Bias in carbon concentration and δ13C measurements of organic matter due to cleaning treatments with organic solvents

We acknowledge the financial support from the UnivEarths Labex program of Sorbonne Paris Cite (ANR 11-IDEX-00005-02). CH and AL acknowledge support from the Max Planck Society. EES and RB were funded by the NASA Exobiology grant NNX16AI37G and the Virtual Planetary Laboratory of the NASA Astrobiology Institute and were technically assisted by Andy Schauer.Interpreting the organic carbon content (TOC) and stable carbon isotopic composition (δ13C) of organic matter in the sedimentary rock record depends on our capability to accurately measure them, while excluding sources of contamination. This however becomes increasingly problematic as we analyze samples with ever-lower organic carbon content. Accordingly, organic solvents are sometimes used to remove contaminating traces of modern organic matter from ancient rock samples. However, especially for very low TOC samples, traces of solvents or their impurities remaining in the sample may contribute a significant organic contamination that can impact the bulk measurements of both TOC and δ13C values. This study, including three independent investigations performed in different laboratories, is the first detailed examination of the effect of cleaning treatments on the reliability of TOC and δ13C values in a range of natural rock samples and synthetic materials with low TOC content from below detection limit to 3330 ppm. We investigated the four most common organic solvents used to remove modern organic matter: dichloromethane (DCM), n-hexane, methanol and ethanol, and evaluated the effect of grain size and mineralogy. We find that (i) cleaning treatments with methanol, n-hexane and dichloromethane contaminate rock samples when used directly on sample powder, regardless of the grain size; (ii) this pollution buffers the natural variability and homogenizes the δ13C values of samples around the isotopic composition of the solvent, i.e. between −27 and −29‰; (iii) the extent of contamination depends on the solvent used, DCM being the most contaminating (up to 6000 ppm) and ethanol the only solvent that does not seem to contaminate rock samples above our detection limit; (iv) sample mineralogy also exerts an influence on the extent of contamination, clay minerals being more prone to adsorb contaminants. We conclude that the response of carbon concentrations and the stable carbon isotopic composition of organic matter in geological samples to cleaning treatments is neither negligible nor systematic when investigating samples with low carbon content.PostprintPeer reviewe

Origin of Paleoarchean Sulfate Deposits

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Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

International audienceSulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between −1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere

The use of chromium reduction in the analysis of organic carbon and inorganic sulfur isotope compositions in Archean rocks

International audienceOne of the most serious issues with deciphering the evolution of organisms and their biogeochemical environments from the ancient rock record is the difficulty in obtaining well-preserved samples. Although not much can be done to avoid diagenetic and metamorphic alteration when they have occurred, alteration due to weathering can be avoided by working on drill core samples. This implies however that the amount of sample is limited, which may in turn restrain the number of possible chemical and isotopic analyses that can be performed. In order to save sample we show here that the chemical protocol used for the sulfur sulfide extraction (for later sulfur isotope analyses) is also suitable to decarbonate samples (for later organic carbon isotope analyses). In the case of carbonated rocks, both sulfur sulfide extraction and decarbonation require high amounts of sample so that coupling them may save a significant amount of sample and time. In addition it allows both organic carbon (TOC and δ 13 C) and sulfur isotope composition measurements to be performed on the exact same powder , which is essential when trying to understand couplings between S and C cycles in heterogeneous samples. We thus tested the efficiency of the acidic chromium solution, commonly used to extract sulfur from sulfide, for sample decarbonation on various Archean rocks. Our results show that no significant carbon isotope fraction-ation is caused by this new decarbonation protocol, even for the samples with low organic carbon content. The chromium solution seems to be perfectly adapted for the analysis of organic matter in the ancient rock record, at least when the rock samples have experienced low greenschist facies metamorphism. Further tests will be needed to verify if this protocol can also be used for less mature organic matter

Primary sulfur isotope signatures preserved in high-grade Archean barite deposits of the Sargur Group, Dharwar Craton, India

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Biotic-abiotic influences on modern Ca-Si-rich hydrothermal spring mounds of the Pastos Grandes volcanic caldera (Bolivia).

