Direct measurements of chemical composition of shock-induced gases from calcite: an intense global warming after the Chicxulub impact due to the indirect greenhouse effect of carbon monoxide

doi:10.1016/j.epsl.2009.02.037

Earth and Planetary Science Letters

Volume 282, Issues 1–4, 30 May 2009, Pages 56-64

https://doi.org/10.1016/j.epsl.2009.02.037 Get rights and content

Abstract

Shock-induced devolatilization in hypervelocity impacts has been considered to play important roles in the atmospheric evolution and mass extinctions in Earth's history. Although the chemical composition of shock-induced gas species from carbonate rocks has been considered as a key to understand the environmental change after the Chicxulub impact, it has not been investigated extensively before. Here, we conduct direct measurements of the chemical composition (CO/CO₂) of shock-induced gas species from calcite (CaCO₃) using both a laser gun system and an isotopic labeling technique. The CO/CO₂ ratio of the shock-induced gas species from calcite is measured to be 2.02 ± 0.41, suggesting that gaseous CO has been dominant in the shock-induced gases in the Chicxulub impact. In order to evaluate the environmental effects of the injection of CO gas, we investigated the post-impact atmospheric chemistry by incorporating our experimental results into a tropospheric photochemical model. The results suggest that an intense (2–5 °C) global warming would have lasted for several years after a Chicxulub-size impact mainly due to the greenhouse effect of tropospheric O₃, which is produced via photochemical reactions associated with CO gas. Such an intense global warming could have damaged the biosphere in the mass extinction at the Cretaceous–Paleogene (K–P) boundary.

Introduction

Shock waves generated by hypervelocity impacts of large asteroids or comets on planets induce devolatilization of the impactors and crustal materials, and thereby a large amount of gases are released into the atmosphere. Since the released gases, such as H₂O, SO₂, and CO₂, significantly may affect the global environment including the biosphere through the global warming (e.g., O'Keefe and Ahrens, 1989), sunlight shielding (e.g., Sigurdsson et al., 1992, Pope et al., 1994), and acid rain (e.g., Pope et al., 1994), the shock-induced devolatilization has been considered to play important roles in the atmospheric evolution and mass extinctions in Earth's history. In especially, it is now widely accepted that the Cretaceous–Paleogene (K–P) extinction at 65 Ma is caused by the Chicxulub impact event. Thus, studying the shock-induced devolatilization is critical for understanding the mechanisms responsible for the mass extinction.

Here we focused on hypervelocity impacts on carbonate rocks which occupy 15–20% by volume of Earth's sedimentary rocks. Since carbonate rocks are distributed widely on the surface of the Earth, the Earth has experienced a large number of impacts on carbonate rocks represented by the Chicxulub impact (Grieve and Robertson, 1979, Hildebrand et al., 1991). Carbonate rocks are thermodynamically unstable at high temperatures induced by shock heating (Tyburczy and Ahrens, 1986) and are devolatilized to form carbon-bearing gas species in the impacts (Boslough et al., 1982). Previous studies have discussed the prolonged global warming caused by injection of shock-induced CO₂ from carbonates by assuming the following decomposition reaction;CaCO₃ → CaO + CO₂(e.g., O'Keefe and Ahrens, 1989, Pierazzo et al., 1998, Ivanov et al., 1996). In the Chicxulub impact, the increase in surface temperature due to the greenhouse effect of shock-induced CO₂ has been estimated to be ~ 1–2 °C (Pope et al., 1997, Pierazzo et al., 1998).

In this study, we examine the importance of production of CO in shock-induced devolatilization of carbonate rocks. Considering the thermodynamic stability of CO among carbon-bearing gases at high-temperature conditions (e.g., Kress and McKay, 2004), CO would be produced by the devolatilization of carbonate rocks via the following reaction as well as CO₂;CaCO₃ → CaO + CO + O.

