pCO2 Estimates Research Articles

Seasonality of pCO2 and air-sea CO2 fluxes in the Central Labrador Sea

The Labrador Sea in the subpolar North Atlantic is known for its large air-to-sea CO2 fluxes, which can be around 40% higher than in other regions of intense ocean uptake like the Eastern Pacific and within the Northwest Atlantic. This region is also a hot-spot for storage of anthropogenic CO2. Deep water is formed here, so that dissolved gas uptake by the surface ocean directly connects to deeper waters, helping to determine how much atmospheric CO2 may be sequestered (or released) by the deep ocean. Currently, the Central Labrador Sea acts as a year-round sink of atmospheric CO2, with intensification of uptake driven by biological production in spring and lasting through summer and fall. Observational estimates of air-sea CO2 fluxes in the region rely upon very limited, scattered data with a distinct lack of wintertime observations. Here, we compile surface ocean observations of pCO2 from moorings and underway measurements, including previously unreported data, between 2000 and 2020, to create a baseline seasonal climatology for the Central Labrador Sea. This is used as a reference to compare against other observational-based and statistical estimates of regional surface pCO2 and air-sea fluxes from a collection of global products. The comparison reveals systematic differences in the representation of the seasonal cycle of pCO2 and uncertainties in the magnitude of air-sea CO2 fluxes. The analysis reveals the paramount importance of long-term, seasonally-resolved data coverage in this region in order to accurately quantify the size of the present ocean sink for atmospheric CO2 and its sensitivity to climate perturbations.

Spatiotemporal upscaling of sparse air-sea pCO2 data via physics-informed transfer learning.

Global measurements of ocean pCO2 are critical to monitor and understand changes in the global carbon cycle. However, pCO2 observations remain sparse as they are mostly collected on opportunistic ship tracks. Several approaches, especially based on direct learning, have been used to upscale and extrapolate sparse point data to dense estimates using globally available input features. However, these estimates tend to exhibit spatially heterogeneous performance. As a result, we propose a physics-informed transfer learning workflow to generate dense pCO2 estimates that are grounded in real-world measurements and remainphysically consistent. The models are initially trained on dense input predictors against pCO2 estimates from Earth system model simulation, and then fine-tuned to sparse SOCAT observational data. Compared to the benchmark direct learning approach, our transfer learning framework shows major improvements of up to 56-92%. Furthermore, we demonstrate that using models that explicitly account for spatiotemporal structures in the data yield better validation performances by 50-68%. Our strategy thus presents a new monthly global pCO2 estimate that spans for 35 years between 1982-2017.

The importance of adding unbiased Argo observations to the ocean carbon observing system

The current coverage of direct, high-quality ship-based observations of surface ocean pCO2 includes large gaps in time and space, and has been declining since 2017. These ocean observations provide the basis for the data products that reconstruct surface ocean pCO2 and estimate ocean carbon uptake. Improved data coverage is needed to advance our understanding of the ocean carbon sink and air–sea CO2 exchange. Targeted sampling from autonomous platforms, such as biogeochemical floats, combined with traditional shipboard measurements represents a promising path forward to improve surface ocean pCO2 reconstructions. However, floats provide indirect pCO2 estimates derived from pH, and thus have higher uncertainty and are biased compared to direct shipboard measurements. Here, we use a Large Ensemble Testbed (LET) of Earth System Models and the pCO2-Residual method to reconstruct surface ocean pCO2 globally to test the impact of additional float observations, both with and without measurement uncertainties. Through comparison to the ‘model truth’, the LET allows for robust evaluation of the reconstructions. With only shipboard sampling, surface ocean pCO2 is overestimated, and the 2000–2016 global ocean carbon sink is underestimated by 0.1 Pg C year−1. Additional float observations significantly reduce this underestimation, and deviate from the ‘model truth’ by as little as 0.01 Pg C year−1, even when floats have random uncertainties of ± 11 μatm. However, systematic bias in the float observations significantly degrades the accuracy of pCO2 reconstructions, leading to an even stronger underestimation of the global ocean carbon sink of up to 0.32 Pg C year−1. We conclude that adding float-based observations to the global observing system can significantly improve reconstructions of global surface ocean pCO2, but only if these data are unbiased.

