Search

A sulfurous spring emerges at an outcrop of Bowland Shale Formation on Crimpton Brook, Lancashire. The spring is marked by the precipitation of white and yellow jarosite. Comparable light sulfur isotope compositions suggest that the jarosite was derived from surface oxidation of pyritic shale. The shale contains anomalous concentrations of selenium and other trace elements, in common with other exposures of the Bowland Shale Formation in the north of England. The selenium is resident in the pyrite, and was released during oxidation and incorporated into the jarosite in Crimpton Brook. The small scale of the water flow at the site and the remote situation pose no environmental problem, but the data exemplify the potential danger of pyrite weathering into groundwater on a larger scale.

Graphite deposits may form alternatively by metamorphism of sedimentary rocks and from fluids. Both types occur in supracrustal successions within the Lewisian Complex of Northwest Scotland, and similarly in Palaeoproterozoic supracrustal rocks across the North Atlantic region in Canada, Greenland and Scandinavia. Carbon isotope compositions show that the graphite in Scotland had a mixed origin from metamorphism of sedimentary organic matter (schists) and the decarbonation of limestones (marbles). Raman spectroscopy shows that most of the graphite in Scotland exhibits some structural disorder, unlike the complete order in graphite vein ore deposits across the region. Exceptionally, where graphite was precipitated from fluid, in albitized rock in Tiree and Scardroy, it is fully ordered. While organic matter may survive granulite facies metamorphism without being transformed to fully ordered graphite, it can yield commercially more valuable ordered graphite when mobilized in a fluid.

Proterozoic limestone in a north British terrane contains a newly recognised occurrence of Nb-REE minerals. The mineralized Loch Shin Limestone is in the Lewisian Complex of the Northern Highlands ...

Carbonaceous residues occur in mudstones and turbidites of the Lower Paleozoic accretionary prism in Ireland and Scotland (Longford-Down, Southern Uplands). The accretionary prism was host to fluid migration during both the Lower Paleozoic and Carboniferous–Triassic, so the age of the carbonaceous fluids is uncertain. Raman spectroscopy data for the carbonaceous residues in the Lower Paleozoic rocks indicate palaeotemperatures similar to those measured in their host rocks, and much higher than those in the Carboniferous cover rocks or in residues in the cover rocks. These data show that residues in the prism rocks are of Lower Paleozoic age, and were not contributed by younger mineralizing fluids. The residues represent hydrocarbons generated from source rocks in the prism that were part of the Ordovician–Silurian deposits of the Iapetus Ocean.

The role of subduction zones has been considered critical to understand carbon fluxes among the Earth’s reservoirs. At plate margins, most of the carbon is stored in carbonate sediments. Nevertheless, the past decade saw an increasing focus also on reduced carbon - kerogen and graphite – to understand its role in the deep carbon cycle. Most of reduced carbon derive from seafloor organic-rich sediments, even if, a little portion can form by decarbonation during metamorphism.In the Palaeoproterozoic supracrustal rocks of the Lewisian Complex, graphitic marbles were found in a mixed succession of metasediments at Gott Bay, Island of Tiree (Scotland). Such marbles show bedding-parallel slip surfaces associated with chlorite that are absent in other marbles on the island that are devoid of graphite. Marbles and schists-hosted graphite were analysed showing marked differences in carbon isotopic composition and structural ordering measured by means of Raman spectroscopy.Petrographic and chemical evidence support the hypothesis of an abiotic origin of the marble-hosted graphite and the mechanisms that led to its formation could explain the heavy isotopic composition of many Proterozoic marbles in the world.

The geological record following the c. 2.3 billion years old Great Oxidation Event includes evidence for anomalously high burial of organic carbon and the emergence of widespread mountain building. Both carbon burial and orogeny occurred globally over the period 2.1 to 1.8 billion years ago. Prolific cyanobacteria were preserved as peak black shale sedimentation and abundant graphite. In numerous orogens, the exceptionally carbonaceous sediments were strongly deformed by thrusting, folding, and shearing. Here an assessment of the timing of Palaeoproterozoic carbon burial and peak deformation/metamorphism in 20 orogens shows that orogeny consistently occurred less than 200 million years after sedimentation, in a time frame comparable to that of orogens through the Phanerozoic. This implies that the high carbon burial played a critical role in reducing frictional strength and lubricating compressive deformation, which allowed crustal thickening to build Palaeoproterozoic mountain belts. Further, this episode left a legacy of weakening and deformation in 2 billion year-old crust which has supported subsequent orogenies up to the building of the Himalayas today. The link between Palaeoproterozoic biomass and long-term deformation of the Earth’s crust demonstrates the integral relationship between biosphere and lithosphere. High burial of organic carbon in sediments around 2 billion years ago acted to enhance crustal deformation and led to intensified mountain building both in the Paleoproterozoic and since, suggests an assessment of the timing of carbon burial and deformation

