Tissue Decay Tested in Modern Metasequoia Leaves: Implications for Early Diagenesis of Leaves in Fossil Lagerstätten

Sedimentary deposits yielding extraordinarily-preserved fossils (known as Lagerstätten) may provide significant insights into the physiology and environments of ancient plants, particularly when the fossils represent their original characteristics with limited diagenetic modifications. To better understand molecular, isotopic, and morphological changes during the early stages of diagenesis, degradation experiments were conducted in two time series: 1) a laboratory decay series using fungi on leaves over the course of a month and 2) a natural decay series with leaves collected from different stages of leaf senescence and early diagenesis. Both experiments used modern leaves of the dawn redwood Metasequoia glyptostroboides, referred to as a “living fossil” due to the morphological stability of the genus Metasequoia over the past 100 million years. Both decay series demonstrate that microbial degradation of polysaccharides occurs on extremely short timescales and results in cell collapse, first in the exclusively cellulose-based primary cell walls and then much later in the lignin-strengthened secondary cell walls. Despite morphological and molecular changes, the stable carbon isotopic composition of bulk leaves and n-alkanes remained virtually unchanged. Together, these findings suggest that: 1) rapid burial and tissue stabilization is essential in the formation of Lagerstätte fossils, 2) polysaccharides play a key role in maintaining three-dimensional fossil leaf structures and thus polysaccharide preservation implies rapid burial and minimal microbial degradation, and 3) carbon isotope signals, including at the molecular level, altered little during diagenesis. Thus, interpretations of physiological and environmental signals from conifer leaves in Lagerstätten are not likely impacted by early diagenesis

Novel hydrocarbon-utilizing soil mycobacteria synthesize unique mycocerosic acids at a Sicilian everlasting fire

Soil bacteria rank among the most diverse groups of organisms on Earth and actively impact global processes of carbon cycling, especially in the emission of greenhouse gases like methane, CO2 and higher gaseous hydrocarbons. An abundant group of soil bacteria are the mycobacteria, which colonize various terrestrial, marine and anthropogenic environments due to their impermeable cell envelope that contains remarkable lipids. These bacteria have been found to be highly abundant at petroleum and gas seep areas, where they might utilize the released hydrocarbons. However, the function and the lipid biomarker inventory of these soil mycobacteria are poorly studied. Here, soils from the Fuoco di Censo seep, an everlasting fire (gas seep) in Sicily, Italy, were investigated for the presence of mycobacteria via 16S rRNA gene sequencing and fatty acid profiling. The soils contained high relative abundances (up to 34% of reads assigned) of mycobacteria, phylogenetically close to the Mycobacterium simiae complex and more distant from the wellstudied M. tuberculosis and hydrocarbon-utilizing M. paraffinicum. The soils showed decreasing abundances of mycocerosic acids (MAs), fatty acids unique for mycobacteria, with increasing distance from the seep. The major MAs at this seep were tentatively identified as 2,4,6,8-tetramethyl tetracosanoic acid and 2,4,6,8,10-pentamethyl hexacosanoic acid. Unusual MAs with mid-chain methyl branches at positions C-12 and C-16 (i.e., 2,12-dimethyl eicosanoic acid and 2,4,6,8,16-pentamethyl tetracosanoic acid) were also present. The molecular structures of the Fuoco di Censo MAs are different from those of the well-studied mycobacteria like M. tuberculosis or M. bovis and have relatively 13C-depleted values (38a to48), suggesting a direct or indirect utilization of the released seep gases like methane or ethane. The structurally unique MAs in combination with their depleted-13C values identified at the Fuoco di Censo seep offer a new tool to study the role of soil mycobacteria as hydrocarbon gas consumers in the carbon cycle

Limits of oxygen isotope palaeoaltimetry in Tibet

Measurements of stable water isotopes (oxygen and hydrogen) are commonly used to estimate palaeoelevation and quantify past changes in surface height across Tibet. Isotope palaeoaltimetry is often based on simple Rayleigh fractionation of a “parcel of air”, but must make a considerable number of approximations and assumptions. In this paper, we elaborate on the practicability of oxygen water isotopes in palaeoaltimetry, and evaluate a recent challenge to the palaeoaltimetry community. First, we examine the isotopic composition of oxygen (ẟ18O) versus altitude relationship in a set of five topographic realisations of Tibet using an isotope-enabled palaeoclimate model for the mid-Eocene, a period where a variety of topographic ‘uplift’ models have been proposed, and compare it to modern relationships. Second, we investigate whether isotopic composition is a good predictor of more modest changes in topography, such as the introduction of a valley system or uplift of only part of the Tibetan region. The aim of the paper is not to perform a direct comparison to data, but to use the model to further refine knowledge of the strengths and limitations of using oxygen isotopes in palaeoaltimetry. We find that oxygen isotope palaeoaltimetry works surprisingly well, with the exception that it could not identify low elevation valley systems bounded by high elevations because the isotopic composition of the water in the air becomes depleted at the first high elevation that an air parcel passes over and does not recover when it descends into the valley. Hence, isotope-based elevations are biased towards mountain range peaks. Overall, the application of oxygen isotope palaeoaltimetry does have value, but would be further strengthened when employed together with isotope-enabled models. In conjunction with other techniques such as terrestrial thermal lapse rates and energy conservation approaches, over a wide spatial region, a more accurate and fully three-dimension view of complex palaeo-topography is increasingly possible, which will in turn improve the precision of these palaeoaltimeters

