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.     

Techniques for assessing spatial heterogeneity of carbonate δ13C values: Implications for craton‐wide isotope gradients

The sedimentary record of carbonate carbon isotopes (δ¹³C_carb) provides one of the best methods for correlating marine strata and understanding the long‐term evolution of the global carbon cycle. This work focuses on the Late Ordovician Guttenberg isotopic carbon excursion, a ca 2·5‰ positive δ¹³C_carb excursion that is found in strata globally. Substantial variability in the apparent magnitude and stratigraphic morphology of the Guttenberg excursion at different localities has hampered high‐resolution correlations and led to divergent reconstructions of ocean chemistry and the biogeochemical carbon cycle. This work investigates the magnitude, spatial scale and sources of isotopic variability of the Guttenberg excursion in two sections from Missouri, USA. Centimetre‐scale isotope transects revealed variations in δ¹³C_carb and δ¹⁸O_carb greater than 2‰ across individual beds. Linear δ¹³C_carb to δ¹⁸O_carb mixing lines, together with petrographic and elemental abundance data, demonstrate that much of the isotopic scatter in single beds is due to mixing of isotopically distinct components. These patterns facilitated objective sample screening to determine the ‘least‐altered’ data. A δ¹⁸O_carb filter based on empirical δ¹⁸O_carb values of well‐preserved carbonate mudstones allowed further sample discrimination. The resulting ‘least‐altered’ δ¹³C_carb profile improves the understanding of regional as well as continental‐scale stratigraphic relations in this interval. Correlations with other Laurentian sections strongly suggest that: (i) small‐scale variability in Guttenberg excursion δ¹³C_carb values may result in part from local diagenetic overprinting; (ii) peak‐Guttenberg excursion δ¹³C_carb values of the Midcontinent are not distinct from their Taconic equivalents; and (iii) no primary continental‐scale spatial gradient in δ¹³C_carb (for example, arising from chemically distinct ‘aquafacies’) is required during Guttenberg excursion‐time. This study demonstrates the importance of detailed petrographic and geochemical screening of samples to be used for δ¹³C_carb chemostratigraphy and for enhancing understanding of epeiric ocean chemistry.     

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.     

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.     

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.     

Carbon and sulfur isotopic fluctuations associated with the end-Guadalupian mass extinction in South China

Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ¹³C_carb, δ¹³C_org), and sulfur isotopic compositions of carbonate associated sulfate (δ³⁴S_sulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ¹³C_carb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ¹³C_carb values, Δ¹³C_carb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ³⁴S_sulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.     

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.     

Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of ²⁴Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of ²⁶Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ²⁶Mg_sw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ²⁶Mg_sw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ²⁶Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in ²⁴Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ²⁶Mg_sw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ²⁶Mg_sw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ²⁶Mg of the Huangjin limestone makes it difficult to reconstruct δ²⁶Mg_sw using bulk carbonate/calcareous sediments. Finally, δ²⁶Mg_sw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.     

Kinetic isotopic fractionation during carbonate dissolution in laboratory experiments: Implications for detection of microbial CO2 signatures using δC-DIC

Laboratory experiments on reagent-grade calcium carbonate and carbonate rich glacial sediments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis and early stages of carbonate dissolution driven by atmospheric CO₂. There is preferential dissolution of Ca¹²CO₃ during hydrolysis, resulting in δ¹³C-DIC values that are significantly lighter isotopically than the bulk carbonate. The fractionation factor for this kinetic isotopic effect is defined as ε_carb. ε_carb is greater on average for glacial sediments (−17.4‰) than for calcium carbonate (−7.8‰) for the < 63 μm size fraction, a sediment concentration of 5 g L⁻¹ and closed system conditions at 5°C. This difference is most likely due to the preferential dissolution of highly reactive ultra-fine particles with damaged surfaces that are common in subglacial sediments. The kinetic isotopic fractionation has a greater impact on δ¹³C-DIC at higher CaCO₃:water ratios and is significant during at least the first 6 h of carbonate dissolution driven by atmospheric CO₂ at sediment concentrations of 5 g L⁻¹. Atmospheric CO₂ dissolving into solution following carbonate hydrolysis does not exhibit any significant equilibrium isotopic fractionation for at least ∼ 6 h after the start of the experiment at 5°C. This is considerably longer than previously reported in the literature. Thus, kinetic fractionation processes will likely dominate the δ¹³C-DIC signal in natural environments where rock:water contact times are short <6-24 h (e.g., glacial systems, headwaters in fluvial catchments) and there is an excess of carbonate in the sediments. It will be difficult apply conventional isotope mass balance techniques in these types of environment to identify microbial CO₂ signatures in DIC from δ¹³C-DIC data.     

Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.     

Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4

The stable boron isotope ratio (¹¹B/¹⁰B) in marine carbonates is used as a paleo-pH recorder and is one of the most promising paleo-carbonate chemistry proxies. Understanding the thermodynamic basis of the proxy is of fundamental importance, including knowledge on the equilibrium fractionation factor between dissolved boric acid, B(OH)₃, and borate ion, B(OH)₄⁻ (, hereafter α_(B3-B4)). However, this factor has hitherto not been determined experimentally and a theoretically calculated value (Kakihana and Kotaka, 1977, hereafter KK77) has therefore been widely used. I examine the calculations underlying this value. Using the same spectroscopic data and methods as KK77, I calculate the same α_(B3−B4) = 1.0193 at 300 K. Unfortunately, it turns out that in general the result is sensitive to the experimentally determined vibrational frequencies and the theoretical methods used to calculate the molecular forces. Using analytical techniques and ab initio molecular orbital theory, the outcome for α_(B3-B4) varies between ∼1.020 and ∼1.050 at 300 K. However, several arguments suggest that α_(B3-B4) ? 1.030. Measured isotopic shifts in various ¹⁰B-, ²D-, and ¹⁸O-labeled isotopomers do not provide a constraint on stable boron isotope fractionation. I conclude that in order to anchor the fundamentals of the boron pH proxy, experimental work is required. The critics of the boron pH proxy should note, however, that uncertainties in α_(B3-B4) do not bias pH reconstructions provided that organism-specific calibrations are used.     

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.     

An explanation of the effect of seawater carbonate concentration on foraminiferal oxygen isotopes

Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ¹⁸O of the foraminiferal calcite decreases with increasing CO₃²⁻ concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H₂CO₃] + [HCO₃⁻] + [CO₃²⁻] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO₃ also decreases with increasing pH. The slope of shell δ¹⁸O vs. [CO₃²⁻] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg⁻¹)⁻¹ (Spero et al., 1997), whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg⁻¹)⁻. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed.     

A modeling study of the impact of the δO value of near-surface soil water on the δO value of the soil-surface CO2 flux

Measurements of ¹⁸O in atmospheric CO₂ have been used to partition site-level measured net ecosystem CO₂ fluxes into gross fluxes and as a constraint on land surface biophysical processes at regional and global scales. However, these approaches require prediction of the δ¹⁸O value of the net CO₂ flux between the soil and atmosphere (δ_F), a quantity that is difficult to measure and accurately predict. δ_F depends on the depth-dependent δ¹⁸O value of soil water (δ_sw), soil moisture and temperature, soil CO₂ production, and the δ¹⁸O value of above-surface CO₂. I applied numerical model manipulations, regression analysis, a simple estimation method, and an analysis of the characteristic times of relevant processes to study the impacts of these parameters on δ_F. The results indicate that ignoring δ_sw gradients in the near-surface soil can lead to large errors. In particular, in systems where δ_sw gradients exist, generalizing previous experimental observations to infer that a bulk (e.g., 5-10 cm or 5-15 cm depth) estimate of δ_sw can be used to estimate δ_F is problematic. These results highlight the need for further experiments and argue for the importance of accurately resolving near-surface δ_sw in the context of partitioning ecosystem CO₂ fluxes and CO₂ source attribution.     

NIST RM 8301 Boron Isotopes in Marine Carbonate (Simulated Coral and Foraminifera Solutions): Inter‐laboratory δ11B and Trace Element Ratio Value Assignment

The boron isotopic ratio of ¹¹B/¹⁰B (δ¹¹B_SRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ¹¹B_SRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ¹¹B_SRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.     

Carbon and oxygen isotopes in the Frasnian–Famennian section of the Kuznetsk basin (southern West Siberia)

The first detailed isotope-geochemical study of carbonate deposits has been performed in the Lower Famennian stratotype section of the northwestern Kuznetsk Basin (Kosoy Utyos), which was localized in the middle latitudes of the Northern Hemisphere in the Late Devonian. The δ¹³C_carb, δ¹³C_org, and δ¹⁸O variation curves were constructed for the section deposits. Geochemical and petrographic studies of carbonates allowed allocation of samples that underwent postsedimentation alteration and exclude them from further interpretation. Compared with coeval sections in the other world's regions, the Kosoy Utyos section is characterized by higher δ¹³C_carb values, up to 5.4‰, whereas the maximum value in subequatorial area sections is 4‰. The isotope shift amplitude of the studied section reaches 4.6‰, which is 1.5‰ higher than those in other regions. The δ¹⁸O values are 3‰ lower than the ones of the world's coeval sections. The results obtained show that δ¹³C and δ¹⁸O variation trends differ from those of coeval subequatorial sections. The high shift amplitude and maximum δ¹³C_carb values in the Kosoy Utyos section are due to the shallow-water carbonate sedimentation environments on the Siberian continental shelf and, probably, the lower temperatures of waters in the middle latitudes as compared with the subequatorial areas.     