Temperature-dependent carbon isotope fractionation in coccolithophores

Introduction: The stable carbon isotope ratio of long-chain alkenones produced by marine haptophyte phytoplankton has often been used to estimate past variations in atmospheric CO2 throughout the Cenozoic. However, previous experimental studies and surveys of alkenones from surface sediment and suspended particulate matter document additional environmental and physiological influences on carbon isotopic fractionation in alkenones.Methods: To clarify the non-CO2 effects on the alkenone carbon isotope fractionations, an important alkenone producer, Gephyrocapsa oceanica, was cultured in laboratory. To separate effects of different environment parameters, G. oceanica was grown in continuous cultures under a matrix of environmental conditions in order to explore the influence of temperature independently of CO2(aq). Through careful manipulation of the media carbon system, we can control the variation of the media CO2(aq) independently of temperature solubility. Carbon isotope fractionations from alkenones, coccolith, and particulate organic carbon were measured from this steady state system.Results and Discussion: We find εp in alkenones and particulate organic carbon inversely correlates with temperature, and temperature affects εp more strongly than CO2(aq). The magnitude of the temperature effect can be explained by higher growth rates at warmer temperatures with a similar growth rate dependence as observed in previous cultures in which growth rate was regulated by other factors. Where the past temperature influence on growth rate could be constrained using the UK’37 alkenone index in the same samples, our finding offers an approach to deconvolve an important physiological factor affecting ancient alkenones εp, and may therefore improve past pCO2 estimates.

Alkenone-derived estimates of Cretaceous pCO2

Alkenones are long-chain ketones produced by phytoplankton of the order Isochrysidales. They are widely used in reconstructing past sea surface temperatures, benefiting from their ubiquitous occurrence in the Cenozoic ocean. Carbon isotope fractionation (εp) between alkenones and dissolved inorganic carbon may also be used as a proxy for past atmospheric pCO2 and has provided continuous pCO2 estimates back to ca. 45 Ma. Here, an extended occurrence of alkenones from ca. 130 Ma is reported. We characterize the molecular structure and distribution of these Mesozoic alkenones and evaluate their potential phylogenetic relationship with Cenozoic alkenones. Using δ13C values of the C37 methyl alkenone (C37:2Me), the first alkenone-based pCO2 estimates for the Mesozoic are derived. These estimates suggest elevated pCO2 with a range of 548−4090 ppm (908 ppm median) during the super-greenhouse climate of the Early Cretaceous, in agreement with phytane-based pCO2 reconstructions. Finally, insights into the identity of the Cretaceous coccolithophores that possibly synthesized alkenones are also offered.

A regional pCO2 climatology of the Baltic Sea from in situ pCO2 observations and a model-based extrapolation approach

Abstract. Ocean surface pCO2 estimates are of great interest for the calculation of air–sea CO2 fluxes, oceanic uptake of anthropogenic CO2, and eventually the Global Carbon Budget. They are accessible from direct observations, which are discrete in space and time and thus always sparse, or from biogeochemical models, which only approximate reality. Here, a combined method for the extrapolation of pCO2 observations is presented that uses (1) model-based patterns of variability from an empirical orthogonal function (EOF) analysis of variability with (2) observational data to constrain EOF pattern amplitudes in (3) an ensemble approach, which locally adjusts the spatial scale of the mapping to the density of the observations. Thus, data-constrained, gap- and discontinuity-free mapped fields including local error estimates are obtained without the need for or dependence on ancillary data (e.g. satellite sea surface temperature maps). This extrapolation approach is generic in that it can be applied to any oceanic or coastal region covered by a suitable model and observations. It is used here to establish a regional pCO2 climatology of the Baltic Sea (Bittig et al., 2023: https://doi.org/10.1594/PANGAEA.961119), largely based on ICOS-DE ship of opportunity (SOOP) Finnmaid surface pCO2 observations between Lübeck-Travemünde (Germany) and Helsinki (Finland). The climatology can serve as improved input for atmosphere–ocean CO2 flux estimation in this coastal environment.

