C3 plant carbon isotope discrimination does not respond to CO2 concentration on decadal to centennial timescales.

Plant carbon isotope discrimination is complex, and could be driven by climate, evolution and/or edaphic factors. We tested the climate drivers of carbon isotope discrimination in modern and historical plant chemistry, and focus in particular on the relationship between rising [CO2 ] over Industrialization and carbon isotope discrimination. We generated temporal records of plant carbon isotopes from museum specimens collected over a climo-sequence to test plant responses to climate and atmospheric change over the past 200 yr (including Pinus strobus, Platycladus orientalis, Populus tremuloides, Thuja koraiensis, Thuja occidentalis, Thuja plicata, Thuja standishii and Thuja sutchuenensis). We aggregated our results with a meta-analysis of a wide range of C3 plants to make a comprehensive study of the distribution of carbon isotope discrimination and values among different plant types. We show that climate variables (e.g. mean annual precipitation, temperature and, key to this study, CO2 in the atmosphere) do not drive carbon isotope discrimination. Plant isotope discrimination is intrinsic to each taxon, and could link phylogenetic relationships and adaptation to climate quantitatively and over ecological to geological time scales.

Terrestrial cooling in Northern Europe during the eocene-oligocene transition.

Geochemical and modeling studies suggest that the transition from the "greenhouse" state of the Late Eocene to the "icehouse" conditions of the Oligocene 34-33.5 Ma was triggered by a reduction of atmospheric pCO2 that enabled the rapid buildup of a permanent ice sheet on the Antarctic continent. Marine records show that the drop in pCO2 during this interval was accompanied by a significant decline in high-latitude sea surface and deep ocean temperature and enhanced seasonality in middle and high latitudes. However, terrestrial records of this climate transition show heterogeneous responses to changing pCO2 and ocean temperatures, with some records showing a significant time lag in the temperature response to declining pCO2. We measured the Δ47 of aragonite shells of the freshwater gastropod Viviparus lentus from the Solent Group, Hampshire Basin, United Kingdom, to reconstruct terrestrial temperature and hydrologic change in the North Atlantic region during the Eocene-Oligocene transition. Our data show a decrease in growing-season surface water temperatures (~10 °C) during the Eocene-Oligocene transition, corresponding to an average decrease in mean annual air temperature of ~4-6 °C from the Late Eocene to Early Oligocene. The magnitude of cooling is similar to observed decreases in North Atlantic sea surface temperature over this interval and occurs during major glacial expansion. This suggests a close linkage between atmospheric carbon dioxide concentrations, Northern Hemisphere temperature, and expansion of the Antarctic ice sheets.

Comparing Methodologies for Stomatal Analyses in the Context of Elevated Modern CO2.

Leaf stomata facilitate the exchange of water and CO2 during photosynthetic gas exchange. The shape, size, and density of leaf pores have not been constant over geologic time, and each morphological trait has potentially been impacted by changing environmental and climatic conditions, especially by changes in the concentration of atmospheric carbon dioxide. As such, stomatal parameters have been used in simple regressions to reconstruct ancient carbon dioxide, as well as incorporated into more complex gas-exchange models that also leverage plant carbon isotope ecology. Most of these proxy relationships are measured on chemically cleared leaves, although newer techniques such as creating stomatal impressions are being increasingly employed. Additionally, many of the proxy relationships use angiosperms with broad leaves, which have been increasingly abundant in the last 130 million years but are absent from the fossil record before this. We focus on the methodology to define stomatal parameters for paleo-CO2 studies using two separate methodologies (one corrosive, one non-destructive) to prepare leaves on both scale- and broad-leaves collected from herbaria with known global atmospheric CO2 levels. We find that the corrosive and non-corrosive methodologies give similar values for stomatal density, but that measurements of stomatal sizes, particularly guard cell width (GCW), for the two methodologies are not comparable. Using those measurements to reconstruct CO2 via the gas exchange model, we found that reconstructed CO2 based on stomatal impressions (due to inaccurate measurements in GCW) far exceeded measured CO2 for modern plants. This bias was observed in both coniferous (scale-shaped) and angiosperm (broad) leaves. Thus, we advise that applications of gas exchange models use cleared leaves rather than impressions.

