Physiological and isotopic responses of scleractinian corals to ocean acidification

Uptake of anthropogenic CO₂ by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (Ω_arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistillata, exposed to high pCO₂ (or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistillata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO₂ conditions, corresponding to pH_T values of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater Ω_arag < 1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C), and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density, and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO₂ (low pH) conditions. Both species showed similar trends of δ¹¹B depletion and δ¹⁸O enrichment under reduced pH, whereas the δ¹³C results imply species-specific metabolic response to high pCO₂ conditions. The skeletal δ¹¹B values plot above seawater δ¹¹B vs. pH borate fractionation curves calculated using either the theoretically derived α_B value of 1.0194 (Kakihana et al. (1977) Bull. Chem. Soc. Jpn.50, 158) or the empirical α_B value of 1.0272 (Klochko et al. (2006) EPSL248, 261). However, the effective α_B must be greater than 1.0200 in order to yield calculated coral skeletal δ¹¹B values for pH conditions where Ω_arag ? 1. The δ¹¹B vs. pH offset from the seawater δ¹¹B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal δ¹³C and δ¹⁸O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeletons.     

Evidence for ocean acidification in the Great Barrier Reef of Australia

Geochemical records preserved in the long-lived carbonate skeleton of corals provide one of the few means to reconstruct changes in seawater pH since the commencement of the industrial era. This information is important in not only determining the response of the surface oceans to ocean acidification from enhanced uptake of CO₂, but also to better understand the effects of ocean acidification on carbonate secreting organisms such as corals, whose ability to calcify is highly pH dependent. Here we report an ∼200 year δ¹¹B isotopic record, extracted from a long-lived Porites coral from the central Great Barrier Reef of Australia. This record covering the period from 1800 to 2004 was sampled at yearly increments from 1940 to the present and 5-year increments prior to 1940. The δ¹¹B isotopic compositions reflect variations in seawater pH, and the δ¹³C changes in the carbon composition of surface water due to fossil fuel burning over this period. In addition complementary Ba/Ca, δ¹⁸O and Mg/Ca data was obtained providing proxies for terrestrial runoff, salinity and temperature changes over the past 200 years in this region. Positive thermal ionization mass spectrometry (PTIMS) method was utilized in order to enable the highest precision and most accurate measurements of δ¹¹B values. The internal precision and reproducibility for δ¹¹B of our measurements are better than ±0.2‰ (2σ), which translates to a precision of better than ±0.02 pH units. Our results indicate that the long-term pre-industrial variation of seawater pH in this region is partially related to the decadal-interdecadal variability of atmospheric and oceanic anomalies in the Pacific. In the periods around 1940 and 1998 there are also rapid oscillations in δ¹¹B compositions equivalent changes in pH of almost 0.5 U. The 1998 oscillation is co-incident with a major coral bleaching event indicating the sensitivity of skeletal δ¹¹B compositions to loss of zooxanthellate symbionts. Importantly, from the 1940s to the present-day, there is a general overall trend of ocean acidification with pH decreasing by about 0.2-0.3 U, the range being dependent on the value assumed for the fractionation factor α_(B3-B4) of the boric acid and borate species in seawater. Correlations of δ¹¹B with δ¹³C during this interval indicate that the increasing trend towards ocean acidification over the past 60 years in this region is the result of enhanced dissolution of CO₂ in surface waters from the rapidly increasing levels of atmospheric CO₂, mainly from fossil fuel burning. This suggests that the increased levels of anthropogenic CO₂ in atmosphere has already caused a significant trend towards acidification in the oceans during the past decades. Observations of surprisingly large decreases in pH across important carbonate producing regions, such as the Great Barrier Reef of Australia, raise serious concerns about the impact of Greenhouse gas emissions on coral calcification.     