If CO is released into the atmosphere, the abundances of CH₄ and tropospheric O₃ will increase through photochemical reactions in the troposphere (e.g., Intergovernmental Panel on Climate Change (IPCC), 2007). Consequently, CO has more intense indirect radiative forcing than CO₂ owing to strong greenhouse effect of CH₄ and tropospheric O₃ (Daniel and Solomon, 1998), although CO itself has little direct radiative forcing. Therefore, the injection of shock-induced CO can rise the surface temperature higher than the previous estimates considering CO₂ only.

Despite such importance in the post-impact environmental effect, the chemical composition (i.e., CO/CO₂ ratio) of the gas species produced by devolatilization of carbonate rocks has been poorly constrained by laboratory experiments. This is because direct measurements of shock-induced gases have been difficult in previous studies using single-stage powder guns and 2-stage light-gas guns. In the previous studies, gun debris and CO₂-rich combustion gases flowing into a target chamber may have mixed with the shock-induced gases (Tyburczy and Ahrens, 1986). Boslough et al. (1982) investigated the chemical composition of the shock-induced gases from calcite using a gas-recovery system with a liquid nitrogen trap. Although they have showed that CO may be dominant in the shock-induced gases at shock pressure of ~ 19 GPa, the chemical composition of the shock-induced gases has not been investigated systematically. Since the chemical composition of shock-induced gases from carbonate rocks has been uncertain, it has been difficult to assess the possible environmental influence of large impacts on carbonate targets that have occurred on the Earth.

In this study, we conduct direct measurements of the chemical composition of shock-induced gases from calcite using both a laser gun that is free from gun debris and CO₂-rich combustion gases (Ohno et al., 2008) and an isotopic labeling technique. First, we describe the experimental system of the shock-induced devolatilization using a laser gun in Section 2. The chemical composition of the shock-induced gases as a function of peak shock pressure is shown in Section 3. Based on our experimental data, we calculate radiative forcings of shock-induced gases produced by the Chicxulub impact using a tropospheric one-box photochemical model and discuss the environmental effect in Section 5.

Section snippets

Experimental

We conduct shock-induced devolatilization experiments with a laser gun described by Ohno et al. (2008) and use isotopic-labeled calcite (Ca¹³CO₃) samples as the targets for identification of the shock-induced gases. In this section, we first describe the principle and experimental conditions of the laser gun method. Then, the chemical property and preparation of the target are discussed. Finally we describe our experimental procedure.

A schematic diagram of the experimental system is shown in

Detection of shock-induced ¹³CO and ¹³CO₂ from calcite

Fig. 2 shows the time variations of QMS signals of m/z = 4 (He), 29 (¹³CO), and 45 (¹³CO₂) in the shot onto the ¹³C-labeled calcite. The signal intensities of m/z = 29 and 45 increased rapidly by 2 to 3 orders of magnitude immediately after the impact, while that of m/z = 4 did not change significantly during the experimental run. These results indicate that the gas species of m/z = 29 and 45 are produced by the impact. Fig. 2 also shows the results of a blank shot with dotted lines. In the blank shot,

Mechanism for the CO production

Considering the thermodynamical stability of CO, a high temperature in target materials is required for the production of shock-induced gases with CO/CO₂ ~ 2. Using the Gibbs free energy minimization method, we estimate the equilibrium temperature of gas species required for the stable existence of comparable amount of CO with that of CO₂. The results show that the temperature of gas species becomes more than 6000 K in the range of peak shock pressure in our experiments. Such a high temperature

Implications for the environmental change after the Chicxulub impact

For evaluating the importance of the injection of CO gas on the environmental change after the Chicxulub impact, we estimate the radiative forcing of the shock-induced CO by incorporating our experimental data into a simple tropospheric photochemical model. As described in Section 1, the presence of CO in the troposphere enhances the abundances of CH₄ and O₃. If the abundance of CO increases in the troposphere, it consumes OH radical and thereby inhibits the loss of CH₄ through the reaction

Conclusion

We investigated the chemical composition (CO/CO₂) of shock-induced gas species from calcite in order to estimate the increase in surface temperature after the Chicxulub impact. Based on gas analyses of the direct measurements of shock-induced gases using both the laser gun method and isotope labeling technique, we have shown that gaseous CO as much as ~ 2 times that of CO₂ is produced by shock-induced devolatilization of calcite. These experimental results suggest that gaseous CO has been

Acknowledgements

K.K. would like to thank K. Saiki of the Univ. of Tokyo who made him use the XPS and provided useful comments. Y.S. would like to thank N.O. Ogawa and N. Ohkouchi of the JAMSTEC for advice on pre-treatment technique of metal foil for avoiding organic contaminations. This research was partly supported by the Grand in Aide from the Japan Society for the Promotion of Science.