International audience; Data returned by NASA’s Mars Science Laboratory Curiosity rover showed evidence for abundant secondary materials, including Fe-oxides, phyllosilicates, and an amorphous component on and below Vera Rubin ridge in the Murray formation. We have used equilibrium thermochemical modeling to test the hypothesis that these altered sediments were deposited predominantly as detrital igneous grains and subsequently underwent diagenetic alteration. Chemical compositions of the altered components were calculated using data returned by the Chemistry and Mineralogy X-ray diffraction instrument and the Alpha Particle X-ray Spectrometer on board Curiosity. Reaction of these alteration compositions with a CO2-poor and oxidizing dilute aqueous solution was modeled at 25 – 100 °C, with varying amounts of Fe3+/Fetot of the host rock. The modeled alteration assemblages contained abundant phyllosilicates and Fe-oxides at >100 water to rock ratios, and were directly comparable to the abundances of hematite and clay minerals observed by Curiosity at 10,000 water to rock at 50 – 100 °C with pH ranging from 7.9 to 9.3. Our modeling results suggest that the hematite-clay mineral assemblage is primarily the result of enhanced groundwater flow compared to the Sheepbed mudstone in the Bradbury Group observed at Yellowknife Bay, and underwent further, localized alteration to produce the mineralogy observed by Curiosity.

Pyritized burrows from three localities were analysed using LA-ICP-MS to determine their trace element content and assess their ability to sequester trace elements. Pyritic burrows from Hock Cliff (Jurassic), Wren's Nest (Silurian) and Southerham Grey Pit (Cretaceous) have anomalous levels of Se, Cu and Pb and are enriched relative to their host sediments. Sequestration rates were calculated using sedimentation rates from similar depositional environments. Results show that pyritic burrows, mediated by bacterial sulphate reduction, can sequester Se, Cu and Pb up to 3 orders of magnitude greater than the rate of Fe–Mn crusts, which are considered rich sources of trace elements, demonstrating that bioturbated marine sediments are significant sinks of trace elements.

A carbon‐rich melt fragment from the Gardnos impact structure has been studied for a better understanding of the preservation and structural form(s) of carbon that have been processed by impact melting. The carbon was analyzed in situ in its original petrographic context within the melt fragment, using high‐resolution techniques including focused ion beam‐transmission electron microscopy and electron energy loss spectroscopy. Results show that the carbon is largely uniform and has a nanocrystalline grain size. The Gardnos carbon has a graphitic structure but with a large c/a ratio indicating disorder. The disorder could be a result of rapid heating to high temperatures during impact, followed by rapid cooling, with not enough time to crystallize into highly ordered graphite. However, temperature distribution during impact is extremely heterogenous, and the disordered Gardnos carbon could also represent material that avoided extreme temperatures, and thus, it was preserved. Understanding the structure of carbon during terrestrial impacts is important to help determine if the history of carbon within extraterrestrial samples is impact related. Furthermore, the degree of preservation of carbon during impact is key for locating and detecting organic compounds in extraterrestrial samples. This example from Gardnos, together with previous studies, shows that not all carbon is lost to oxidation during impact but that impact melting can encapsulate and preserve carbon where it is available.