Interpreting an Archaean paleoenvironment through 3D imagery of microbialites.

While stromatolites, and to a lesser extent thrombolites, have been extensively studied in order to unravel Precambrian (>539 Ma) biological evolution, studies of clastic-dominated microbially induced sedimentary structures (MISS) are relatively scarce. The lack of a consolidated record of clastic microbialites creates questions about how much (and what) information on depositional and taphonomic settings can be gleaned from these fossils. We used µCT scanning, a non-destructive X-ray-based 3D imaging method, to reconstruct morphologies of ancient MISS and mat textures in two previously described coastal Archaean samples from the ~3.48 Ga Dresser Formation, Pilbara, Western Australia. The aim of this study was to test the ability of µCT scanning to visualize and make 3D measurements that can be used to interpret the biotic-environmental interactions. Fossil MISS including mat laminae with carpet-like textures in one sample and mat rip-up chips in the second sample were investigated. Compiled δ13C and δ34S analyses of specimens from the Dresser Fm. are consistent with a taxonomically diverse community that could be capable of forming such MISS. 3D measurements of fossil microbial mat chips indicate significant biostabilization and suggest formation in flow velocities >25 cm s-1. Given the stratigraphic location of these chips in a low-flow lagoonal layer, we conclude that these chips formed due to tidal influence, as these assumed velocities are consistent with recent modeling of Archaean tides. The success of µCT scanning in documenting these microbialite features validates this technique both as a first step analysis for rare samples prior to the use of more destructive techniques and as a valuable tool for gaining insight into microbialite taphonomy.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low-oxygen cyanobacterial mats.

The sedimentary pyrite sulfur isotope (δ34 S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ34 S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ34 S geochemistry. Pyrite δ34 S values often capture δ34 S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ34 S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ34 S trends and δ34 S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment-water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ34 S signatures in early Earth environments. Porewater sulfide δ34 S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ34 S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ34 S values of pyrite are similar to porewater sulfide δ34 S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ34 S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.

Associations between redox-sensitive trace metals and microbial communities in a Proterozoic ocean analogue.

Constraints on Precambrian ocean chemistry are dependent upon sediment geochemistry. However, diagenesis and metamorphism can destroy primary biosignatures, making it difficult to consider biology when interpreting geochemical data. Modern analogues for ancient ecosystems can be useful tools for identifying how sediment geochemistry records an active biosphere. The Middle Island Sinkhole (MIS) in Lake Huron is an analogue for shallow Proterozoic waters due to its low oxygen water chemistry and microbial communities that exhibit diverse metabolic functions at the sediment-water interface. This study uses sediment trace metal contents and microbial abundances in MIS sediments and an oxygenated Lake Huron control site (LH) to infer mechanisms for trace metal burial. The adsorption of trace metals to Mn-oxyhydroxides is a critical burial pathway for metals in oxic LH sediments, but not for the MIS mat and sediments, consistent with conventional understanding of Mn cycling. Micronutrient trace metals (e.g., Zn) are associated with organic matter regardless of oxygen and sulfide availability. Although U and V are conventionally considered to be organically complexed in suboxic and anoxic conditions, U and organic covary in oxic LH sediments, and Mn-oxyhydroxide cycling dominates V deposition in the anoxic MIS sediments. Significant correlations between Mo and organic matter across all redox regimes have major implications for our interpretations of Mo isotope systematics in the geologic record. Finally, while microbial groups vary between the sampling locales (e.g., the cyanobacteria in the MIS microbial mat are not present in LH sediments), LH and MIS ultimately have similar relationships between microbial assemblages and metal burial, making it difficult to link trace metal burial to microbial metabolisms. Together, these results indicate that bulk sediment trace metal composition does not capture microbiological processes; more robust trace metal geochemistry such as isotopes and speciation may be critical for understanding the intersections between microbiology and sediment geochemistry.