References (51)

BosloughM.B. et al.
Shock-induced devolatilization of calcite
Earth Planet. Sci. Lett.
(1982)
GrieveR.A.F. et al.
The terrestrial cratering record 1. Current status of observations
Icarus
(1979)
GuptaS.C. et al.
Shock temperature in calcite (CaCO₃) at 95–160 GPa
Earth Planet. Sci. Lett.
(2002)
KressM.E. et al.
Formation of methane in comet impacts: implications for Earth, Mars, and Titan
Icarus
(2004)
LangeM.A. et al.
Shock-induced CO₂ loss from CaCO₃; implications for early planetary atmospheres
Earth Planet. Sci. Lett.
(1986)
OhnoS. et al.
Sulfur chemistry in laser-simulated impact vapor clouds: implications for the K/T impact event
Earth Planet. Sci. Lett.
(2004)
PierazzoE. et al.
Hydrocode modeling of Chicxulub as an oblique impact event
Earth Planet. Sci. Lett.
(1999)
PopeK.O. et al.
Impact winter and the Cretaceous/Tertiary extinctions: results of a Chicxulub asteroid impact model
Earth Planet. Sci. Lett.
(1994)
ShustorovichE.
The bond-order conservation approach to chemisorptions and heterogeneous catalysis: applications and implications
Adv. Catal.
(1990)
SigurdssonH. et al.
The impact of the Cretaceous–Tertiary bolide on evaporate terrane and generation of major sulfuric acid aerosol
Earth Planet. Sci. Lett.
(1992)

TorrisiL. et al.

Energy distribution of particles ejected by laser-generated aluminium plasma

Nucl. Instrum. Methods B

(2006)

WiegandA.N. et al.

Review of empirical methods for the calculation of the diurnal NO₂ photolysis rate coefficient

Atmos. Environ.

(2000)

AlvarezL.W. et al.

Extraterrestrial cause for the Cretaceous–Tertiary extinction

Science

(1980)

AshmoreM.R.

Assessing the future global impacts of ozone on vegetation

Plant Cell Environ.

(2005)

BelcherC.M. et al.

Fireball passes and nothing burns—the role of thermal radiation in the Cretaceous–Tertiary event: evidence from the charcoal record of North America

Geology

(2003)

CrutzenP.J.

Acid rain at the K/T boundary

Nature

(1987)

DanielJ.S. et al.

On the climate forcing of carbon monoxide

J. Geophys. Res.

(1998)

DeMoreW.B. et al.

Chemical kinetics and photochemical data for use in stratospheric modeling

GerasimovM.V. et al.

Physics and chemistry of impacts

Earth Moon Planets

(1998)

GradyD.E.

Shock deformation of brittle solids

J. Geophys. Res.

(1980)

GulickS.P.S. et al.

Importance of pre-impact crustal structure for the asymmetry of the Chicxulub impact crater

Nat. Geosci.

(2008)

HansonD.R. et al.

Heterogeneous reactions in sulfuric acid aerosols: a framework for model calculations

J. Geophys. Res.

(1994)

HildebrandA.R. et al.