CMEMS-LSCE: a global, 0.25°, monthly reconstruction of the surface ocean carbonate system

Abstract. Observation-based data reconstructions of global surface ocean carbonate system variables play an essential role in monitoring the recent status of ocean carbon uptake and ocean acidification, as well as their impacts on marine organisms and ecosystems. So far, ongoing efforts are directed towards exploring new approaches to describe the complete marine carbonate system and to better recover its fine-scale features. In this respect, our research activities within the Copernicus Marine Environment Monitoring Service (CMEMS) aim to develop a sustainable production chain of observation-derived global ocean carbonate system datasets at high space–time resolutions. As the start of the long-term objective, this study introduces a new global 0.25∘ monthly reconstruction, namely CMEMS-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) for the period 1985–2021. The CMEMS-LSCE reconstruction derives datasets of six carbonate system variables, including surface ocean partial pressure of CO2 (pCO2), total alkalinity (AT), total dissolved inorganic carbon (CT), surface ocean pH, and saturation states with respect to aragonite (Ωar) and calcite (Ωca). Reconstructing pCO2 relies on an ensemble of neural network models mapping gridded observation-based data provided by the Surface Ocean CO2 ATlas (SOCAT). Surface ocean AT is estimated with a multiple-linear-regression approach, and the remaining carbonate variables are resolved by CO2 system speciation given the reconstructed pCO2 and AT; 1σ uncertainty associated with these estimates is also provided. Here, σ stands for either the ensemble standard deviation of pCO2 estimates or the total uncertainty for each of the five other variables propagated through the processing chain with input data uncertainty. We demonstrate that the 0.25∘ resolution pCO2 product outperforms a coarser spatial resolution (1∘) thanks to higher data coverage nearshore and a better description of horizontal and temporal variations in pCO2 across diverse ocean basins, particularly in the coastal–open-ocean continuum. Product qualification with observation-based data confirms reliable reconstructions with root-mean-square deviation from observations of less than 8 %, 4 %, and 1 % relative to the global mean of pCO2, AT (CT), and pH. The global average 1σ uncertainty is below 5 % and 8 % for pCO2 and Ωar (Ωca), 2 % for AT and CT, and 0.4 % for pH relative to their global mean values. Both model–observation misfit and model uncertainty indicate that coastal data reproduction still needs further improvement, wherein high temporal and horizontal gradients of carbonate variables and representative uncertainty from data sampling would be taken into account as a priority. This study also presents a potential use case of the CMEMS-LSCE carbonate data product in tracking the recent state of ocean acidification. The data associated with this study are available at https://doi.org/10.14768/a2f0891b-763a-49e9-af1b-78ed78b16982 (Chau et al., 2023).

Comparing the EMMA capnograph with sidestream capnography and arterial carbon dioxide pressure at 284 kPa.

Capnography aids assessment of the adequacy of mechanical patient ventilation. Physical and physiological changes in hyperbaric environments create ventilation challenges which make end-tidal carbon dioxide (ETCO2) measurement particularly important. However, obtaining accurate capnography in hyperbaric environments is widely considered difficult. This study investigated the EMMA capnograph for hyperbaric use. We compared the EMMA capnograph to sidestream capnography and the gold standard arterial carbon dioxide blood gas analysis in a hyperbaric chamber. In 12 resting subjects breathing air at 284 kPa, we recorded ETCO2 readings simultaneously derived from the EMMA and sidestream capnographs during two series of five breaths (total 24 measurements). An arterial blood gas sample was also taken simultaneously in five participants. Across all measurements there was a difference of about 0.1 kPa between the EMMA and sidestream capnographs indicating a very slight over-estimation of ETCO2 by the EMMA capnograph, but fundamentally good agreement between the two end-tidal measurement methods. Compared to arterial blood gas pressure the non-significant difference was about 0.3 and 0.4 kPa for the EMMA and sidestream capnographs respectively. In this study, the EMMA capnograph performed equally to the sidestream capnograph when compared directly, and both capnography measures gave clinically acceptable estimates of arterial PCO2.