Algal biomarkers as a proxy for pCO2: Constraints from late Quaternary sapropels in the eastern Mediterranean

Records of carbon dioxide concentrations (partial pressure expressed as pCO2) over Earth’s history provide trends that are critical to understand our changing world. To better constrain pCO2 estimations, here we test organic pCO2 proxies against the direct measurements of pCO2 recorded in ice cores. Based on the concept of stable carbon isotopic fractionation due to photosynthetic CO2 fixation (Ɛp), we use the stable carbon isotopic composition (δ13C) of the recently proposed biomarker phytol (from all photoautotrophs), as well as the conventionally used alkenone biomarkers (from specific species) for comparison, to reconstruct pCO2 over several Quaternary sapropel formation periods (S1, S3, S4, and S5) in the eastern Mediterranean Sea. The reconstructed pCO2 values are within error of the ice core values but consistently exceed the ice core values by ca. 100 µatm. This offset corresponds with atmospheric disequilibrium of present day CO2[aq] concentrations in the Mediterranean Sea from global pCO2, equivalent to ca. 100 µatm, although pCO2 estimates derived from individual horizons within each sapropel do not covary with the ice core values. This may possibly be due to greater variability in local CO2[aq] concentration changes in the Mediterranean, as compared with the global average pCO2, or possibly due to biases in the proxy, such as variable growth rate or carbon-concentrating mechanisms. Thus, the offset is likely a combination of physiological or environmental factors. Nevertheless, our results demonstrate that alkenone- and phytol-based pCO2 proxies yield statistically similar estimations (P-value = 0.02, Pearson’s r-value = 0.56), and yield reasonable absolute estimations although with relatively large uncertainties (± 100 µatm)

Molecular fossils from phytoplankton reveal secular PCO2 trend over the phanerozoic

Past changes in the atmospheric concentration of carbon dioxide (PCO2) have had a major impact on earth system dynamics; yet, reconstructing secular trends of past PCO2 remains a prevalent challenge in paleoclimate studies. The current long-term PCO2 reconstructions rely largely on the compilation of many different proxies, often with discrepancies among proxies, particularly for periods older than 100 million years (Ma). Here, we reconstructed Phanerozoic PCO2 from a single proxy: the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) that increases as PCO2 increases. This concept has been widely applied to alkenones, but here, we expand this concept both spatially and temporally by applying it to all marine phytoplankton via a diagenetic product of chlorophyll, phytane. We obtained data from 306 marine sediments and oils, which showed that Ɛp ranges from 11 to 24, agreeing with the observed range of maximum fractionation of Rubisco (i.e., 25 to 28). The observed secular PCO2 trend derived from phytane-based Ɛp mirrors the available compilations of PCO2 over the past 420 Ma, except for two periods in which our higher estimates agree with the warm climate during those time periods. Our record currently provides the longest secular trend in PCO2 based on a single marine proxy, covering the past 500 Ma of Earth history

Algal biomarkers as a proxy for pCO2: Constraints from late quaternary sapropels in the eastern Mediterranean

Records of carbon dioxide concentrations (partial pressure expressed as pCO2) over Earth's history provide trends that are critical to understand our changing world. To better constrain pCO2 estimations, here we test organic pCO2 proxies against the direct measurements of pCO2 recorded in ice cores. Based on the concept of stable carbon isotopic fractionation due to photosynthetic CO2 fixation (Ɛp), we use the stable carbon isotopic composition (δ13C) of the recently proposed biomarker phytol (from all photoautotrophs), as well as the conventionally used alkenone biomarkers (from specific species) for comparison, to reconstruct pCO2 over several Quaternary sapropel formation periods (S1, S3, S4, and S5) in the eastern Mediterranean Sea. The reconstructed pCO2 values are within error of the ice core values but consistently exceed the ice core values by ca. 100 µatm. This offset corresponds with atmospheric disequilibrium of present day CO2[aq] concentrations in the Mediterranean Sea from global pCO2, equivalent to ca. 100 µatm, although pCO2 estimates derived from individual horizons within each sapropel do not covary with the ice core values. This may possibly be due to greater variability in local CO2[aq] concentration changes in the Mediterranean, as compared with the global average pCO2, or possibly due to biases in the proxy, such as variable growth rate or carbon-concentrating mechanisms. Thus, the offset is likely a combination of physiological or environmental factors. Nevertheless, our results demonstrate that alkenone- and phytol-based pCO2 proxies yield statistically similar estimations (P-value = 0.02, Pearson's r-value = 0.56), and yield reasonable absolute estimations although with relatively large uncertainties (±100 µatm)