Chicxulub crater: a possible Cretaceous/Tertiary boundary impact crater on the Yukatan Peninsula, Mexico

Geology

(1991)

Intergovernmental Panel on Climate Change (IPCC)

Climate Change 2001: The Scientific Basis

(2001)

IPCC

Climate Change 2007: The Physical Science Basis

(2007)

Cited by (36)

Densification of raw and torrefied biomass: A review
2024, Biomass and Bioenergy
Densification and torrefaction are potential technologies to valorize lignocellulosic residues into cleaner and sustainable alternative energy carriers for domestic, institutional, commercial and industrial thermal energy applications. Therefore, this review paper has focused on sources of lignocellulosic biomass for energy production. Furthermore, the processes involved in production of raw and torrefied briquettes/pellets have been discussed. Additionally, the physicomechanical, emissions and combustion properties of raw and torrefied briquettes produced from lignocellulosic residues have been presented. Also, the economics of briquetting lignocellulosic biomass materials have also been reviewed. The quality of densified solid biomass fuels from lignocellulosic residues was found to dependent on the feedstock and pretreatment conditions. Additionally, torrefaction and densification have been reported to upgrade the energy properties of loose biomass materials, as potential alternative fuel to firewood and charcoal. Finally, the economic profitability of densification projects has been found to be dependent on the availability of feedstocks, technology used and market potential of the product.
High-pressure melting behaviors of calcite from first-principles simulation
2024, Physica B: Condensed Matter
Calcite is a widely distributed and highly significant mineral on Earth. Understanding the physical properties and melting behavior of calcite facilitates the study of global carbon cycling, mantle dynamics, geological processes, and the structure and evolution of Earth and Earth-like planets. The existing experimental and theoretical data regarding calcite are not entirely consistent, and there is a lack of high-pressure melting data. Employing first-principles molecular dynamics (FPMD) combined with the Z method, we study the melting behavior of calcite at high pressures, determining the melting temperature up to 370 GPa. Through mean square displacement (MSD), radial distribution function (RDF), coordination number (CN), and diffusion coefficient (D), the melting temperature of calcite was established, enabling further exploration of its microscopic structural characteristics. The shock melting temperatures of PANDA and ANEOS models are lower than our FPMD melting curves. Compared with two-stage light gas gun experiments, the shock melting temperature is in good agreement, but the melting curve is different from static high-pressure experiment and laser shock experiment. The calcite melting curve exceeds the mantle melting curve, suggesting that the calcium-dominated carbonate system does not undergo melting throughout the entire mantle.
Global spatiotemporal completion of daily high-resolution TCCO from TROPOMI over land using a swath-based local ensemble learning method
2022, ISPRS Journal of Photogrammetry and Remote Sensing
At present, the daily global Total Column carbon monoxide (CO) (TCCO) product from TROPOMI is performed at the highest spatial resolution, which has been broadly adopted in atmospheric CO-related researches. Unfortunately, missing data emerges in the TROPOMI TCCO and the studies for the recovery of its missing pixels on a globe-scale are scarce. To address this issue, we develop a novel framework to recover missing data in global TROPOMI TCCO product over land from Jun. 01, 2018 to May. 31, 2021 by fusing multisource data. A finely devised Swath-based Local Ensemble Learning (SLEL) method is proposed due to the spatiotemporal discrepancy of missing pixels. In our study, three validation schemes are employed, including a Cross-Validation technique for each swath, in-situ validation against NDACC and TCCON, and transverse comparison with MOPITT and CAMS TCCO products. Validation results show that the developed framework presents an expected accuracy for recovering missing data in each swath, with daily average R and MB fluctuating around 0.9 and 0 mol/m², respectively. Meanwhile, the accuracy of recovered results is satisfactory and close to that of TROPOMI, with the R of 0.885 against NDACC and 0.918 against TCCON. Furthermore, the recovered results achieve a small (distinctly) better performance than those of MOPITT (CAMS). The spatial pattern of the recovered TCCO is consistent with that of the MOPITT TCCO and can specify much finer spatial details by comparison with CAMS. As for daily examples, the SLEL method well recovers the missing pixels in global TROPOMI TCCO with rich spatial details, even for some critical missing cases. Seasonal variations of global CO spatial patterns are also clearly captured in our results. The daily full-coverage high-resolution (0.07°) TCCO can help obtain spatiotemporally continuous global changes of CO and support related researches, which is accessible on https://doi.org/10.5281/zenodo.7213104.
Hugoniot and released state of calcite above 200 GPa with implications for hypervelocity planetary impacts
2022, Icarus
Citation Excerpt :
A comparison of Hugoniot between calcite and carbon dioxide may shed a light on this problem. There are several experimental studies on the degassing of carbonates through the shock recovery techniques and in-situ measurements on the shock-compressed carbonates (Ivanov and Deutsch, 2002; Kawaragi et al., 2009; Lange and Ahrens, 1986; Kurosawa et al., 2012). However, the Hugoniot for calcite has not been experimentally investigated at pressures above 100 GPa.
