Low atmospheric CO2 levels before the rise of forested ecosystems.

The emergence of forests on Earth (~385 million years ago, Ma)1 has been linked to an order-of-magnitude decline in atmospheric CO2 levels and global climatic cooling by altering continental weathering processes, but observational constraints on atmospheric CO2 before the rise of forests carry large, often unbound, uncertainties. Here, we calibrate a mechanistic model for gas exchange in modern lycophytes and constrain atmospheric CO2 levels 410-380 Ma from related fossilized plants with bound uncertainties of approximately ±100 ppm (1 sd). We find that the atmosphere contained ~525-715 ppm CO2 before continents were afforested, and that Earth was partially glaciated according to a palaeoclimate model. A process-driven biogeochemical model (COPSE) shows the appearance of trees with deep roots did not dramatically enhance atmospheric CO2 removal. Rather, shallow-rooted vascular ecosystems could have simultaneously caused abrupt atmospheric oxygenation and climatic cooling long before the rise of forests, although earlier CO2 levels are still unknown.

Massive perturbations to atmospheric sulfur in the aftermath of the Chicxulub impact.

SignificanceSulfur isotopes confirm a key role for atmospheric sulfur gases in climatic cooling, mass extinction, and the demise of dinosaurs and other global biota after the Chicxulub bolide impact at the Cretaceous-Paleogene boundary. The sulfur isotope anomalies are confined to beds containing ejecta and, in the immediately overlying sediments, are temporally unrelated to known episodes of volcanism that also bracket this event, further addressing the controversial role of the Deccan Traps in the extinction.

Carbon cycle dynamics and ecology revealed by the carbon isotopic composition of single organic microfossils during the Late Devonian Biotic Crisis.

We apply a new approach for the δ13 C analysis of single organic-walled microfossils (OWM) to three sites in the Appalachian Basin of New York (AB) that span the Late Devonian Biotic Crisis (LDBC). Our data provide new insights into the nature of the Frasnian-Famennian carbon cycle in the AB and also provide possible constraints on the paleoecology of enigmatic OWM ubiquitous in Paleozoic shale successions. The carbon isotope compositions of OWM are consistent with normal marine organic matter of autochthonous origins and range from -32 to -17‰, but average -25‰ across all samples and are consistently 13 C-enriched compared to bulk sediments (δ13 Cbulk ) by ~0-10‰. We observe no difference between the δ13 COWM of leiospheres (smooth-walled) and acanthomorphic (spinose) acritarch OWM, indicating that our data are driven by ecological rather than taxonomic signals. We hypothesize that the offset between δ13 COWM and δ13 Cbulk is in part due to a large δ13 C gradient in the AB water column where OWM utilized relatively 13 C-enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating 13 C-depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ13 COWM and δ13 Cbulk of 3‰ from shoreward to open-ocean facies that may reflect the effect of 13 C-enriched dissolved inorganic carbon (DIC) derived from riverine sources in the relatively enclosed AB. The hypothesized steep carbon isotope gradient in the AB could be due to a strong biological pump; this in turn may have contributed to low oxygen bottom water conditions during the LDBC. This is the first time single-microfossil δ13 Corg analyses of eukaryotes have been directly compared to bulk δ13 Corg in the deep-time fossil record.

Microbially influenced lacustrine carbonates: A comparison of Late Quaternary Lahontan tufa and modern thrombolite from Fayetteville Green Lake, NY.