MC‐ICP‐MS Isotope Measurements with Direct Injection Nebulisation (d‐DIHEN): Optimisation and Application to Boron in Seawater and Carbonate Samples

We report here an optimisation of the demountable direct injection high efficiency nebuliser (d‐DIHEN) for isotopic measurements with a Neptune (ThermoFisher Scientific, Bremen, Germany) multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS) and describe a method for boron isotopic ratio determination. With direct injection nebulisation 100% of the analyte was introduced into the ICP‐MS plasma and wash times were drastically reduced for elements such as boron and thorium. Compared to the classical stable introduction system (SIS: double Scott/cyclonic spray chamber), sensitivity for boron was 2–5 times higher with d‐DIHEN and wash times up to ten times shorter. Repeatability of ¹¹B/¹⁰B sample‐calibrator bracketing measurements reached 0.25‰ (2s) for seawater and coral samples. Method accuracy and reproducibility were tested on mixed reference solutions having δ¹¹B values in the ranges ?90 to +40‰ and ?2 to +2.5‰, demonstrating our ability to distinguish δ¹¹B values with differences of only 0.25‰. The international seawater reference material NRCC NASS‐5 (National Research Council, Ottawa, Canada), analysed in different sessions over a 10‐month period, yielded an average δ¹¹B value of +39.89 ± 0.25‰, in the upper range of previously published seawater values. A comparison between δ¹¹B determined by d‐DIHEN MC‐ICP‐MS and positive‐TIMS (P‐TIMS) for four modern corals showed an excellent agreement (with bias of less than 0.4‰).     

Boron isotope geochemistry of Paleozoic brachiopod calcite: Implications for a secular change in the boron isotope geochemistry of seawater over the Phanerozoic

Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO₂. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ¹¹B values are significantly lower in comparison to δ¹¹B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in ¹¹B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of ¹¹B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.     

A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates

The boron isotope-pH technique is founded on a theoretical model of carbonate δ¹¹B variation with pH that assumes that the boron isotopic composition of carbonates mirrors the boron isotopic composition of borate in solution (δ¹¹B_carb = δ¹¹B_borate). Knowledge of the fractionation factor for isotope exchange between boric acid and borate in solution (α_4-3), the equilibrium constant for the dissociation of boric acid (pK_B*), as well as the isotopic composition of boron in seawater (δ¹¹B_sw) are required parameters of the model.The available data suggests that both the value of α_4-3 and the history of δ¹¹B_sw are poorly constrained. However, if one assumes that δ¹¹B_carb = δ¹¹B_borate, an empirical value for α_4-3 can be estimated from the results of inorganic carbonate precipitation experiments. This exercise yields an α_4-3 value of ∼0.974 in accordance with recent theoretical estimates, but substantially deviates from the theoretical value of 0.981 often used to estimate paleo-ocean pH. Re-evaluation of ocean pH using an α_4-3 value of 0.974 and published foraminiferal δ¹¹B values for the Cenozoic yield pH estimates that are relatively invariant, but unrealistically high (∼8.4-8.6). Uncertainty increases as foraminiferal ‘vital effects’ are considered and different models for secular changes in seawater δ¹¹B are applied.The inability to capture realistic ocean pH possibly reflects on our understanding of the isotopic relationship between carbonate and borate, as well as the mechanism of boron incorporation in carbonates. Given the current understanding of boron systematics, pH values estimated using this technique have considerable uncertainty, particularly when reconstructions exceed the residence time of boron in the ocean.     

Boron isotopes as pH proxy: A new look at boron speciation in deep-sea corals using B MAS NMR and EELS

Dissolved boron in modern seawater occurs in the form of two species, trigonal boric acid B(OH)₃ and tetrahedral borate ion . One of the key assumption in the use of boron isotopic compositions of carbonates as pH proxy is that only borate ions, , are incorporated into the carbonate. Here, we investigate the speciation of boron in deep-sea coral microstructures (Lophelia pertusa specimen) by using high field magic angle spinning nuclear magnetic resonance (¹¹B MAS NMR) and electron energy-loss spectroscopy (EELS). We observe both boron coordination species, but in different proportions depending on the coral microstructure, i.e. centres of calcification versus fibres. These results suggest that careful sampling is necessary before performing boron isotopic measurements in deep-sea corals. By combining the proportions of B(OH)₃ and determined by NMR and our previous ion microprobe boron isotope measurements, we propose a new equation for the relation between seawater pH and boron isotopic composition in deep-sea corals.     