Validation of carbon isotope fractionation in algal lipids as a pCO2 proxy using a natural CO2 seep (Shikine Island, Japan)

Carbon dioxide concentrations in the atmosphere play an integral role in many Earth system dynamics, including its influence on global temperature. The past can provide insights into these dynamics, but unfortunately reconstructing long-term trends of atmospheric carbon dioxide (expressed in partial pressure; pCO2) remains a challenge in paleoclimatology. One promising approach for reconstructing past pCO2 utilizes the isotopic fractionation associated with CO2 fixation during photosynthesis into organic matter (εp). Previous studies have focused primarily on testing estimates of εp derived from the δ13C of species-specific alkenone compounds in laboratory cultures and mesocosm experiments. Here, we analyze εp derived from the δ13C of more general algal biomarkers, i.e., compounds derived from a multitude of species from sites near a CO2 seep off the coast of Shikine Island (Japan), a natural environment with CO2 concentrations ranging from ambient (ca. 310 µatm) to elevated (ca. 770 µatm) pCO2. We observed strong, consistent δ13C shifts in several algal biomarkers from a variety of sample matrices over the steep CO2 gradient. Of the three general algal biomarkers explored here, namely loliolide, phytol, and cholesterol, εp positively correlates with pCO2, in agreement with εp theory and previous culture studies. pCO2 reconstructed from the εp of general algal biomarkers show the same trends throughout, as well as the correct control values, but with lower absolute reconstructed values than the measured values at the elevated pCO2 sites. Our results show that naturally occurring CO2 seeps may provide useful testing grounds for pCO2 proxies and that general algal biomarkers show promise for reconstructing past pCO2

Algal biomarkers as a proxy for pCO2: Constraints from late quaternary sapropels in the eastern Mediterranean

Records of carbon dioxide concentrations (partial pressure expressed as pCO2) over Earth's history provide trends that are critical to understand our changing world. To better constrain pCO2 estimations, here we test organic pCO2 proxies against the direct measurements of pCO2 recorded in ice cores. Based on the concept of stable carbon isotopic fractionation due to photosynthetic CO2 fixation (Ɛp), we use the stable carbon isotopic composition (δ13C) of the recently proposed biomarker phytol (from all photoautotrophs), as well as the conventionally used alkenone biomarkers (from specific species) for comparison, to reconstruct pCO2 over several Quaternary sapropel formation periods (S1, S3, S4, and S5) in the eastern Mediterranean Sea. The reconstructed pCO2 values are within error of the ice core values but consistently exceed the ice core values by ca. 100 µatm. This offset corresponds with atmospheric disequilibrium of present day CO2[aq] concentrations in the Mediterranean Sea from global pCO2, equivalent to ca. 100 µatm, although pCO2 estimates derived from individual horizons within each sapropel do not covary with the ice core values. This may possibly be due to greater variability in local CO2[aq] concentration changes in the Mediterranean, as compared with the global average pCO2, or possibly due to biases in the proxy, such as variable growth rate or carbon-concentrating mechanisms. Thus, the offset is likely a combination of physiological or environmental factors. Nevertheless, our results demonstrate that alkenone- and phytol-based pCO2 proxies yield statistically similar estimations (P-value = 0.02, Pearson's r-value = 0.56), and yield reasonable absolute estimations although with relatively large uncertainties (±100 µatm)

Testing algal-based pCO2 proxies at a modern CO2 seep (Vulcano, Italy)

Understanding long-term trends in atmospheric concentrations of carbon dioxide (pCO2) has become increasingly relevant as modern concentrations surpass recent historic trends. One method for estimating past pCO2, the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) has shown promise over the past several decades, in particular using species-specific biomarker lipids such as alkenones. Recently, the Ɛp of more general biomarker lipids, organic compounds derived from a multitude of species, have been applied to generate longer-spanning, more ubiquitous records than those of alkenones but the sensitivity of this proxy to changes in pCO2 has not been constrained in modern settings. Here, we test Ɛp using a variety of general biomarkers along a transect taken from a naturally occurring marine CO2 seep in Levante Bay of the Aeolian island of Vulcano in Italy. The studied general biomarkers, loliolide, cholesterol, and phytol, all show increasing depletion in 13C over the transect from the control site towards the seep, suggesting that CO2 exerts a strong control on isotopic fractionation in natural phytoplankton communities. The strongest shift in fractionation was seen in phytol, and pCO2 estimates derived from phytol confirm the utility of this biomarker as a proxy for pCO2 reconstruction