Carbonate minerals, for example calcite and magnesite, exist on the planetary surfaces of the Earth, Mars, and Venus, and are subjected to hypervelocity collisions. The physical properties of planetary materials at extreme conditions are essential for understanding their dynamic behaviors at hypervelocity collisions and the mantle structure of rocky planets including Super-Earths. Here we report laboratory investigations of laser-shocked calcite at pressures of 200–960 GPa (impact velocities of 12–30 km/s and faster than escape velocity from the Earth) using decay shock techniques. Our measured temperatures above 200 GPa indicated a large difference from the previous theoretical models. The present shock Hugoniot data and temperature measurements, compared with the previous reports, indicate melting without decomposition at pressures of ~110 GPa to ~350 GPa and a bonded liquid up to 960 GPa from the calculated specific heat. Our temperature calculations of calcite at 1 atm adiabatically released from the Hugoniot points suggest that the released products vary depending on the shock pressures and affect the planetary atmosphere by the degassed species. The present results on calcite newly provide an important anchor for considering the theoretical EOS at the extreme conditions, where the model calculations show a significant diversity at present.
Physical characterization of a simulated impact-vapor plume using laser ablation of Chicxulub sediments
2021, Planetary and Space Science
An asteroid impacted the Yucatan carbonate platform in the Southern Gulf of Mexico about 66 million years ago. The ejecta and impact-vapor plume introduced massive amounts of gases and dust into the atmosphere causing major global environmental effects that led to the Cretaceous-Paleogene mass extinction. The physical parameters of the Chicxulub impact-vapor plume are not completely known and are important to constrain its evolution and the aftermath of the event. Here we reconstruct the impact-vapor plume by laser ablation of target sediments recovered from the Yaxcopoil-1 borehole in the Chicxulub impact crater. The ablation experiment was performed under a reconstructed late Cretaceous atmosphere composed of 0.16% CO₂, 30% O₂, and 69.84% N₂ at 1000 mbar. The initial propagation velocities of the shockwave and impact-vapor plume were ~4.5 km s⁻¹ and ~2.3 km s⁻¹, respectively. The temperature and electron density of a simulated Chicxulub impact-vapor plume were determined using calcium emission lines. The initial temperature and electron density were estimated to be ~1.8(±0.1)×10⁴ K and ~5.9(±0.7)×10¹⁷ cm⁻³, respectively. The plume expanded adiabatically with a specific heat ratio of 1.31 ± 0.03. Its initial pressure was computed to be ~103 bar. These parameters are required in gas dynamic codes to develop chemical models to study the evolution of the simulated impact-vapor plume and predict the fluxes and nature of gases, vapors and mineral phases injected in the atmosphere. Such chemical models will allow scaling from laboratory to planetary conditions to better constrain the chemical effects to the environment and the biosphere by the asteroid impact.
Multiproxy analysis of paleoenvironmental, paleoclimatic and paleoceanographic changes during the early Danian in the Caravaca section (Spain)
2021, Palaeogeography, Palaeoclimatology, Palaeoecology
Citation Excerpt :
Nevertheless, all of different records suggest a broadly consistent age for Dan-C2 and a termination of the event near the C29r/C29n reversal. Worldwide, the K-PgB dark clay bed was deposited above the Chicxulub-linked air-fall layer under conditions of global climatic warming and alterations in oceanic productivity and acidity (D'Hondt et al., 1998; Coxall et al., 2006; Kawaragi et al., 2009; Birch et al., 2016; Henehan et al., 2016, 2019). At Caravaca, as in most continuous marine sections, the K-PgB dark clay bed is characterized by very low values in %CaCO3, δ18O and δ13C (Fig. 8A, B and Fig. 10D, E) (see Schulte et al., 2010, and references therein).
After the Chicxulub impact and mass extinction at the Cretaceous-Paleogene boundary (K-PgB), ecosystems haltingly recovered under unstable conditions. An early Danian (65.9 Ma) perturbation of the carbon cycle known as Dan-C2, which includes two carbon isotopic excursions (CIEs), has been ascribed to inputs of greenhouse gases through large-scale volcanism of the Deccan Traps. However, the relationship between Dan-C2, volcanism and environmental and climatic changes during the early Danian remains ambiguous. Based on stable isotopes, calcium carbonate content, magnetic susceptibility and planktic foraminifera, we present a paleoenvironmental, paleoclimatic and paleoceanographic reconstruction of the early Danian from the Caravaca section, Spain, one of the most complete and continuous K-PgB sections worldwide. The paleobiological response of planktic foraminifera suggests very volatile environmental conditions during the first 230 kyr of the Danian, as reflected in the rapid succession of opportunistic/generalist blooms and episodic high occurrences of aberrant specimens. According to our age model, the Dan-C2 has been identified at the Caravaca section from 65.92 to 65.74 Ma. No evidence of strong carbonate dissolution through ocean acidification was observed in the Dan-C2 interval or the rest of the studied section, excluding the K-PgB clay bed. We find that blooms of highly eutrophic Chiloguembelitria and increases in aberrant planktic foraminifera coincided with a major early Danian eruptive episode of Deccan Traps (Ambelani Formation), occurring before the Dan-C2. Conversely, during both Dan-C2 CIEs, less opportunistic taxa thrived, indicating changes in the upper part of the water column. This study demonstrates that the relationship between marine biota and climate change was very complex and rapidly changing during the early Danian. In addition, we propose that the Deccan volcanism had adverse effects on marine plankton, mostly through strong eutrophication, while an increased water column stratification during the Dan-C2 event resulted in a transient boost in the recovery of ecosystems.