A compilation of new and previously published vitrinite reflectance (R0) data from Carboniferous coals constitutes the most comprehensive map of reflectance across Great Britain. Values of R0 range from 0.38 to 3.29%, recording an ambient thermal maturity in the early oil window (standard reference point for reflectance studies), modified by elevated heat flow in northern England and along the Variscan orogenic front. The map provides a context for other geological datasets. Supplementary material: A statistical summary of vitrinite reflectance data is available at https://doi.org/10.6084/m9.figshare.c.4529969

Putative stromatolites and associated carbonate minerals in 1.1 Ga Stoer Group lacustrine sedimentary rocks were analysed to deduce their likely origins. Potential stromatolite examples included finely laminated and sometimes wrinkled carbonate-siliciclastic rocks of the Clachtoll Formation at Clachtoll and Bay of Stoer, and laminated limestone domes of the Poll a’Mhuilt Member (Bay of Stoer Formation) from Enard Bay.\ud \ud Petrography shows that the lamination and wrinkling of Clachtoll Formation specimens can most logically be explained by abiotic siliclastic sedimentary processes, namely rippling and soft-sediment deformation probably related to de-watering. Electron backscatter diffraction shows that the carbonate in these laminated Clachtoll Formation specimens was calcite, and petrography combined with clumped isotope palaeothermometry indicates it was likely to be part syn-depositional and part burial diagenetic in origin.\ud \ud The laminated domes of the Poll a’Mhuilt Member are shown to comprise clasts of limestone interlayered with clay, quartz, Na-rich feldspars and micas. Cathodoluminescence revealed the limestone clasts to be composite and built of sub-grains that must have been derived from an earlier, potentially Palaeoproterozoic, carbonate unit. Support for this hypothesis comes from clumped isotope palaeotemperature measurements that indicate the limestone clasts were precipitated or recrystallized under higher temperature conditions than the burial diagenetic calcite found in the Clachtoll Formation. Raman spectra of an organic carbon particle within a laminated dome of the Poll a’Mhuilt Member at Enard Bay are consistent with the organic carbon having been re-worked from the ∼2 Ga Loch Maree Group, and we speculate that this might also be true of the calcite.\ud \ud Microbial fossils are well known from elsewhere in the Stoer Group, but no conclusive examples were found within the thin-sections examined herein. No conclusive evidence was found to suggest that any of the examined putative stromatolites were biogenic, leading to the conclusion that they are best considered stromatolite-like sedimentary rocks (pseudostromatolites).

The direct measurement of gases trapped in sulphide minerals shows that samples from gold-bearing deposits in Britain and Ireland are anomalously rich in methane. Chalcopyrite samples in de...

The distribution of oil residues in fractured Upper Devonian reservoir sandstones of Caithness help us to understand relationships between oil charge and episodes of fracturing. The sandstones are cut by an extensive set of tightly cemented deformation bands in the vicinity of the Brough Fault, and calcite-mineralized open fractures. The deformation bands compartmentalized the reservoir, which subsequently was charged by oil to varying extent in different compartments. Petrographic and biomarker data distinguish two charges of oil. The first charge of oil was unaltered. The later mineralized fractures introduced a heavier biodegraded oil that spread into the sandstone pores and displaced/overprinted the earlier oil. Two distinct oil charges are also evident from two generations of oil fluid inclusions, firstly in overgrowths on quartz grains, and secondly in the calcite veins, exhibiting distinct fluorescence characteristics. Migration and trapping of oil depended on the combination of two fracturing episodes of different character, in which the first episode created sealed compartments which were then filled by oil introduced by the second episode.

Carbonatitic magmatism and metasomatism are rare in Great Britain & Ireland. However, REE-Nb minerals were identified in impure marbles and calc-silicates on the Aird of Shin and Arscaig near Lairg, Scotland. They belong to the Palaeoproterozoic Shin Group, a supercrustal succession of amphibolites, banded silicic gneisses, marbles and calc-silicates. The Shin Group is one of several Palaeoproterozoic to Neoproterozoic marble inliers in the North Highlands of Scotland that present evidence of Caledonian orogen carbonatitic metasomatism. The Proterozoic Bayan Obo ore complex in China was similarly deposited as a dolomite-limestone and later subject to alkali intrusions and carbonatitic metasomatism during the Caledonian orogeny. The Bayan Obo complex hosts REE-Nb-Fe carbonatitic fine-grained dolomites, REE-Nb deficient coarse dolomites, carbonatitic dykes, limestones and dolostones. The Aird of Shin marble mineralogy comprises niobium and tantalum Ca-bearing oxides, scheelite, strontian barite, ilmenite, REE-bearing monazite, REE-epidote and Fe-Mo sulphides in an impure Na-Fe-K calcite fabric. The Arscaig Qtz-Na-K calc-silicates are enriched in REE-bearing monazite, Mg-Fe chlorite and Fe-oxides, with minor REE-bearing xenotime, Mn-Fe garnet and strontian barite. The REE-Nb Aird of Shin marble and the REE-phosphate bearing Arscaig calc-silicates are comparable with carbonatitic mineral phases in the Bayan Obo complex. This study adds support to previous recognition of Caledonian carbonatitic magmatism and carbonatitic metasomatism of Proterozoic limestones and calc-silicates in Scotland.