Intra-shell boron isotope ratios in the symbiont-bearing benthic foraminiferan Amphistegina lobifera: Implications for δB vital effects and paleo-pH reconstructions

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ¹¹B has some limitations such as the knowledge of the fractionation factor (α_4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α_4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ¹¹B (Δ¹¹B) for each seawater pH. This Δ¹¹B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α_4-3, or the δ¹¹B_sw through time. It may also be independent of the pK_B (the dissociation constant of boric acid) value. Therefore, Δ¹¹B in foraminifera can potentially reconstruct paleo-pH of seawater.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

Production and Certification of a Unique Set of Isotope and Delta Reference Materials for Boron Isotope Determination in Geochemical,Environmental and Industrial Materials

Isotopic reference materials are essential to enable reliable and comparable isotope data. In the case of boron only a very limited number of such materials is available, thus preventing adequate quality control of measurement results and validation of analytical procedures. To address this situation a unique set of two boron isotope reference materials (ERM‐AE102a and ‐AE104a) and three offset δ¹¹B reference materials (ERM‐AE120, ‐AE121 and ‐AE122) were produced and certified. The present article describes the production and certification procedure in detail. The isotopic composition of all the materials was adjusted by mixing boron parent solutions enriched in ¹⁰B or ¹¹B with a boron parent solution having a natural isotopic composition under full gravimetric control. All parent solutions were analysed for their boron concentration as well as their boron isotopic composition by thermal ionisation mass spectrometry (TIMS) using isotope dilution as the calibration technique. For all five reference materials the isotopic composition obtained on the basis of the gravimetric data agreed very well with the isotopic composition obtained from different TIMS techniques. Stability and homogeneity studies that were performed showed no significant influence on the isotopic composition or on the related uncertainties. The three reference materials ERM‐AE120, ERM‐AE121 and ERM‐AE122 are the first reference materials with natural δ¹¹B values not equal to 0‰. The certified δ¹¹B values are ?20.2‰ for ERM‐AE120, 19.9‰ for ERM‐AE121 and 39.7‰ for ERM‐AE122, each with an expanded uncertainty (k = 2) of 0.6‰. These materials were produced to cover about three‐quarters of the known natural boron isotope variation. The ¹⁰B enriched isotope reference materials ERM‐AE102a and ERM‐AE104a were produced for industrial applications utilising ¹⁰B for neutron shielding purposes. The certified ¹⁰B isotope abundances are 0.29995 for ERM‐AE102a and 0.31488 for ERM‐AE104a with expanded uncertainties (k = 2) of 0.00027 and 0.00028, respectively. Together with the formerly certified ERM‐AE101 and ERM‐AE103 a unique set of four isotope reference materials and three offset δ¹¹B reference materials for boron isotope determination are now available from European Reference Materials.     

Controlling factors of the δ 11B-pH proxy and its research direction

Significant boron isotope fractionation occurs in nature (?70 ‰ to +75 ‰) due to the high geochemical reactivity of boron and the large relative mass difference between ¹⁰B and ¹¹B. Since the 1990s, reconstruction of ancient seawater pH using the isotopic composition of boron in bio-carbonates (δ ¹¹B_carb), and then calculation of the past pCO₂ have become important issues for the international isotope geochemistry community, and are called the δ ¹¹B-pH proxy. Although many achievements have been made by this proxy, various aspects of boron systematics require rigorous evaluation. Based on the previous researches, mechanism of boron isotope fractionation, variation of boron isotope (δ ¹¹B) in nature (especially in bio-carbonates) and controlling factors of the δ ¹¹B-pH proxy, such as the dissociation constant of B(OH)₃ in seawater (pK_a), the δ ¹¹B of seawater (δ ¹¹B_SW), the boron isotopic fractionation factor between B(OH) ₄ ^? and B(OH)₃ (α _4–3), and the incorporated species of boron into bio-carbonates, are reviewed in detail and the research directions of this proxy are proposed. Generally, the controversy about pK_a, δ ¹¹B_sw, and α _4–3 is relatively less, but whether boron incorporated into bio-carbonates only in the form of B(OH) ₄ ^? remains doubtful. In the future, it is required that the physicochemical processes that control boron incorporation into carbonates be rigorously characterized and that the related chemical and isotopic fractionation be quantified. It is also necessary and important to establish a “best-fit empirically equation” between δ ¹¹B_carb and pH of seawater based on the precipitation experiments of inorganic or culture experiments of corals or foraminifera. In addition, extended application of the δ ¹¹B-pH proxy to the earlier part of the Phanerozoic relying on the Brachiopods is worthy of studying. Like other geochemical indicators, there are limiting factors of δ ¹¹B; however, it remains a very powerful tool in the reconstruction of past seawater pH at present.     

Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill,Staten Island,New York,USA

A study was conducted at the Fresh Kills landfill, Staten Island, New York to investigate the use of B and Li isotopes as tracers of mixing and flow in the groundwater environment. Four end-member waters are present at the Fresh Kills: freshwater, seawater, a geochemically distinct transitional groundwater (that occurs in the zone of mixing between seawater and freshwater) and landfill leachate. The δ¹¹B and δ⁶Li values of end-member waters are distinct and have isotopic compositions that reflect the solute sources: freshwater δ¹¹B∼+30‰, δ⁶Li∼−22‰; transition zone groundwaters δ¹¹B∼+20‰, δ⁶Li∼−27‰; seawater δ¹¹B+40 to +75‰, δ⁶Li−37 to−44‰; leachate δ¹¹B∼+10‰ (δ⁶Li not determined). Those wells influenced by seawater exhibited a clear chemical mixing trend, with seawater contributions ranging from 3 to 85%. Well waters with a high percentage of seawater (>30%) had δ¹¹B values that were within 1‰ of the seawater value (+40‰), whereas a trend of increasing δ¹¹B values (+55 to +75‰) was observed for wells with a lower percentage of seawater (<30%). δ⁶Li values for well waters impacted by mixing with seawater ranged from−37 to−44‰, significantly more negative than pure seawater (−31‰). This deviation from the isotopic composition of seawater, for both δ¹¹B and δ⁶Li values, represents non-conservative behavior and is likely the result of isotopic fractionation during ion exchange reactions. The wide range of δ¹¹B and δ⁶Li values and the distinct isotopic compositions of end-member waters makes B and Li isotopes useful for recognizing solute sources, however isotopic fractionation may limit their use as simple tracers of groundwater flow and mixing.     

Stable nitrogen and carbon isotope (δN and δC) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ¹⁵N and δ¹³C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ¹⁵N and δ¹³C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ¹⁵N and δ¹³C values between sites was present. Skeletal δ¹⁵N values significantly increased and δ¹³C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of −0.013‰ m⁻¹ and +0.023‰ m⁻¹ are recommended for δ¹⁵N and δ¹³C, respectively. Average depth-corrected δ¹⁵N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ¹³C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ¹³C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ¹⁵N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ¹⁵N record, and suggests that these corals may be useful for δ¹⁵N-based paleoceanographic reconstructions. Variability in δ¹³C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ¹⁵N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ¹³C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.     

Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed

Boron isotopic fractionation during adsorption onto Ca-flocculated Aldrich humic acid (HA) has been investigated experimentally as a function of solution pH at 25°C and I = 0.15 M. Boron aqueous concentration and isotopic composition were determined by Cs₂BO₂⁺ Positive Thermal Ionization Mass Spectrometry analysis, while the structure of B surface complexes on HA was characterized using ¹¹B Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Significant B sorption on HA was observed at 6 < pH < 12 with a maximum value of Kd, the partition coefficient between adsorbed and aqueous boron, equal to 40 at pH = 9.5-10. Combined ¹¹B MAS NMR analysis and FITEQL modeling of B sorption on HA showed that this element forms tetrahedrally coordinated five- or six-membered ring chelates, most likely 1,2-diol and 1,3-diol complexes at alkaline pH (8 < pH < 11) and dicarboxylic complexes at near neutral conditions (6 < pH < 9). Results of this study demonstrate for the first time that boron sorption on HA induces a strong pH-dependent isotope fractionation—with ¹¹B depleted at the surface of HA—that reaches a maximum at 5 < pH < 9 (α = 0.975, Δ = −25‰) and decreases sharply at pH >9. The measured isotope fractionation cannot be modeled assuming that the isotopic composition of the sorbed borate species is identical to that of B(OH)₄^- species in the parent solution. It is shown that the extent of isotopic fractionation depends not only on B aqueous speciation but also on the distribution and structure of the borate surface complexes formed. In agreement with energetic constrains, calculation of the isotope fractionation factors between aqueous boric acid and boron surface complexes suggests that the formation of the strained six-membered ring 1,3-diol complex yields a much higher fractionation (α_BLP1−III = 0.954-0.960, Δ = −41/-47‰) than that of the very stable five-membered ring 1,2-diol (α_BLP2−III = 0.983, Δ = −18‰). The results of this study open new perspectives to understand and model boron biogeochemical cycle. It is predicted that boron sorption onto organic matter can have important consequences for the boron isotopic composition of surface water reservoirs (seawater, groundwater, soil waters) in which either abundant organic surfaces or significant boron concentrations are available. In addition, the large isotope fractionation between aqueous boric acid and surface boron-organic complexes found in the present work makes boron a promising tracer of biologic activity.     

