A series of dramatic oceanic and atmospheric events occurred in the immediate aftermath of the Marinoan “snowball Earth” meltdown ∼635 My ago. However, at the 10- to 100-ky timescale, the order, rate, duration, and causal-feedback relationships of these individual events remain nebulous. Nonetheless, rapid swings in regional marine sulfate concentrations are predicted to have occurred in the aftermath of a snowball Earth, due to the nonlinear responses of its two major controlling fluxes: oxidative weathering on the continents and pyrite burial in marine sediments. Here, through the application of multiple isotope systems on various carbon and sulfur compounds, we determined extremely 13 C-depleted calcite cements in the basal Ediacaran in South China to be the result of microbial sulfate reduction coupled to anaerobic oxidation of methane, which indicates an interval of high sulfate concentrations in some part of the postmeltdown ocean. Regional chemostratigraphy places the 13 C-depleted cements at the equivalent of the earliest Ediacaran 17 O-depletion episode, thus confining the timing of this peak in sulfate concentrations within ∼50 ky since the onset of the deglaciation. The dearth of similarly 13 C-depleted cements in other Proterozoic successions implies that the earliest Ediacaran peak in marine sulfate concentration is a regional and likely transient event.
more »
« less
The triple oxygen isotope composition of marine sulfate and 130 million years of microbial control
The triple oxygen isotope composition (Δ’ 17 O) of sulfate minerals is widely used to constrain ancient atmospheric p O 2 / p CO 2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O 2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the δ 18 O and Δ’ 17 O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ’ 17 O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably.
more »
« less
- PAR ID:
- 10395159
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 119
- Issue:
- 31
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The sedimentary pyrite sulfur isotope (δ34S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ34S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ34S geochemistry. Pyrite δ34S values often capture δ34S 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 δ34S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ34S trends and δ34S 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 δ34S signatures in early Earth environments. Porewater sulfide δ34S 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 δ34S variability, instead of variations in average cell‐specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ34S values of pyrite are similar to porewater sulfide δ34S 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 δ34S 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.more » « less
-
Reconstructing the history of biological productivity and atmospheric oxygen partial pressure ( p O 2 ) is a fundamental goal of geobiology. Recently, the mass-independent fractionation of oxygen isotopes (O-MIF) has been used as a tool for estimating p O 2 and productivity during the Proterozoic. O-MIF, reported as Δ′ 17 O, is produced during the formation of ozone and destroyed by isotopic exchange with water by biological and chemical processes. Atmospheric O-MIF can be preserved in the geologic record when pyrite (FeS 2 ) is oxidized during weathering, and the sulfur is redeposited as sulfate. Here, sedimentary sulfates from the ∼1.4-Ga Sibley Formation are reanalyzed using a detailed one-dimensional photochemical model that includes physical constraints on air–sea gas exchange. Previous analyses of these data concluded that p O 2 at that time was <1% PAL (times the present atmospheric level). Our model shows that the upper limit on p O 2 is essentially unconstrained by these data. Indeed, p O 2 levels below 0.8% PAL are possible only if atmospheric methane was more abundant than today (so that p CO 2 could have been lower) or if the Sibley O-MIF data were diluted by reprocessing before the sulfates were deposited. Our model also shows that, contrary to previous assertions, marine productivity cannot be reliably constrained by the O-MIF data because the exchange of molecular oxygen (O 2 ) between the atmosphere and surface ocean is controlled more by air–sea gas transfer rates than by biological productivity. Improved estimates of p CO 2 and/or improved proxies for Δ′ 17 O of atmospheric O 2 would allow tighter constraints to be placed on mid-Proterozoic p O 2 .more » « less
-