Iron oxide grain coatings in red sandstones contain trace metals that are released upon dissolution of the coatings. Analyses by ICP-MS following acid leaching of the grain coatings show that the dissolved metals can constitute an ore-forming fluid, as hypothesized in models for sandstone-hosted ore deposits. Median compositions of 37 samples, mostly of Triassic to Devonian age, from across Britain and Ireland are 6.3 ppm copper, 2.4 ppm cobalt, 10.1 ppm vanadium, and 0.3 ppm uranium. These contents at the basin scale are adequate to form the observed range of ore deposits in red beds. The migration of hydrocarbons or brines can cause the dissolution of grain coatings and contributes to controlling the distribution of ore deposits. Future measurements should test red beds derived from uplifted, mineralized plate margins, in which sandstones may be preloaded with ore metals.

We welcome the comments of Smith and Rippon (2021) about our map of vitrinite reflectance data derived from Carboniferous coal in Britain. The essence of their contribution is that our map is based upon a limited database (103 samples). We are well aware that data is available for other localities, at a range of depths within mines, and in some cases with details of statistical accuracy. Smith and Rippon conclude that the data available is too extensive to make it possible to produce a summary map. That is possibly why, despite the heritage of coal studies in Britain, such a map has not been published. However, the scale at which we have resolved variations in the reflectance values, simplified further in Figure 1, allows realization of the tremendous educational potential in the data. Our purpose was to produce a map, and we have employed a data base appropriate to do so, rather than assemble a national data base, which is the responsibility of others.

Gold grains, up to 40 &mu, m in size and containing variable percentages of admixed platinum, have been identified in coals from the Leinster Coalfield, Castlecomer, SE Ireland, for the first time. Gold mineralisation occurs in sideritic nodules in coals and in association with pyrite and anomalous selenium content. Mineralisation here may have reflected very high heat flow in foreland basins north of the emerging Variscan orogenic front, responsible for gold occurrence in the South Wales Coalfield. At Castlecomer, gold (&ndash, platinum) is attributed to precipitation with replacive pyrite and selenium from groundwaters at redox interfaces, such as siderite nodules. Pyrite in the cores of the nodules indicates fluid ingress. The underlying Caledonian basement bedrock is mineralised by gold, and thus likely provided a source for gold. The combination of the gold occurrences in coal in Castlecomer and in South Wales, proximal to the Variscan orogenic front, suggests that these coals along the front could comprise an exploration target for low-temperature concentrations of precious metals.

Microbial reduction of soluble selenium (Se) or tellurium (Te) species results in immobilization as elemental forms and this process has been employed in soil bioremediation. However, little is known of direct and indirect fungal interactions with Se-/Te-bearing ores. In this research, the ability of Phoma glomerata to effect transformation of selenite and tellurite was investigated including interaction with Se and Te present in sulfide ores from the Kisgruva Proterozoic volcanogenic deposit. Phoma glomerata could precipitate elemental Se and Te as nanoparticles, intracellularly and extracellularly, when grown with selenite or tellurite. The nanoparticles possessed various surface capping molecules, with formation being influenced by extracellular polymeric substances. The presence of sulfide ore also affected the production of exopolysaccharide and protein. Although differences were undetectable in gross Se and Te ore levels before and after fungal interaction using X-ray fluorescence, laser ablation inductively coupled plasma mass spectrometry of polished flat ore surfaces revealed that P. glomerata could effect changes in Se/Te distribution and concentration indicating Se/Te enrichment in the biomass. These findings provide further understanding of fungal roles in metalloid transformations and are relevant to the geomicrobiology of environmental metalloid cycling as well as informing applied approaches for Se and Te immobilization, biorecovery or bioremediation.

