A window into the abiotic carbon cycle – Acetate and formate in fracture waters in 2.7 billion year-old host rocks of the Canadian Shield

Lollar, Barbara Sherwood; Heuer, Verena B; McDermott, J. M.; Tille, Stephanie; Warr, Oliver; Moran, James J.; Telling, Jon; Hinrichs, Kai−Uwe

doi:10.1016/j.gca.2020.11.026

Cited by 40 publications

(56 citation statements)

References 132 publications

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“…The demonstrated technique may be instrumental in helping address these issues in the near future through application to a larger and more extensive sample suite and potentially through adaptation to measure parameters like δ 13 C CO2 and δ 2 H isotope signatures of hydrocarbons, and potentially even clumped isotopologues ( 13 CH 3 D and 12 CH 2 D 2 ) which require a much larger volume of analyte than conventional δ 13 C and δ 2 H measurements 14 . The ability to measure these and the stable isotope signatures of other different volatile components contained within the trapped volatiles will likely lead to a better understanding of the sources and mechanisms of hydrocarbon formation in the subsurface of Earth, and on other planets and moons where abiotic organic synthesis is being investigated such as Enceladus and Titan 18 …”

Section: Discussionmentioning

confidence: 99%

“…Recent discoveries continue to challenge paradigms concerning the deep carbon cycle, from the discovery of microorganisms capable of surviving even in ocean sediments up to 120°C 17 ; to abiotic organic synthesis of CH 4 , acetate and formate in the deep continental crust on Earth 18 ; to reports of CH 4 in the Mars atmosphere 19 . An enduring debate continues concerning the role and mechanisms for abiotic CH 4 production in both marine and continental settings.…”

Section: Introductionmentioning

confidence: 99%

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Advances in carbon isotope analysis of trapped methane and volatile hydrocarbons in crystalline rock cores

Sanz-Robinson

Brisco

Warr

et al. 2021

Rapid Comm Mass Spectrometry

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Rationale The isotopic composition of hydrocarbons trapped in rocks on the microscale (fluid inclusions, mineral grain boundaries, microfractures) can provide powerful information on geological and biological processes but are an analytical challenge due to low concentrations. We present a new approach for the extraction and carbon isotopic analysis of methane (CH4) and hydrocarbons in trapped volatiles in crystalline rocks. Methods An off‐line crusher with cryogenic trapping and a custom‐made silica glass U‐trap were attached to an external injector port on a continuous flow gas chromatograph/combustion/isotope ratio mass spectrometer to demonstrate the accuracy, reproducibility, and sensitivity of δ13C measurements for CH4. Results The method can isotopically characterize CH4 in crushed rock samples with concentrations as low as 3.5 × 10−9 mol/g of rock, and both sample and isotopic standards are analyzed with an accuracy and reproducibility of ±0.5‰. High H2O/CH4 ratios of 98 to 500 have no effect on measured δ13CCH4 values. The method is successfully applied to natural samples from the north range of Sudbury Basin, Ontario, Canada. The δ13C isotopic signatures of CH4 trapped microscopically in rock from the north range overlap significantly with that of CH4 contained in larger scale flowing fracture fluids from the same part of the Sudbury Basin, indicating a potential genetic link. Conclusions A novel method for δ13CCH4 analysis was developed for the extraction of nanomole quantities of CH4 trapped microscopically in rocks. The technique has an accuracy and reproducibility comparable to that of on‐line crushing techniques but importantly provides the capability of crushing larger rock quantities (up to 100 g). The benefit is improved detection levels for trace hydrocarbon species. Such a capability will be important for future extension of such crushing techniques for measurement of 2H/1H for CH4, clumped isotopologues of CH4 and other trapped volatiles species, such as C2H6, C3H8, C4H10, CO2 and N2.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Advances in carbon isotope analysis of trapped methane and volatile hydrocarbons in crystalline rock cores

Sanz-Robinson

Brisco

Warr

et al. 2021

Rapid Comm Mass Spectrometry

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“…Perchlorate activities were estimated at equilibrium with Cl − . Acetate activities were estimated to be nearly equal to measured dissolved organic carbon (DOC) concentrations based on our preliminary data and reference 43 . For aqueous CO, we substituted activities for concentrations averaged over six measurements taken between September 2016 and November 2017.…”

Section: Methodsmentioning

confidence: 99%

Iron-Fueled Life in the Continental Subsurface: Deep Mine Microbial Observatory, South Dakota, USA