Liquid-vapor fractionation of boron and boron isotopes: Experimental calibration at 400°C/23 MPa to 450°C/42 MPa

We experimentally determined the boron partitioning and boron isotope fractionation between coexisting liquid and vapor in the system H₂O−NaCl−B₂O₃. Experiments were performed along the 400 and 450°C isotherms. Pressure conditions ranged from 23 to 28 MPa at 400°C and from 38 to 42 MPa at 450°C. Boron partitions preferentially into the liquid. Its overall liquid-vapor fractionation is, however, weak: Calculated boron distribution coefficients D_B^liquid-vapor are < 2.5 at all run conditions. With decreasing pressure (i.e. increasing opening of the solvus) D_B^liquid-vapor increases along the individual isotherms. Extrapolation to salt saturated conditions yields maximum boron liquid-vapor fractionations of D_B^liquid-vapor = 1.8 at 450°C and D_B^liquid-vapor = 2.7 at 400°C. ¹¹B preferentially fractionates into the vapor. Calculated Δ¹¹B_vapor-liquid = {[(¹¹B/¹⁰B)_vapor - (¹¹B/¹⁰B)_liquid]/(¹¹B/¹⁰B)_{NBS 951}}*1000 are small and range from 0.2 (± 0.7) to 0.9 (± 0.5) ‰ at 450°C and from 0.1 (± 0.6) to 0.7 (± 0.6) ‰ at 400°C. The data indicate increasing isotopic fractionation with decreasing pressure (i.e. increasing opening of the solvus). Extrapolation to salt saturated conditions yields maximum boron isotope liquid-vapor fractionations of Δ¹¹B_vapor-liquid = 1.5 (± 0.7) ‰ at 450°C and Δ¹¹B_vapor-liquid = 1.3 (± 0.6) ‰ at 400°C. The weak boron isotope fractionation suggests similar trigonal speciation in liquid and vapor. Although the boron and boron isotope fractionation between liquid and vapor is only weak, mass balance calculations indicate that for high degrees of fractionation liquid-vapor phase separation in an open system can significantly alter the boron and boron isotope signature of low-salinity hydrous fluids in hydrothermal systems. Comparing the model calculations with natural oceanic hydrothermal fluids, however, indicate that other processes than fluid phase separation dominate the boron geochemistry in oceanic hydrothermal fluids.     

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.     

Late Cenomanian environmental conditions at the submerged Tatric Ridge,Central Western Carpathians during the period preceding Oceanic Anoxic Event 2 – A palaeontological and isotopic approach

Micropalaeontological and isotopic studies of the upper Cenomanian turbiditic/hemipelagic sediments from the High-Tatric unit (Central Western Carpathians; Polish part of the Tatra Mountains) has been undertaken to characterize the sedimentary conditions in the Tatric basin, a part of the Western Tethys, related to the interval preceding the late Cenomanian oceanic anoxic event (OAE2). The deposition of these sediments, including organic-rich layers (TOC up to 0.7%), corresponds to the Rotalipora cushmani foraminiferal Zone. Microfacial, foraminiferal and palynological analyses show that the sea floor was located at upper bathyal depths and the water column was poorly oxygenated. The intrabasinal carbonate material indicates moderate primary productivity with rare periods of upwellings. The scarcity of marine fossils in redeposited material and features of carbonate lithoclasts suggest very low productivity in the nearshore surface water, most probably due to a low-density hyposaline cap as surface runoff from the southern margin of the basin. The carbon isotopic study documents the negative values of δ¹³C_carb in the whole section as an effect of transfer of isotopically light carbon sourced from various sources. Such negative values of δ¹³C_carb are characteristic of the upper Cenomanian sediments, deposited in relatively shallow water basins, characterized by input of terrestrial organic matter and/or carbonate particles known from the Western Interior sections, the Atlantic coastal plain, the northwestern African margin, the eastern margin of the Apulian Platform and shelf sediments in the NW Europe and Tethyan Himalayas. Most probably, all of these events could be related to the global sea level fluctuations that occurred ca. 95.5–94.5 Ma comparing with the Haq (2014) eustatic curve.