Satellite Estimation of pCO2 and Quantification of CO2 Fluxes in China’s Chagan Lake in the Context of Climate Change

The massive increase in the amount of greenhouse gases in the atmosphere, especially carbon dioxide (CO2), has had a significant impact on the global climate. Research has revealed that lakes play an important role in the global carbon cycle and that they can shift between the roles of carbon sources and sinks. This study used Landsat satellite images to analyze the spatiotemporal characteristics and factors influencing the CO2 changes in Chagan Lake in China. We conducted six water sampling campaigns at Chagan Lake in 2020–2021 and determined the partial pressure of carbon dioxide (pCO2) from 110 water samples. Landsat surface reflectance was matched with water sampling events within ±7 days of satellite overpasses, yielding 75 matched pairs. A regression analysis indicated strong associations between pCO2 and both the band difference model of the near-infrared band and green band (Band 5-Band 3, R2 = 0.83, RMSE = 27.55 μatm) and the exponential model [((exp(b3) − exp(b5))2/(exp(b3) + exp(b5))2, R2 = 0.82, RMSE = 27.99 μatm]. A comparison between the performances of a linear regression model and a machine learning model found that the XGBoost model had the highest fitting accuracy (R2 = 0.94, RMSE = 16.86 μatm). We used Landsat/OLI images acquired mainly in 2021 to map pCO2 in Chagan Lake during the ice-free period. The pCO2 in the surface water of Chagan Lake showed considerable spatiotemporal variability within a range of 0–200 μatm. pCO2 also showed significant seasonal variations, with the lowest and highest mean values in autumn (30–50 μatm) and summer (120–150 μatm), respectively. Spatially, the pCO2 values in the southeast of Chagan Lake were higher than those in the northwest. The CO2 fluxes were calculated based on the pCO2 and ranged from −3.69 to −2.42 mmol/m2/d, indicating that Chagan Lake was absorbing CO2 (i.e., it was a weak carbon sink). Temperature, chlorophyll a, total suspended matter, and turbidity were found to have reinforcing effects on the overall trend of pCO2, while the Secchi disk depth was negatively correlated with pCO2. The results of this study provide valuable insights for assessing the role of lakes in the carbon cycle in the context of climate change.

Subantarctic pCO2 estimated from a biogeochemical float: comparison with moored observations reinforces the importance of spatial and temporal variability

Understanding the size and future changes of natural ocean carbon sinks is critical for the projection of atmospheric CO2 levels. The magnitude of the Southern Ocean carbon flux has varied significantly over past decades but mechanisms behind this variability are still under debate. While high accuracy observations, e.g. from ships and moored platforms, are important to improve models they are limited through space and time. Observations from autonomous platforms with emerging biogeochemical capabilities, e.g. profiling floats, provide greater spatial and temporal coverage. However, the absolute accuracy of CO2 partial pressure (pCO2) derived from float pH sensors is not well constrained. Here we capitalize on data collected for over a year by a biogeochemical Argo float near the Southern Ocean Time Series observatory to evaluate the accuracy of pCO2 estimates from floats beyond the initial in water comparisons at deployment. A latitudinal gradient of increasing pCO2 southward and spatial variability contributed to observed discrepancies. Comparisons between float estimated pCO2 and mooring observations were therefore restricted by temperature and potential density criteria (~ 7 µatm difference) and distance (1° latitude and longitude, ~ 11 µatm difference). By utilizing high quality moored and shipboard underway pCO2 observations, and estimates from CTD casts, we therefore found that over a year, differences in pCO2 between platforms were within tolerable uncertainties. Continued validation efforts, using measurements with known and sufficient accuracy, are vital in the continued assessment of float-based pCO2 estimates, especially in a highly dynamic region such as the subantarctic zone of the Southern Ocean.

