decrease being more pronounced in P. damicornis. The dissolved inorganic carbon concentration at the site of calcification (DICcf) was estimated using geochemical proxies (B/Ca and δ11B) and found to be double that of seawater DIC, and increased in both species as seawater pH decreased. As a consequence, the decline of the saturation state at the site of calcification (Ωcf) with OA was partially moderated by the DICcf increase. These results highlight that while pHcf, DICcf and Ωcf are important in the mineralization process, some corals are able to maintain their calcification rates despite shifts in their calcifying fluid carbonate chemistry.

Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH.

Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pHCF) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pHCF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (AT). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pHCF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [AT], revealing that seawater pH is not the sole driver of pHCF Notably, when we synthesize our results with published data, we identify linear relationships of pHCF with the seawater [DIC]/[H+] ratio, [AT]/ [H+] ratio and [[Formula: see text]]. Our findings contribute new insights into the mechanisms determining the sensitivity of coral calcification to changes in seawater carbonate chemistry, which are needed for predicting effects of environmental change on coral reefs and for robust interpretations of isotopic palaeoenvironmental records in coral skeletons.

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

Abstract. Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures, and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

A refined method for calculating paleotemperatures from linear correlations in bamboo coral carbon and oxygen isotopes

AbstractBamboo corals represent an emerging paleoclimate archive with the potential to record variability at intermediate depths throughout much of the global ocean. Realizing this potential has been complicated by biologically mediated vital effects, which are evident in linear correlations of skeletal carbon (δ13C) and oxygen (δ18O) isotope composition. Previous efforts to develop a bamboo coral δ18O paleothermometer by accounting for such vital effects have not been completely successful as they still rely on empirical calibrations that are offset from the temperature dependence of abiogenic experiments. Here we describe an approach that better corrects for bamboo coral vital effects and allows paleotemperatures to be calculated directly from the abiogenic temperature dependence. The success of the method lies in calculating apparent equilibrium carbon and oxygen isotope fractionation at the temperature, pH, and growth rate of each coral, as well as in the use of model II regressions. Rigorous propagation of uncertainty suggests typical errors of ±2–3°C, but in select cases errors as low as ±0.98°C can be achieved for densely sampled and strongly correlated data sets. This lower limit approaches the value attributed to uncertainty in pH and growth rate estimates alone, as predicted by a series of pseudoproxy experiments. The incorporation of isotopically light metabolic CO2 appears to be negligible in most Pacific corals, but may be significant in Atlantic specimens, potentially requiring an additional correction. The success of the method therefore hinges on how well complex environmental systems and biomineralization strategies are constrained, with the most reliable temperatures occurring when calcifying fluid pH, growth rate, and incorporation of metabolic carbon into skeletal calcite are constrained using multiple geochemical proxies.

Deep‐sea coral δ13C: A tool to reconstruct the difference between seawater pH and δ11B‐derived calcifying fluid pH

AbstractThe boron isotopic composition (δ11B) of coral skeleton is a proxy for seawater pH. However, δ11B‐based pH estimates must account for the pH difference between seawater and the coral calcifying fluid, ΔpH. We report that skeletal δ11B and ΔpH are related to the skeletal carbon isotopic composition (δ13C) in four genera of deep‐sea corals collected across a natural pH range of 7.89–8.09, with ΔpH related to δ13C by ΔpH = 0.029 × δ13C + 0.929, r2 = 0.717. Seawater pH can be reconstructed by determining ΔpH from δ13C and subtracting it from the δ11B‐derived calcifying fluid pH. The uncertainty for reconstructions is ±0.12 pH units (2 standard deviations) if estimated from regression prediction intervals or between ±0.04 and ±0.06 pH units if estimated from confidence intervals. Our new approach quantifies and corrects for vital effects, offering improved accuracy relative to an existing δ11B versus seawater pH calibration with deep‐sea scleractinian corals.

PH up-regulation as a potential mechanism for the cold-water coral <i>Lophelia pertusa</i> to sustain growth in aragonite undersaturated conditions

Abstract. Cold-water corals are important habitat formers in deep-water ecosystems and at high latitudes. Ocean acidification and the resulting change in aragonite saturation are expected to affect these habitats and impact coral growth. Counter to expectations, the deep water coral Lophelia pertusa has been found to be able to sustain growth even in undersaturated conditions. However, it is important to know whether such undersaturation modifies the skeleton and thus its ecosystem functioning. Here we used Synchrotron X-Ray Tomography and Raman spectroscopy to examine changes in skeleton morphology and fibre orientation. We combined the morphological assessment with boron isotope analysis to determine if changes in growth are related to changes in control of calcification pH. We compared the isotopic composition and structure formed in their natural environment to material grown in culture at lower pH conditions. Skeletal morphology is highly variable but shows no distinctive differences between natural and low pH conditions. Raman investigations found no difference in macromorphological skeletal arrangement of early mineralization zones and secondary thickening between the treatments. The δ11B analyses show that L. pertusa up-regulates the internal calcifying fluid pH (pHcf) during calcification compared to ambient seawater pH and maintains a similar elevated pHcf at increased pCO2 conditions. We suggest that as long as the energy is available to sustain the up-regulation, i.e. individuals are well fed, there is no detrimental effect to the skeletal morphology.

Coral calcifying fluid pH dictates response to ocean acidification.

Ocean acidification driven by rising levels of CO2 impairs calcification, threatening coral reef growth. Predicting how corals respond to CO2 requires a better understanding of how calcification is controlled. Here we show how spatial variations in the pH of the internal calcifying fluid (pHcf) in coral (Stylophora pistillata) colonies correlates with differential sensitivity of calcification to acidification. Coral apexes had the highest pHcf and experienced the smallest changes in pHcf in response to acidification. Lateral growth was associated with lower pHcf and greater changes with acidification. Calcification showed a pattern similar to pHcf, with lateral growth being more strongly affected by acidification than apical. Regulation of pHcf is therefore spatially variable within a coral and critical to determining the sensitivity of calcification to ocean acidification.

Boron isotopic fractionation and trace element incorporation in various species of modern corals in Sanya Bay, South China Sea

The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron (KD) ranged from 0.83×10−3 to 1.69×10−3, which are in good agreement with previous studies. As the analyzed coral skeleton (∼5 g) spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account, (11B/10B)coral values of all living corals spread over the curves of (11B/10B)borate vs. (11B/10B)sw with the α4−3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH (i.e., Δ(pHbiol-pHsw)) for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.