View all citing articles on Scopus

View full text

Direct measurements of chemical composition of shock-induced gases from calcite: an intense global warming after the Chicxulub impact due to the indirect greenhouse effect of carbon monoxide

Abstract

Introduction

Section snippets

Experimental

Detection of shock-induced 13CO and 13CO2 from calcite

Mechanism for the CO production

Implications for the environmental change after the Chicxulub impact

Conclusion

Acknowledgements

Earth Planet. Sci. Lett.

Icarus

Earth Planet. Sci. Lett.

Icarus

Earth Planet. Sci. Lett.

Earth Planet. Sci. Lett.

Earth Planet. Sci. Lett.

Earth Planet. Sci. Lett.

Adv. Catal.

Earth Planet. Sci. Lett.

Nucl. Instrum. Methods B

Atmos. Environ.

Extraterrestrial cause for the Cretaceous–Tertiary extinction

Science

Assessing the future global impacts of ozone on vegetation

Plant Cell Environ.

Fireball passes and nothing burns—the role of thermal radiation in the Cretaceous–Tertiary event: evidence from the charcoal record of North America

Geology

Acid rain at the K/T boundary

Nature

On the climate forcing of carbon monoxide

J. Geophys. Res.

Chemical kinetics and photochemical data for use in stratospheric modeling

Physics and chemistry of impacts

Earth Moon Planets

Shock deformation of brittle solids

J. Geophys. Res.

Importance of pre-impact crustal structure for the asymmetry of the Chicxulub impact crater

Nat. Geosci.

Heterogeneous reactions in sulfuric acid aerosols: a framework for model calculations

J. Geophys. Res.

Chicxulub crater: a possible Cretaceous/Tertiary boundary impact crater on the Yukatan Peninsula, Mexico

Geology

Climate Change 2001: The Scientific Basis

Climate Change 2007: The Physical Science Basis

Detection of shock-induced ¹³CO and ¹³CO₂ from calcite