Remote sensing and machine learning method to support sea surface pCO2 estimation in the Yellow Sea

With global climate changing, the carbon dioxide (CO2) absorption rates increased in marginal seas. Due to the limited availability of in-situ spatial and temporal distribution data, the current status of the sea surface carbon dioxide partial pressure (pCO2) in the Yellow Sea is unclear. Therefore, a pCO2 model based on a random forest algorithm has been developed, which was trained and tested using 14 cruise data sets from 2011 to 2019, and remote sensing satellite sea surface temperature, chlorophyll concentration, diffuse attenuation of downwelling irradiance, and in-situ salinity were used as the input variables. The seasonal and interannual variations of modeled pCO2 were discussed from January 2003 and December 2021 in the Yellow Sea. The results showed that the model developed for this study performed well, with a root mean square difference (RMSD) of 43 μatm and a coefficient of determination (R2) of 0.67. Moreover, modeled pCO2 increased at a rate of 0.36 μatm year-1 (R2 = 0.27, p < 0.05) in the YS, which is much slower than the rate of atmospheric pCO2 (pCO2air) rise. The reason behind it needs further investigation. Compared with pCO2 from other datasets, the pCO2 derived from the RF model exhibited greater consistency with the in-situ pCO2 (RMSD = 55 μatm). In general, the RF model has significant improvement over the previous models and the global data sets.

Surface ocean carbon budget in the 2017 south Georgia diatom bloom: Observations and validation of profiling biogeochemical argo floats

Estimates of the partial pressure of CO2 (pCO2) derived from biogeochemical Argo floats have the potential to improve our knowledge of the highly variable and partially observed Southern Ocean carbon sink through sampling at improved temporal and spatial resolution. Here we use the data from six biogeochemical Argo floats to characterise near-surface dissolved inorganic carbon (DIC) concentrations and fluxes at the site of an intense (Chl-a >3 mg m−3) mesoscale diatom bloom situated northwest of South Georgia. Concurrently, we provide independent analysis and validation of the methodology used by the Southern Ocean Carbon and Climate Observational and Modelling (SOCCOM) project for deriving surface pCO2 from float-based pH and oxygen measurements. We compare the float observations with co-located ship data from bottle samples over a month-long period. When compared to data sampled within 24 h and 25 km of each float profile, we find good agreement with a mean offset of −0.005 ± 0.018 (1σ) between float pH and bottle-derived pH. This translates to comparable pCO2 estimates between ship measurements and floats with a mean difference of 2.6 ± 12.8 (1σ) μatm, providing support for the use of biogeochemical Argo float data to supplement shipboard pCO2 measurements in the Southern Ocean. Based on float-derived pCO2 we calculate a sizeable local flux of CO2 of 24 ± 7 mmol C m−2 d−1 (over a 27-day period) from the atmosphere into the surface mixed layer, driven by a large air-sea pCO2 gradient and strong but variable winds. Despite the considerable air-sea flux, the local mixed layer carbon budget appears to be dominated by entrainment and detrainment of carbon-rich waters into and out of the mixed layer. However, given the large uncertainties associated with these fluxes and the significant challenges associated with closing the mixed layer budget, further research is required to refine float-based mixed layer DIC fluxes.

Controlling of the Late Palaeozoic glaciation on reef evolution: A case study of a late Kasimovian coral reef in southern Guizhou, South China