Casar

Momper

Kruger

et al. 2021

Appl Environ Microbiol

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Iron-bearing minerals are key components of the Earth’s crust and potentially critical energy sources for subsurface microbial life. The Deep Mine Microbial Observatory (DeMMO) is situated in a range of iron-rich lithologies, and fracture fluids here reach concentrations as high as 8.84 mg/L. Iron cycling is likely an important process given the high concentrations of iron in fracture fluids and detection of putative iron cycling taxa via marker gene surveys. However, a previous metagenomic survey detected no iron cycling potential at two DeMMO localities. Here, we revisit the potential for iron cycling at DeMMO using a new metagenomic dataset including all DeMMO sites and FeGenie, a new annotation pipeline that is optimized for the detection of iron cycling genes. We annotate functional genes from whole metagenomic assemblies and metagenome-assembled genomes and characterize putative iron cycling pathways and taxa in the context of local geochemical conditions and available metabolic energy estimated from thermodynamic models. We re-annotated previous metagenomic data, revealing iron cycling potential that was previously missed. Across both metagenomic datasets, we find that not only is there genetic potential for iron cycling at DeMMO, iron is likely an important source of energy across the system. In response to the dramatic differences we observed between annotation approaches, we recommend the use of optimized pipelines where the detection of iron cycling genes is a major goal. Importance We investigated iron cycling potential among microbial communities inhabiting iron-rich fracture fluids to a depth of 1.5km in the continental crust. A previous study found no iron cycling potential in the communities despite the iron-rich nature of the system. A new tool for detecting iron cycling genes was recently published, which we used on a new dataset. We combined this with a number of other approaches to get a holistic view of metabolic strategies across the communities, revealing iron cycling to be an important process here. In addition, we used the tool on the data from the previous study, revealing previously missed iron cycling potential. Iron is common in continental crust; thus, our findings are likely not unique to our study site. Our new view of important metabolic strategies underscores the importance of choosing optimized tools for detecting the potential for metabolisms like iron cycling that may otherwise be missed.

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“…Without the ability to sample early Earth environments, our understanding of Earth's prebiotic organic chemistry relies heavily on theory and experimental simulations of abiotic organic synthesis. Some extreme Earth systems have been identified where abiotic organic synthesis plays an important role, such as marine hydrothermal vents [20,21] and million to billion year residence fracture fluids isolated in Precambrian rocks kilometers below the surface [22]. While such environments yield insights into the type of non-biological water-rock reactions that would have dominated a prebiotic Earth, even in these extreme environments the influence of biologically driven reactions cannot be ruled out.…”

Section: Organic Moleculesmentioning

confidence: 99%

“…Particularly notable is the work carried out by Huber and Wächtershäuser [60], showing that several iron sulfur minerals are able to spontaneously catalyze carbon fixation reactions, producing prebiotic molecules. Non-metals may also drive production of simple organic molecules as recent studies of radiolysis reactions driven by U, Th and K decay demonstrate production of simple organic acids such as acetate, formate and oxalate in addition to the more well known H 2 production [22,61]. It is believed that the earliest forms of proto-life may have had metabolisms catalyzed by environmentally available metal-bearing nanominerals [8].…”

Section: Metal Catalysismentioning

confidence: 99%

The Grayness of the Origin of Life

Smith

Hyde

Simkus

et al. 2021

Life

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In the search for life beyond Earth, distinguishing the living from the non-living is paramount. However, this distinction is often elusive, as the origin of life is likely a stepwise evolutionary process, not a singular event. Regardless of the favored origin of life model, an inherent “grayness” blurs the theorized threshold defining life. Here, we explore the ambiguities between the biotic and the abiotic at the origin of life. The role of grayness extends into later transitions as well. By recognizing the limitations posed by grayness, life detection researchers will be better able to develop methods sensitive to prebiotic chemical systems and life with alternative biochemistries.

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A window into the abiotic carbon cycle – Acetate and formate in fracture waters in 2.7 billion year-old host rocks of the Canadian Shield

Cited by 40 publications

References 132 publications

Advances in carbon isotope analysis of trapped methane and volatile hydrocarbons in crystalline rock cores

Advances in carbon isotope analysis of trapped methane and volatile hydrocarbons in crystalline rock cores

Iron-Fueled Life in the Continental Subsurface: Deep Mine Microbial Observatory, South Dakota, USA

The Grayness of the Origin of Life

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