Asteroid and comet impacts are known to have caused profound disruption to multicellular life, yet their influence on habitats for microorganisms, which comprise the majority of Earth's biomass, is less well understood. Of particular interest are geological changes in the target lithology at and near the point of impact that can persist for billions of years. Deep subsurface and surface-dwelling microorganisms are shown to gain advantages from impact-induced fracturing of rocks. Deleterious changes are associated with impact-induced closure of pore spaces in rocks. Superimposed on these long-term geological changes are post-impact alterations such as changes in the hydrological system in and around a crater. The close coupling between geological changes and the conditions for microorganisms yields a synthesis of the fields of microbiology and impact cratering. We use these data to discuss how craters can be used in the search for life beyond Earth.

The West Cumbria iron ore field exhibits kilometre-scale compartmentalization of fluid sources, as evidenced by sulphur isotope data. Barite accompanying haematite ore from 13 mines in an along-strike width of 5 km has δ34S(VCDT) isotopic compositions ranging from +7.9 to +23.6‰. The large variation is strongly controlled by NNW-SSE faulting, in which the heaviest compositions are to the north and lightest in the south. The heavy and light compositions are comparable with those of Carboniferous and Permian evaporites respectively, both of which occur in West Cumbria and are the assumed primary sources of the barite sulphur, though input from the oxidation of Carboniferous coal pyrite may have provided a minor component. The derivation of sulphur from stratigraphically distinct sources shows that faults isolated fluid flow in compartments on a local scale. Published data for barite from an adjacent fault block in a potential waste disposal site at Sellafield are further distinct, indicative of a primary pyrite source. These data emphasize that fluid sources can be highly compartmentalized in a faulted system and require supporting evidence to confirm if they can be correlated.

The subsurface ‘deep biosphere’ represents one-tenth to one-third of Earth9s total global present-day biomass. The rest is dominated by land plants, a relatively recent development in geological history. Before c. 400 Ma, a relatively low surface biomass with high productivity and fast turnover supplied carbon to a deep biosphere with high biomass but low productivity and slow turnover. Here, we argue that the deep biosphere outweighed the surface biosphere by about one order of magnitude for at least half of the history of life on Earth. This result offers a new perspective on the history of life on Earth with important implications for the search for life on other worlds.

Standard mode and collision/reaction cell mass spectroscopy methods have been utilised in order to overcome spectral interferences and provide ultra-low quantification of selenium (Se) and tellurium (Te) in British coals for the first time. The accurate detection of Se and Te in coals is becoming increasingly important, as coals and pyrite have been identified as potentially significant trace element sources. The mean Se concentration of British coals bear comparison to that of world coals, with anomalous Se content (concentrations above 4 mg/kg) across westerly exposures, often coinciding with high sulphur (S) content and visible pyrite. New Te data for British coals gives a mean concentration of 0.02 mg/kg, with anomalous Te in Ayrshire. There is a positive correlation in the Te/Se ratio across the sample set. The close relationship between Se and Te, as well as Se-Te with both early syngenetic and later cleat filling pyrite, confirms an important role for sulphides in Se and Te sequestration in British coals. The high Se-Bowland Shale and/or Ordovician volcanics may have provided the trace element source British coals of similar or younger age. Regional intrusive activity (shallow Se and Te concentrations of British coals LB draft manuscript tabular intrusions or more extensive plutons) and episodes of intense deformation can alter the thermal maturity of coals, and may have driven the movement of trace element-rich fluids through strata, locally enriching coals in Se and Te.

A method is proposed for the determination of selenium at low concentration in coal by collision/reaction cell technology inductively coupled plasma mass spectrometry (CRC-ICP-MS). Samples were decomposed by high pressure microwave-assisted wet digestion (MAWD) using 250 mg of coal, a mixture of 5 mL of 14.4 mol L−1 HNO3 and 1 mL of 40% HF and 70 min of heating program (200 °C and 40 bar). Hydrogen gas used in the collision/reaction cell was investigated to minimize the argon-based interferences at m/z 77, 78 and 80. The rejection parameter (RPq) and the H2 gas flow rate were set to 0.45 and 4.8 mL min−1, respectively. The use of H2 in the cell resulted in other polyatomic interferences, such as 76Ge1H+, 79Br1H+ and 81Br1H+, which impaired Se determination using 77Se, 80Se and 82Se isotopes, thus Se determination was carried out by monitoring only 78Se isotope. Selenium was determined in certified reference materials of coal (NIST 1635 and SARM 20) and an agreement better than 95% was observed between the results obtained by CRC-ICP-MS and the certified values. Under optimized conditions, the instrumental limit of detection was 0.01 μg L−1 and the method limit of detection was 0.01 μg g−1, which was suitable for Se determination at very low concentration in coal.