A late Kasimovian (Pennsylvanian) coral reef is reported in the Yanbanzhai (YBZ) area, southern Guizhou Province, South China. The YBZ coral reef, with a thickness of approximately 5.5 m and a lateral exposure of nearly 50 m, is primarily composed of the colonial rugose coral Fomichevella. The fusulinids collected from the reef indicates a late Kasimovian age. Five microfacies types have been identified, including coated bioclastic grainstone, coral (Fomichevella) framestone, bioclastic wackestone, bioclastic grainstone, and peloidal grainstone. The vertical evolution of the microfacies in the YBZ coral reef indicates major sedimentary environmental changes associated with relative sea‐level changes. The growth of the reef‐builder Fomichevella was controlled by the transgression and regression. Deep water promoted the upward expansion of Fomichevella, while shallow water inhibited its growth. Published records of atmospheric pCO2 estimation and sea‐surface temperatures, combined with geochemical proxies, confirm a warm climatic period during the late Kasimovian. This is an interglacial period conducive to the growth of the coral reef. Sea‐level and climate changes associated with the Late Palaeozoic ice age (LPIA) are interpreted as significant controls of the development of the YBZ coral reef. This research of the YBZ coral reef in South China provides practical palaeobiological evidence for global sea‐level rising during the late Kasimovian period caused by the high‐latitude Gondwana delaciation.

A practical pCO2 estimation and carbonate dynamics at an event of hypoxic water upwelling in Tokyo Bay

Urban bays have been considered to have a high CO2 absorption function due to the high nutrient load and resultant primary production. It is expected to enhance the function by promoting a blue carbon policy co-beneficial with strengthening ecosystem services such as fisheries. Estimates of CO2 absorption in urban bays have been based mostly on fragmentary information from shipboard observations, and an evaluation based on continuous observation of water quality is necessary considering the large spatiotemporal variability of such bay environment. In particular, Tokyo Bay has a specific feature of water pollution problem of hypoxia and anoxia leading to emitting high CO2. Bottom hypoxic and anoxic waters develop from early summer to autumn in the central part of the bay and enclosed areas such as navigation channels and borrow pits. It is known that pCO2 becomes very high in these waters, and their upwelling (called blue tide in the bay from the discoloration of the sea surface) is thought to cause high CO2 emissions; however, the actual situation is unknown. We developed a practical method for continuous estimation of pCO2 by appropriately combining continuous observation of water quality using sensors and measurements of carbonate parameters by water sampling. The results show that a highly reproducible and practical method for continuous estimation of pCO2 was possible by combining in situ salinity and pH meters and the total alkalinity and calc. pH measured by a total alkalinity titrator for water samples. This method was then applied to the duration of blue tide that occurred in the head of the bay in the summer and autumn of 2021. The pCO2 in the surface water was found to increase significantly and exceed 2000 µatm due to the upwelling of anoxic bottom water containing high pCO2. Mean CO2 emissions of approximately +2150 and +1540 µmol m-2 h-1 were observed at two stations during the upwelling period. The mean values rose to +2390 and +2190 µmol m-2h-1 with the blue tide and lowered to +810 and +1120 µmol m-2 h-1 without it, suggesting that high CO2 emissions may occur due to upwelling, especially with blue tides.

AVALIAÇÃO DE MÉTODOS DIRETOS E INDIRETOS DE MEDIÇÃO DA pCO2 EM AMBIENTES ESTUARINOS

EVALUATING DIRECT AND INDIRECT pCO2 MEASUREMENTS IN ESTUARINE ENVIRONMENTS. Estuaries are dynamic systems globally characterized as sources of CO2 to the atmosphere. However, they present large spatial-temporal variability in both pCO2 and FCO2. Increased CO2 emissions turns imperative to obtain continuous and accurate measurements of pCO2 in air and water to monitor FCO2 in these sensitive and complex environments. Currently, direct measurements of pCO2 and estimates of FCO2 in estuarine regions are still scarce and frequently the indirect pCO2 estimates are used that consists of measurements from at least two other parameters of the carbonate system: total alkalinity, dissolved inorganic carbon or pH. In this work, we evaluated recent direct and indirect measurements of pCO2 in the Jaguaribe River estuary-CE. This study provides a critical analysis of the data obtained through the two main methods mostly used to estimate pCO2, presenting the challenges towards greater consistency in obtaining data for a better understanding of the carbonate system in estuarine waters. We highlight the potential for continuous pCO2 measurements and long-term monitoring in coastal environments, contributing to improve knowledge of regional CO2 exchanges and to elucidate the role of estuaries in the global carbon cycle.

