Exceptional preservation of palaeozoic steroids in a diagenetic continuum

The occurrence of intact sterols has been restricted to immature Cretaceous (~125 Ma) sediments with one report from the Late Jurassic (~165 Ma). Here we report the oldest occurrence of intact sterols in a Crustacean fossil preserved for ca. 380 Ma within a Devonian concretion. The exceptional preservation of the biomass is attributed to microbially induced carbonate encapsulation, preventing full decomposition and transformation thus extending sterol occurrences in the geosphere by 250 Ma. A suite of diagenetic transformation products of sterols was also identified in the concretion, demonstrating the remarkable coexistence of biomolecules and geomolecules in the same sample. Most importantly the original biolipids were found to be the most abundant steroids in the sample. We attribute the coexistence of steroids in a diagenetic continuum-ranging from stenols to triaromatic steroids-to microbially mediated eogenetic processes

Fault-controlled hydration of the upper mantle during continental rifting

Water and carbon are transferred from the ocean to the mantle in a process that alters mantle peridotite to create serpentinite and supports diverse ecosystems1. Serpentinized mantle rocks are found beneath the sea floor at slow- to ultraslow-spreading mid-ocean ridges1 and are thought to be present at about half the world’s rifted margins2, 3. Serpentinite is also inferred to exist in the downgoing plate at subduction zones4, where it may trigger arc magmatism or hydrate the deep Earth. Water is thought to reach the mantle via active faults3, 4. Here we show that serpentinization at the rifted continental margin offshore from western Spain was probably initiated when the whole crust cooled to become brittle and deformation was focused along large normal faults. We use seismic tomography to image the three-dimensional distribution of serpentinization in the mantle and find that the local volume of serpentinite beneath thinned, brittle crust is related to the amount of displacement along each fault. This implies that sea water reaches the mantle only when the faults are active. We estimate the fluid flux along the faults and find it is comparable to that inferred for mid-ocean ridge hydrothermal systems. We conclude that brittle processes in the crust may ultimately control the global flux of sea water into the Earth

Geogenic and atmospheric sources for volatile organic compounds in fumarolic emissions from Mt. Etna and Vulcano Island (Sicily, Italy)

In this paper, fluid source(s) and processes controlling the chemical composition of volatile organic compounds (VOCs) in gas discharges from Mt. Etna and Vulcano Island(Sicily, Italy) were investigated. The main composition of the Etnean and Volcano gas emissions is produced by mixing, to various degrees, of magmatic and hydrothermal components. VOCs are dominated by alkanes, alkenes and aromatics, with minor, though significant, concentrations of O-, S- and Cl(F)-substituted compounds. The main mechanism for the production of alkanes is likely related to pyrolysis of organic-matterbearing sediments that interact with the ascending magmatic fluids. Alkanes are then converted to alkene and aromatic compounds via catalytic reactions (dehydrogenation and dehydroaromatization, respectively). Nevertheless, an abiogenic origin for the light hydrocarbons cannot be ruled out. Oxidative processes of hydrocarbons at relatively high temperatures and oxidizing conditions, typical of these volcanic-hydrothermal fluids, may explain the production of alcohols, esters, aldehydes, as well as O- and S-bearing heterocycles. By comparing the concentrations of hydrochlorofluorocarbons (HCFCs) in the fumarolic discharges with respect to those of background air, it is possible to highlight that they have a geogenic origin likely due to halogenation of both methane and alkenes. Finally, chlorofluorocarbon (CFC) abundances appear to be consistent with background air, although the strong air contamination that affects the Mt. Etna fumaroles may mask a possible geogenic contribution for these compounds. On the other hand, no CFCs were detected in the Vulcano gases, which are characterized by low air contribution. Nevertheless, a geogenic source for these compounds cannot be excluded on the basis of the present data

Predicting effective diffusion coefficients in mudrocks using a fractal model and small-angle neutron scattering measurements