Sousa, Filipa L.; Schleper, Christa M. (Ed.)ABSTRACT Life emerged and diversified in the absence of molecular oxygen. The prevailing anoxia and unique sulfur chemistry in the Paleo-, Meso-, and Neoarchean and early Proterozoic eras may have supported microbial communities that differ from those currently thriving on the earth’s surface. Zodletone spring in southwestern Oklahoma represents a unique habitat where spatial sampling could substitute for geological eras namely, from the anoxic, surficial light-exposed sediments simulating a preoxygenated earth to overlaid water column where air exposure simulates oxygen intrusion during the Neoproterozoic era. We document a remarkably diverse microbial community in the anoxic spring sediments, with 340/516 (65.89%) of genomes recovered in a metagenomic survey belonging to 200 bacterial and archaeal families that were either previously undescribed or that exhibit an extremely rare distribution on the current earth. Such diversity is underpinned by the widespread occurrence of sulfite, thiosulfate, tetrathionate, and sulfur reduction and the paucity of sulfate reduction machineries in these taxa. Hence, these processes greatly expand lineages mediating reductive sulfur-cycling processes in the tree of life. An analysis of the overlaying oxygenated water community demonstrated the development of a significantly less diverse community dominated by well-characterized lineages and a prevalence of oxidative sulfur-cycling processes. Such a transition from ancient novelty to modern commonality underscores the profound impact of the great oxygenation event on the earth’s surficial anoxic community. It also suggests that novel and rare lineages encountered in current anaerobic habitats could represent taxa that once thrived in an anoxic earth but have failed to adapt to earth’s progressive oxygenation. IMPORTANCE Life on earth evolved in an anoxic setting; however, the identity and fate of microorganisms that thrived in a preoxygenated earth are poorly understood. In Zodletone spring, the prevailing geochemical conditions are remarkably similar to conditions prevailing in surficial earth prior to oxygen buildup in the atmosphere. We identify hundreds of previously unknown microbial lineages in the spring and demonstrate that these lineages possess the metabolic machinery to mediate a wide range of reductive sulfur processes, with the capacity to respire sulfite, thiosulfate, sulfur, and tetrathionate, rather than sulfate, which is a reflection of the differences in sulfur-cycling chemistry in ancient versus modern times. Collectively, such patterns strongly suggest that microbial diversity and sulfur-cycling processes in a preoxygenated earth were drastically different from the currently observed patterns and that the Great Oxygenation Event has precipitated the near extinction of a wide range of oxygen-sensitive lineages and significantly altered the microbial reductive sulfur-cycling community on earth.more » « less
-
Carbonate minerals contain stable isotopes of carbon and oxygen with different masses whose abundances and bond arrangement are governed by thermodynamics. The clumped isotopic value Δiis a measure of the temperature-dependent preference of heavy C and O isotopes to clump, or bond with or near each other, rather than with light isotopes in the carbonate phase. Carbonate clumped isotope thermometry uses Δivalues measured by mass spectrometry (Δ47, Δ48) or laser spectroscopy (Δ638) to reconstruct mineral growth temperature in surface and subsurface environments independent of parent water isotopic composition. Two decades of analytical and theoretical development have produced a mature temperature proxy that can estimate carbonate formation temperatures from 0.5 to 1,100°C, with up to 1–2°C external precision (2 standard error of the mean). Alteration of primary environmental temperatures by fluid-mediated and solid-state reactions and/or Δivalues that reflect nonequilibrium isotopic fractionations reveal diagenetic history and/or mineralization processes. Carbonate clumped isotope thermometry has contributed significantly to geological and biological sciences, and it is poised to advance understanding of Earth's climate system, crustal processes, and growth environments of carbonate minerals. ▪ Clumped heavy isotopes in carbonate minerals record robust temperatures and fluid compositions of ancient Earth surface and subsurface environments. ▪ Mature analytical methods enable carbonate clumped Δ47, Δ48, and Δ638measurements to address diverse questions in geological and biological sciences. ▪ These methods are poised to advance marine and terrestrial paleoenvironment and paleoclimate, tectonics, deformation, hydrothermal, and mineralization studies.more » « less