Surface mineral crusts on Earth are highly diverse and usually, contain microbial life. Crusts constitute an attractive target to search for life: they require water for their formation, they efficiently entrap organic matter and are relatively easy to sample and process. They hold a record of life in the form of microbial remains, biomolecules and carbon isotope composition. A miniaturized Raman spectrometer is included in the ExoMars 2020 payload as it is sensitive to a range of photosynthetic pigments. Samples from the Haughton Impact Structure, Canadian High Arctic and others, shows the preservation of pigments in a range of crust types, especially supra-permafrost carbonate crusts and cryptogamic crusts. The Raman spectral signatures of these crusts are shown along with biomarker analysis to showcase these techniques prior to the ExoMars 2020 mission. Carotenoids and other photoprotective microbial pigments are identified in the Haughton surface crusts using Raman spectroscopy. Gas chromatography-mass spectrometry analyses show a distribution of fatty acids which are most likely from a cyanobacterial source. The successful demonstration of these analyses in the Haughton Impact structure shows the biosignature of surface mineral crusts can be easily extracted and provides an excellent target for sampling evidence of life on Mars.

Samples of red bed sediments in several Mesoproterozoic successions contain enrichments of tellurium (Te), including discrete telluride minerals. The tellurides were neoformed during redox-controlled diagenesis, rather than representing mechanical concentrations of heavy minerals. Tellurium is enriched relative to selenium, which may reflect erosion of Archean and Palaeoproterozoic rocks with high Te contents. High continentality during the Mesoproterozoic would have limited the delivery of Te and other trace elements to the oceans, so accumulated Te on the continents.

Carboniferous coals of the Ayrshire Coalfield are enriched in selenium (Se) relative to average UK and world compositions, substituting for sulphur in pyrite. Greenburn surface mine coals are characterized by syngenetic concretionary pyrite ( c. 15% total area), occurring as bedding-parallel banding, and later-formed (epigenetic) cross-cutting pyrite in cleats ( c. 9% total area). In these, sulphur isotope compositions for both syngenetic and epigenetic pyrite include isotopically light and heavy variants, suggesting diagenetic and hydrothermal fluid formation. Late/post-Visean cleat-filling pyrite is enriched in Se (up to 266 ppm) compared to the earlier-formed material (Se up to 181 ppm). Anomalous Se may have been sourced from near-by sulphidic Dalradian metamorphic rocks. Initial Se sequestration is associated with syngenetic pyrite mineralization, absorbed from seawater and pore waters, with additional Se introduced from fluids mobilized during epigenetic pyrite formation. Cleats from local brittle fracturing provided channels for fluid flow and a locus for precipitation of comparatively high-Se pyrite. Permian dolerite intrusions may have provided an enrichment source and/or fluid distribution mechanism. The Se concentrations of the Greenburn coals relate to multi-stage mineralization, with cleat-filling pyrite showing the highest Se content, and highlight the potential for high Se in similarly altered and fractured coal deposits worldwide. Supplementary material: LA-ICP-MS maps for Fe, Se, Ag, As, Cu, Hg, Pb and Te for Greenburn coal samples from seams 9300 Lime and 6900 Burnfoot Bridge are available at https://doi.org/10.6084/m9.figshare.c.3967860

Black sediment veins up to 2 cm width penetrate the Caledonian Helmsdale Granite in the vicinity of the Helmsdale Fault, onshore Moray Firth. The black colour and geochemistry of the veins reflect a high content of organic carbon. Both Devonian and Jurassic shales are conceivable available sources, but sterane compositions relate the organic matter to the Jurassic shales. A content of extractable organic matter higher than in the shales suggests that the carbon in the veins represents oil rather than mechanically mobilized shale. The oil was present during sediment vein emplacement. The veins were emplaced forcefully, which may reflect high fluid pressure associated with post-Jurassic movement on the Helmsdale Fault.