Maastrichtian atmosphericpCO2 and climatic reconstruction from carbonate paleosols of the Marília Formation (southeastern Brazil)

AbstractPaleosols are the product of ancient physical, chemical, and biological processes on the Earth's surface and, as such, may record information that can be used to reconstruct the paleoatmospheric and paleoenvironmental conditions under which they formed. In Brazilian continental sedimentary successions, few studies using ancient soils have focused on the relationship between paleopedogenesis and paleoclimate. The Marilia Formation is a 160-m-thick section of the Bauru Basin in which ∼ 66% of the deposits show some evidence of pedogenic modification as paleosols. In this paper, paleosol profiles in the Marilia Formation containing thick calcrete intervals are described and attributed to three pedotypes: Avencas, Monte Alto, and Garça. Macro and microscopic pedogenic features of each pedotype are described in detail. Moreover, the analysis of clay mineralogy, whole-rock geochemistry, and stable-isotope composition are used to define pedogenic processes, paleoclimate proxies, and atmospheric pCO2 estimates. The Avencas pedotype is composed of six polygenetic profiles with different phases of carbonate precipitation, clay illuviation, and biogenic actions. The Monte Alto pedotype is moderately developed and composed of calcic horizons formed mainly by rhizoliths, with higher degrees of calcification and oxidation compared to Avencas profiles. The Garça pedotype is well developed with five polygenetic profiles presenting high carbonate content and low accumulation of clay minerals (CIA-K) and leaching. Estimates of paleoprecipitation and paleotemperature from the studied paleosols using climofunctions of molar ratio of base to alumina, depth of carbonate accumulation, salinization, oxygen composition, and paleosol weathering index proxy (PWI) show values ranging from 242 to 718 mm/yr and 11° to 14°, respectively. Climofunction values suggest a paleoclimate of semiarid to subhumid during deposition of the Marília Formation. The climate data also suggests that during the Maastrichtian, the Bauru Basin was geographically within the Southern Hot Arid Belt zone, though showing strong influence of the lower latitudinal Equatorial Humid belt. Furthermore, atmospheric pCO2 values calculated from pedogenic carbonates may correlate with a cooling interval during the latest Maastrichtian (68.5–66.25 My).

Testing multiple pCO2 proxies from the Lower Cretaceous of the Laiyang Basin, eastern China

In recent decades, several proxies have been developed to reconstruct atmospheric palaeo-CO2 concentrations (pCO2). The confidence in pCO2 estimates can be increased by comparing results from multiple proxies with multiple species at a single site. Here, we develop a new pCO2 record for the Hauterivian–Barremian using three distinct proxies applied to two fossil coniferous species (Cupressinocladus sp. and Brachyphyllum obtusum) collected from Laiyang Basin, eastern China. The pCO2 values were 579–663 ppmv (recent standardization) and 966–1106 ppmv (Carboniferous standardization) based on the stomatal ratio (SR)-based method, and 472–525 ppmv based on the mechanistic model. All the pCO2 values calculated by these two methods here were highly coincident with those reconstructed by other SR-based and geochemical methods during the early stage of the Early Cretaceous. The pCO2 value estimated using the carbon isotope model was 202–409 ppmv, which is generally lower than the pCO2 value estimated using the other methods. The comparison and discussion of the results and theoretical mechanism from these three proxies indicate that the mechanistic model may be more feasible when used to reconstruct the pCO2 in the geological period. Furthermore, compared with data from other pCO2 records in the Early Cretaceous, the pCO2 values obtained in this study indicate a relatively low atmospheric CO2 concentration during the Hauterivian–Barremian and reflect the cooling climate in the early stage of Early Cretaceous.