The determination of effective diffusion coefficients of gases or solutes in the water‐saturated pore space of mudrocks is time consuming and technically challenging. Yet reliable values of effective diffusion coefficients are important to predict migration of hydrocarbon gases in unconventional reservoirs, dissipation of (explosive) gases through clay barriers in radioactive waste repositories, mineral alteration of seals to geological CO2 storage reservoirs, and contaminant migration through aquitards. In this study, small‐angle and very small angle neutron scattering techniques have been utilized to determine a range of transport properties in mudrocks, including porosity, pore size distributions, and surface and volume fractal dimensions of pores and grains, from which diffusive transport parameters can be estimated. Using a fractal model derived from Archie's law, we calculate effective diffusion coefficients from these parameters and compare them to laboratory‐derived effective diffusion coefficients for CO2, H2, CH4, and HTO on either the same or related mudrock samples. The samples include Opalinus Shale from the underground laboratory in Mont Terri, Switzerland, Boom Clay from a core drilled in Mol, Belgium, and a marine claystone cored in Utah, USA. The predicted values were compared to laboratory diffusion measurements. The measured and modeled diffusion coefficients show good agreement, differing generally by less than factor 5. Neutron or X‐ray scattering analysis is therefore proposed as a novel method for fast, accurate estimation of effective diffusion coefficients in mudrocks, together with simultaneous measurement of multiple transport parameters including porosity, pore size distributions, and surface areas, important for (reactive) transport modeling

Low-molecular-weight hydrocarbon concentrations, organic carbon contents, and Rock-Eval pyrolysis hydrogen indices at DSDP Holes 75-530A and 75-532

A series of C2-C8 hydrocarbons (including saturated, aromatic, and olefinic compounds) from deep-frozen core samples taken during DSDP Leg 75 (Holes 530A and 532) were analyzed by a combined hydrogen-stripping/thermovaporization method. Concentrations representing both hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces vary in Hole 530A from about 10 to 15,000 ng/g of dry sediment weight depending on the lithology (organic-carbon-lean calcareous oozes versus "black shales"). Likewise, the organic-carbon-normalized C2-C8 hydrocarbon concentrations vary from 3,500 to 93,100 ng/g Corg, reflecting drastic differences in the hydrogen contents and hence the hydrocarbon potential of the kerogens. The highest concentrations measured of nearly 10**5 ng/g Corg are about two orders of magnitude below those usually encountered in Type-II kerogen-bearing source beds in the main phase of petroleum generation. Therefore, it was concluded that Hole 530A sediments, even at 1100 m depth, are in an early stage of evolution. The corresponding data from Hole 532 indicated lower amounts (3,000-9,000 ng/g Corg), which is in accordance with the shallow burial depth and immaturity of these Pliocene/late Miocene sediments. Significant changes in the light hydrocarbon composition with depth were attributed either to changes in kerogen type or to maturity related effects. Redistribution pheonomena, possibly the result of diffusion, were recognized only sporadically in Hole 530A, where several organic-carbon lean samples were enriched by migrated gaseous hydrocarbons. The core samples from Hole 530A were found to be severely contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures on board Glomar Challenger

Low-molecular-weight hydrocarbons in sediments at DSDP Sites 89-585 and 89-586

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 38 shipboard sealed, deep-frozen core samples of Deep Sea Drilling Project Sites 585 (East Mariana Basin) and 586 (Ontong-Java Plateau) were determined by a gas stripping-thermovaporization method. Total concentrations, which represent the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediment, vary from 20 to 630 ng/g of rock at Site 585 (sub-bottom depth range 332-868 m). Likewise, organic-carbon normalized yields range from 3*10**4 to 9*10**5 ng/g Corg, indicating that the organic matter is still in the initial, diagenetic evolutionary stage. The highest value (based on both rock weight and organic carbon) is measured in an extremely organic-carbon-poor sample of Lithologic Subunit VB (Core 585-30). In this unit (504-550 m) several samples with elevated organic-carbon contents and favorable kerogen quality including two thin "black-shale" layers deposited at the Cenomanian/Turonian boundary (not sampled for this study) were encountered. We conclude from a detailed comparison of light hydrocarbon compositions that the Core 585-30 sample is enriched in hydrocarbons of the C2-C8 molecular range, particularly in gas compounds, which probably migrated from nearby black-shale source layers. C2-C8 hydrocarbon yields in Site 586 samples (sub-bottom depth range 27-298 m) did not exceed 118 ng/g of dry sediment weight (average 56 ng/g), indicating the immaturity of these samples