Modelling the geochemical cycle of boron: Implications for the long-term δ11B evolution of seawater and oceanic crust

The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ¹¹B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ¹¹B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ¹¹B of Cretaceous seawater was close to the present-day value. Low δ¹¹B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ¹¹B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.     

Comment on “A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates” by M. Pagani, D. Lemarchand, A. Spivack and J. Gaillardet

Pagani et al. [Pagani M., Lemarchand D., Spivack A., and Gaillardet J. (2005). A critical evaluation of the boron isotope-pH proxy: the accuracy of ancient ocean pH estimates. Geochim. Cosmochim. Acta69(4), 953-961] use data from previous boron isotope studies to suggest that the fractionation between boric acid and borate in seawater as well as the history of δ¹¹B in seawater are poorly understood, thus limiting our ability to capture realistic ocean pH with this proxy. Although we agree with the authors that the long recognized uncertainty in the secular variation of δ¹¹B_seawater imposes a temporal limit on paleo-pH reconstructions, their evaluation of the δ¹¹B/pH relationship in carbonates is flawed. Potential complications from vital, temperature and dissolution effects reported in that paper are based on studies that are experimentally and/or analytically poorly constrained. Using published validation studies we will demonstrate that many of the problems outlined by Pagani et al. have already been addressed, or are based on misinterpretations of previous work. Most importantly, statistical evaluation suggests empirical data are best described by a fractionation of ∼20‰. Recent paleoreconstructions confirm that the boron isotope proxy can be used with confidence, if sample selection and analyses are done carefully.     

Boron isotopic composition of atmospheric precipitations and liquid-vapour fractionations

Boron isotope compositions (δ¹¹B) and B concentrations of rains and snows were studied in order to characterize the sources and fractionation processes during the boron atmospheric cycle. The ¹¹B/¹⁰B ratios of instantaneous and cumulative rains and snows from coastal and continental sites show a large range of variations, from −1.5 ± 0.4 to +26.0 ± 0.5‰ and from −10.2 ± 0.5 to +34.4 ± 0.2‰, respectively. Boron concentrations in rains and snows vary between 0.1 and 3.0 ppb. All these precipitation samples are enriched in ¹⁰B compared to the ocean value (δ¹¹B = +39.5‰). An empirical rain-vapour isotopic fractionation of +31‰ is estimated from three largely independent methods. The deduced seawater-vapour fractionation is +25.5‰, with the difference between the rain and seawater fractionations principally reflecting changes in the speciation of boron in the liquid with ∼100% B(OH)₃ present in precipitations. A boron meteoric water line, δD = 2.6δ¹¹B − 133, is proposed which describes the relationship between δD and δ¹¹B in many, but not all, precipitations. Boron isotopic compositions of precipitations can be related to that of the seawater reservoir by the seawater-vapour fractionation and one or more of (1) the rain-vapour isotopic fractionation, (2) evolution of the δ¹¹B value of the atmospheric vapour reservoir via condensation-precipitation processes (Rayleigh distillation process), (3) any contribution of vapour from the evaporation of seawater aerosols, and (4) any contribution from particulate matter, principally sea salt, continental dust and, perhaps more regionally, anthropogenic sources (burning of biomass and fossil fuels). From the δ¹¹B values of continental precipitations, a sea salt contribution cannot be more than a percent or so of the total B in precipitation over these areas.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

南海全新世大暖期海表水的高酸性证据

利用正热电离质谱高精度测定了南海化石珊瑚样品的δ¹¹B 比值,定量地重建了中晚全新世以来南海海表水的pH值。结果显示南海海表水pH值并不像预先设想的那样稳定。其中古海水pH值最低为6100aB.P.前的7.91;   最高为4300aB.P.前和1200aB.P.前的8.29。南海海表水pH值从全新世大暖期开始,整体上呈缓慢增加趋势,而到现代以后明显下降。珊瑚δ¹¹B记录表明南海海表水在中晚全新世有两个高酸性的时期,一个发生在全新世大暖期,一个为现代。全新世大暖期时南海出现的高海平面、偏强的东亚夏季风和偏弱的冬季风可能是导致其海表水出现高酸性的原因。现代南海海表水pH值显著偏低,背离了中晚全新世以来南海海表水pH值逐渐增加的趋势,这很可能说明人类大量排放的CO₂确实改变了南海海表水自然变化的规律,南海在变酸。     