37 pagesInternational audienceThe lacustrine-to-palustrine Pastos Grandes Laguna (Bolivia) is located in a volcanic caldera fed by active hot springs, with a carbonate crust extending over 40 km2. An integrated approach based on geology and hydrochemistry was used to characterize La Salsa, one of its hydrothermal systems, composed of a flat mound with a hydrothermal discharge. The mound is composed of carbonate–diatom aggregates, forming muds that accumulate and undergo slight swelling. The discharge area along the hydrothermal pathway exhibits several facies and microfabrics, with considerable biological activity and microbialite development. Both the downstream evolution of carbonate and silica content in sediments and the distribution of microbialites can be linked to changes in biotic-abiotic processes occurring along the pathway. The spatial distribution of microbialites and their morphologies are related to hydrodynamic conditions, the nature of the substrate on which they grow and, to a lesser extent, to the accommodation space available. The evolution of the physicochemical properties of the water and biological activity mainly impact mineral precipitation but also affect microbialite morphologies and microstructures. This atypical Si- and Ca-rich hydrothermal system therefore provides insights into the diversity of environmental, chemical, and biotic factors controlling mineralization, which also responds to independent thermodynamic controls

Low temperature magnetic properties of the Late Archean Boolgeeda iron formation (Hamersley Group, Western Australia): environmental implications

International audienceThe origin of the iron oxides in Archean and Paleoproterozoic Banded Iron Formations (BIFs) is still a debated question. We report low and high temperature magnetic properties, susceptibility and saturation magnetization results joined with scanning microscope observations within a 35 m section of the Late Archean Boolgeeda Iron Formation of the Hamersley Group, Western Australia. With the exception of two volcanoclastic intervals characterized by low susceptibility and magnetization, nearly pure magnetite is identified as the main magnetic carrier in all iron-rich layers including hematite-rich jasper beds. Two populations of magnetically distinct magnetites are reported from a 2 m-thick interval within the section. Each population shows a specific Verwey transition temperature: one around 120-124 K and the other in the range of 105-110 K. This temperature difference is interpreted to reflect two distinct stoichiometry and likely two episodes of crystallization. The 120-124K transition is attributed to nearly pure stoichiometric magnetite, SEM and microprobe observations suggest that the lower temperature transition is related to chemically impure silician magnetite. Microbial-induced partial substitution of iron by silicon is suggested here. This is supported by an increase in Total Organic Carbon (TOC) in the same interval

Toluene and methylethylketone: effect of combined exposure on their metabolism in rat

<p>1. Multiple exposures are ubiquitous in industrial environments. In this article, we highlight the risks faced by workers and complete the data available on the metabolic impact of a common mixture: toluene (TOL) and methylethylketone (MEK).</p> <p>2. Rats were exposed by inhalation under controlled conditions either to each solvent individually, or to mixtures of the two. How the interaction between the two solvents affected their fate in the blood and brain, their main relevant urinary metabolites (o-cresol, benzylmercapturic acid for TOL and 2,3-butanediols for MEK) and their hepatic metabolism were investigated.</p> <p>3. Although the cytochrome P450 concentration was unchanged, and the activities of CYP1A2 and CYP2E1 isoforms were not additively or synergistically induced by co-exposure, TOL metabolism was inhibited by the presence of MEK (and vice versa). Depending on the relative proportions of each compound in the mixture, this sometimes resulted in a large increase in blood and brain concentrations. Apart from extreme cases (unbalanced mixtures), the amount of o-cresol and benzylmercapturic acid (and to a lesser extent 2,3-butanediols) excreted were proportional to the blood solvent concentrations.</p> <p>4. In a co-exposure context, ortho-cresol and benzylmercapturic acid can be used as urinary biomarkers in biomonitoring for employees to relatively accurately assess TOL exposure.</p