Carbonate microbialites in lakes can serve as valuable indicators of past environments, so long as the biogenicity and depositional setting of the microbialite can be accurately determined. Late Pleistocene to Early Holocene frondose draping tufa deposits from Winnemucca Dry Lake (Nevada, USA), a subbasin of pluvial Lake Lahontan, were examined in outcrop, petrographically, and geochemically to determine whether microbially induced precipitation is a dominant control on deposition. These observations were compared to modern, actively accumulating microbialites from Fayetteville Green Lake (New York, USA) using similar methods. In addition, preserved microbial DNA was extracted from the Lahontan tufa and sequenced to provide a more complete picture of the microbial communities. Tufas are texturally and geochemically similar to modern thrombolitic microbialites from Fayetteville Green Lake, and the stable isotopic composition of organic C, N, inorganic C, and O supports deposition associated with a lacustrine microbial mat environment dominated by photosynthetic processes. DNA extraction and sequencing indicate that photosynthetic microbial builders were present during tufa deposition, primarily Chloroflexi and Proteobacteria with minor abundances of Cyanobacteria and Acidobacteria. Based on the sequencing results, the depositional environment of the tufas can be constrained to the photic zone of the lake, contrasting with some previous interpretations that put tufa formation in deeper waters. Additionally, the presence of a number of mesothermophilic phyla, including Deinococcus-Thermus, indicates that thermal groundwater may have played a role in tufa deposition at sites not previously associated with groundwater influx. The interpretation of frondose tufas as microbially influenced deposits provides new context to interpretations of lake level and past environments in the Lahontan lake basins.

Perturbation to the nitrogen cycle during rapid Early Eocene global warming.

The degree to which ocean deoxygenation will alter the function of marine communities remains unclear but may be best constrained by detailed study of intervals of rapid warming in the geologic past. The Paleocene-Eocene Thermal Maximum (PETM) was an interval of rapid warming that was the result of increasing contents of greenhouse gases in the atmosphere that had wide ranging effects on ecosystems globally. Here, we present stable nitrogen isotope data from the Eastern Peri-Tethys Ocean that record a significant transition in the nitrogen cycle. At the initiation of the PETM, the nitrogen isotopic composition of sediments decreased by ~6‰ to as low as -3.4‰, signaling reorganization of the marine nitrogen cycle. Warming, changes in ocean circulation, and deoxygenation caused a transition to nitrogen cycle to conditions that were most similar to those experienced during Oceanic Anoxic Events of the Mesozoic.

Ediacara biota flourished in oligotrophic and bacterially dominated marine environments across Baltica.

Middle-to-late Ediacaran (575-541 Ma) marine sedimentary rocks record the first appearance of macroscopic, multicellular body fossils, yet little is known about the environments and food sources that sustained this enigmatic fauna. Here, we perform a lipid biomarker and stable isotope (δ15Ntotal and δ13CTOC) investigation of exceptionally immature late Ediacaran strata (<560 Ma) from multiple locations across Baltica. Our results show that the biomarker assemblages encompass an exceptionally wide range of hopane/sterane ratios (1.6-119), which is a broad measure of bacterial/eukaryotic source organism inputs. These include some unusually high hopane/sterane ratios (22-119), particularly during the peak in diversity and abundance of the Ediacara biota. A high contribution of bacteria to the overall low productivity may have bolstered a microbial loop, locally sustaining dissolved organic matter as an important organic nutrient. These oligotrophic, shallow-marine conditions extended over hundreds of kilometers across Baltica and persisted for more than 10 million years.

Nitrogen fixation sustained productivity in the wake of the Palaeoproterozoic Great Oxygenation Event.

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte-Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.

Onset of the aerobic nitrogen cycle during the Great Oxidation Event.

The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal 15N/14N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

Measurement of 13C and 15N isotopic composition on nanomolar quantities of C and N.

We describe a trapping and chromatography system that cryogenically removes CO(2) and N(2) generated from sample combustion in an elemental analyzer (EA) and introduces these gases into a low-flow helium carrier stream for isotopic analysis. The sample size required for measurement by this system (termed nano-EA/IRMS) is almost 3 orders of magnitude less than conventional EA analyses and fills an important niche in the range of analytical isotopic methods. Only 25 nmol of N and 41 nmol of C are needed to achieve 1.0 per thousand precision (2sigma) from a single measurement while larger samples and replicate measurements provide better precision. Analyses of standards demonstrate that nano-EA measurements are both accurate and precise, even on nanomolar quantities of C and N. Conventional and nano-EA measurements on international and laboratory standards are indistinguishable within analytical precision. Likewise, nano-EA values for international standards do not differ statistically from their consensus values. Both observations indicate the nano-EA measurements are comparable to conventional EA analyses and accurately reproduce the VPDB and AIR isotopic scales. Critical to the success of the nano-EA system is the procedure for removing the blank contribution to the measured values. Statistical treatment of uncertainties for this procedure yields an accurate method for calculating internal and external precision.