Rapid response to anthropogenic climate change by Thuja occidentalis: implications for past climate reconstructions and future climate predictions.

Carbon isotope values of leaves (δ13Cleaf) from meta-analyses and growth chamber studies of C3 plants have been used to propose generalized relationships between δ13Cleaf and climate variables such as mean annual precipitation (MAP), atmospheric concentration of carbon dioxide ([CO2]), and other climate variables. These generalized relationships are frequently applied to the fossil record to create paleoclimate reconstructions. Although plant evolution influences biochemistry and response to environmental stress, few studies have assessed species-specific carbon assimilation as it relates to climate outside of a laboratory. We measured δ13Cleaf values and C:N ratios of a wide-ranging evergreen conifer with a long fossil record, Thuja occidentalis (Cupressaceae) collected 1804-2017, in order to maximize potential paleo-applications of our focal species. This high-resolution record represents a natural experiment from pre-Industrial to Industrial times, which spans a range of geologically meaningful [CO2] and δ13Catm values. Δleaf values (carbon isotope discrimination between δ13Catm and δ13Cleaf) remain constant across climate conditions, indicating limited response to environmental stress. Only δ13Cleaf and δ13Catm values showed a strong relationship (linear), thus, δ13Cleaf is an excellent record of carbon isotopic changes in the atmosphere during Industrialization. In contrast with previous free-air concentration enrichment experiments, no relationship was found between C:N ratios and increasing [CO2]. Simultaneously static C:N ratios and Δleaf in light of increasing CO2 highlights plants' inability to match rapid climate change with increased carbon assimilation as previously expected; Δleaf values are not reliable tools to reconstruct MAP and [CO2], and δ13Cleaf values only decrease with [CO2] in line with atmospheric carbon isotope changes.

A paleosol record of the evolution of Cr redox cycling and evidence for an increase in atmospheric oxygen during the Neoproterozoic.

Atmospheric oxygen levels control the oxidative side of key biogeochemical cycles and place limits on the development of high-energy metabolisms. Understanding Earth's oxygenation is thus critical to developing a clearer picture of Earth's long-term evolution. However, there is currently vigorous debate about even basic aspects of the timing and pattern of the rise of oxygen. Chemical weathering in the terrestrial environment occurs in contact with the atmosphere, making paleosols potentially ideal archives to track the history of atmospheric O2 levels. Here we present stable chromium isotope data from multiple paleosols that offer snapshots of Earth surface conditions over the last three billion years. The results indicate a secular shift in the oxidative capacity of Earth's surface in the Neoproterozoic and suggest low atmospheric oxygen levels (<1% PAL pO2 ) through the majority of Earth's history. The paleosol record also shows that localized Cr oxidation may have begun as early as the Archean, but efficient, modern-like transport of hexavalent Cr under an O2 -rich atmosphere did not become common until the Neoproterozoic.

A case for low atmospheric oxygen levels during Earth's middle history.

The oxygenation of the atmosphere - one of the most fundamental transformations in Earth's history - dramatically altered the chemical composition of the oceans and provides a compelling example of how life can reshape planetary surface environments. Furthermore, it is commonly proposed that surface oxygen levels played a key role in controlling the timing and tempo of the origin and early diversification of animals. Although oxygen levels were likely more dynamic than previously imagined, we make a case here that emerging records provide evidence for low atmospheric oxygen levels for the majority of Earth's history. Specifically, we review records and present a conceptual framework that suggest that background oxygen levels were below 1% of the present atmospheric level during the billon years leading up to the diversification of early animals. Evidence for low background oxygen levels through much of the Proterozoic bolsters the case that environmental conditions were a critical factor in controlling the structure of ecosystems through Earth's history.