Boron isotopic constraints on the source of Hawaiian shield lavas

Boron isotopic compositions of lavas from three representative Hawaiian shield volcanoes (Kilauea, Mauna Loa, and Koolau) were analyzed by thermal ionization mass spectrometry. The boron isotopic composition of each sample was analyzed twice, once with and once without acid leaching to evaluate the effect of posteruptive boron contamination. Our acid-leaching procedure dissolved glass, olivine, secondary zeolite, and adsorbed boron; this dissolved boron was completely removed from the residue, which was comprised of plagioclase, pyroxenes, and newly formed amorphous silica. We confirmed that an appropriate acid-leaching process can eliminate adsorbed and incorporated boron contamination from all submarine samples without modifying the original ¹¹B/¹⁰B ratio. On the other hand, when the sample was weathered, i.e., the olivine had an iddingsite rim, ¹¹B/¹⁰B of the acid-resistant minerals are also modified, thus it is impossible to get the preeruptive ¹¹B/¹⁰B value from the weathered samples. Through this elimination and evaluation procedure of posteruptive contamination, preeruptive δ¹¹B values for the shield lavas are −4.5 to −5.4‰ for Koolau (N = 8), −3.6 to −4.6‰ for Kilauea (N = 11), and −3.0 to −3.8‰ for Mauna Loa (N = 6).Historical Kilauea lavas show a systematic temporal trend for B content and Nb/B coupled with other radiogenic isotopic ratios and trace element ratios, at constant δ¹¹B, indicating little or no assimilation of crustal materials in these lavas. Uncorrelated B content and δ¹¹B in Koolau and Mauna Loa lavas may also indicate little or no effect of crustal assimilation in these lavas. The source of KEA-component (identical to the so-called Kea end member in Hawaiian lavas) of the Hawaiian source mantle, represented by Kilauea, should be derived from lower part of subducted oceanic crust or refractory peridotite in the recycled subducted slab. The systematic trend from Kilauea to Koolau—decreasing δ¹¹B coupled with decreasing εNd as well as increasing ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb—is consistent with involvement of subducted sediment components in the EMK(enriched Makapuu)-component, represented by Makapuu-stage of Koolau lavas.     

Calcification rate and the stable carbon, oxygen, and nitrogen isotopes in the skeleton, host tissue, and zooxanthellae of bleached and recovering Hawaiian corals

We tested the effectiveness of stable isotopes as recorders of physiological changes that occur during coral bleaching and recovery. Montipora capitata and Porites compressa fragments were bleached in outdoor tanks with seawater temperature raised to 30 °C (treatment corals) for one month. Additional fragments were maintained at 27 °C in separate tanks (control corals). After one month, (0 months recovery), buoyant weight was measured and a subset of fragments was frozen. Remaining fragments were returned to the reef for recovery. After 1.5, 4, and 8 months, fragments were collected, measured for buoyant weight, and frozen. Fragments were analyzed for stable carbon and oxygen isotopic compositions of the skeleton (δ¹³C_s; δ¹⁸O_s) and nitrogen and carbon isotopic compositions of the host tissue (δ¹⁵N_h; δ¹³C_h) and zooxanthellae (δ¹⁵N_z; δ¹³C_z). δ¹³C_s decreased immediately after bleaching in M. capitata, but not in P. compressa. δ¹⁸O_s of both species failed to record the warming event. During the remaining months of recovery, δ¹³C_s and δ¹⁸O_s were more enriched in treatment than control corals due to decreases in calcification and metabolic fractionation during that time. Increased δ¹⁵N_h of treatment P. compressa may be due to expelled zooxanthellae during bleaching and recovery. Increased δ¹⁵N_z at 1.5 months in treatment fragments of both species reflects the increased incorporation of dissolved inorganic nitrogen to facilitate mitotic cell division and/or chl a/cell recovery. Changes in δ¹³C_h and δ¹³C_z at 1.5 months in treatment M. capitata indicated a large increase in heterotrophically acquired carbon relative to photosynthetically fixed carbon. We experimentally show that isotopes in coral skeleton, host tissue and zooxanthellae can be used to verify physiological changes during bleaching and recovery, but their use as a proxy for past bleaching events in the skeletal record is limited.