Comparison of spectrophotometric and electrochemical pH measurements for calculating freshwater pCO2

AbstractInland waters have an important role in the global carbon cycle, contributing significantly to terrestrial carbon fluxes through downstream export and exchange of CO2 with the atmosphere. However, large uncertainties in freshwater inorganic carbon fluxes remain. One contributing factor is uncertainty in carbonate system calculations for estimating the partial pressure of CO2 (pCO2) from pH and alkalinity in freshwater systems. The uncertainty stems largely from inaccurate pH values caused by glass pH electrode measurements in low ionic strength systems. This study compares indicator‐based spectrophotometric and electrochemical pH measurements and their application for calculating freshwater pCO2. Our study found that, compared to a pCO2 reference method, pH electrode‐based estimates of pCO2 were overestimated by 230 ± 200 μatm (n = 54) where indicator‐based spectrophotometric pH estimates of pCO2 were 58 ± 33 μatm (n = 34) over the range of 100–1600 μatm. Furthermore, we found that when ionic strength was assumed to be zero, calculated pCO2 error was ~ 20% of the reference pCO2. A 19‐d field study using autonomous spectrophotometric pH and pCO2 sensors found an average error in calculated pCO2 of −70 ± 57 μatm (n = 1685). Although, our focus is on riverine CO2, these findings and subsequent conclusions apply to all freshwater systems. Spectrophotometric pH measurements will improve future freshwater pCO2 calculations and better quantify inland waters' role in the global carbon budget.

Quantitative reconstruction of atmospheric pCO2 sources during Eocene hyperthermal events based on data from the Fushun Basin, Northeast China

Eocene hyperthermal events are thought to be closely linked to rapid increases in atmospheric CO2. It is important to better understand the atmospheric triggers of these extreme events; however, reconstruction of pCO2 from sedimentary records remains challenging. Eocene hyperthermal events (Eocene thermal maximum, ETM; Early Eocene Climatic Optimum, EECO; Mid-Eocene Climatic Optimum, MECO) are well documented in the Fushun Basin of northeast China, but the source of organic matter (OM) used as a pCO2 archive in previous studies includes land plants, algae, mixed land and aquatic organisms in the Ypresian, Lutetian and Bartonian intervals, respectively. In this paper, we calculate pCO2 concentrations using δ13CTOC and δ13C27–31 and discuss the factors influencing discrepancies based on various calculations. Results show that both δ13CTOC and δ13C27–31 from single OM sources are reliable proxies for pCO2. During the ETM2, ETM3, EECO and MECO intervals, pCO2 was 638–2277 ppm, and palaeotemperature was approximately 2.6–8.9 °C higher than present. The background and peak values of pCO2 during hyperthermal events were compared with those related to methane hydrate, OM oxidation and volcanic sources of pCO2 carbon. The comparison revealed that pCO2 values associated with the ETM2, ETM3, EECO and MECO events were more consistent with those calculated by OM oxidation and locally overlapped with volcanic sources. These results indicate that these pCO2 estimates of hyperthermal events are predominantly derived from terrestrial OM oxidation and were influenced by volcanism.

Atmospheric pCO2 Reconstruction of Early Cretaceous Terrestrial Deposits in Texas and Oklahoma Using Pedogenic Carbonate and Occluded Organic Matter

Pedogenic carbonate samples collected from three Lower Cretaceous (Aptian–Albian) fossil localities in Texas and Oklahoma were analyzed to develop paleoatmospheric pCO2 estimates by measuring the stable carbon isotopes of pedogenic calcite and their co-existing occluded organic matter. Calcite δ13C values ranged from −10.9‰ to −4.4‰ while occluded organic matter δ13C values ranged from −27.3‰ to −21.1‰. These stable carbon isotope measurements combined with temperature (30 °C) and soil-respired CO2 concentration (839–6047 ppmV) values provided atmospheric pCO2 estimates ranging from 67 ppmV to over 1100 ppmV. These estimates show a significant increase in atmospheric pCO2 during the late Aptian followed by a decrease in atmospheric pCO2 during the late Aptian to early Albian transition period, roughly correlating with the OEA1b event. Given the lack of chronostratigraphic constraints of the Lower Cretaceous geologic units in the study area, these data provide further evidence for the approximate age of the units as well as pertinent paleoclimate insights into greenhouse climate conditions.