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Examines the impact of oil-filled sandstones on quartz cementation rates. Comparison between sandstones from oil and water zones; Effect of oil charging on quartz-cement growth rates; Preservation of porosity by oil charging in the crestal part.

The δ13Ccarb and 87Sr/86Sr secular variations in Neoproteozoic seawater have been used for the purpose of ‘isotope stratigraphy’ but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for ‘blind dating’. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local δ13Ccarb fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative δ13Ccarb excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and ‘blind dating’. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590–544 Myr interval, and two age-groups at 660–610 and 740–690 Myr can be resolved. [ABSTRACT FROM AUTHOR]

Provides information on a study conducted which examines the use of fatty acid biomarker analysis coupled with gas chromatography-isotope ratio mass spectrometry to confirm the presence of hydrothermal vent mussels containing methantrophic and thiotropic bacterial endosymbionts. Where the mussels were collected from; How the stable-carbon-isotope ratios were measured; Information on the methanol used to prepare methyl esters.

The stable isotope record of marine carbon indicates that the Proterozoic Eon began and ended with extreme fluctuations in the carbon cycle. In both the Paleoproterozoic [2500 to 1600 million years ago (Ma)] and Neoproterozoic (1000 to 542 Ma), extended intervals of anomalously high carbon isotope ratios (δ13C) indicate high rates of organic matter burial and release of oxygen to the atmosphere; in the Neoproterozoic, the high δ13C interval was punctuated by abrupt swings to low δ13C, indicating massive oxidation of organic matter. We report a Paleoproterozoic negative δ13C excursion that is similar in magnitude and apparent duration to the Neoproterozoic anomaly. This Shunga-Francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen-rich atmosphere. [ABSTRACT FROM AUTHOR]

• Bacaba and Castanha deposits represent different portions of an IOCG system. • Bacaba deposit records an evolution related to 2.7 and 2.06 Ga hydrothermal events. • Bacaba ore precipitated due to mixing of metalliferous magmatic and non-magmatic fluids. • Castanha was closer to its source of hot overpressured magmatic fluids than Bacaba. • Fluid-rock interaction triggered metal-complex destabilization at Castanha. The evolution of the Bacaba and Castanha iron oxide-copper-gold deposits, located in the Carajás Mineral Province, Brazil, is discussed based on petrography, scanning electron microscopy, stable isotopes, and fluid inclusion analyses. The Castanha deposit is mainly hosted by ca. 2.75 Ga subvolcanic and volcanic rhyodacitic rocks, and gabbros. Early sodic (albite, scapolite) alteration was followed by high-temperature calcic-iron (actinolite-magnetite), potassic (biotite), and minor chlorite and sericite alteration. Calcite, REE carbonate, and epidote represent a late and proximal alteration to ore bodies. Ore breccias with Durchbewegung structure comprise chalcopyrite + pyrrhotite + pyrite ± cobaltpentlandite ± sphalerite ± marcasite and are notable due to their nickel-(zinc) enrichment. The Bacaba Deposit is hosted by the ca. 3.00 Ga Bacaba Tonalite, 2.85 Ga Serra Dourada Granite, and gabbro bodies. Early (ca. 2.70 Ga) alteration at Bacaba includes sodic (albite, scapolite), iron (magnetite), and potassic-iron (K feldspar-magnetite, biotite) associations. Well-developed late chlorite, albite, sericite, calcite-hematite-(musketovite) alteration formed during a Paleoproterozoic overprinting (ca. 2.06 Ga). The Bacaba ore is composed of (I) chalcopyrite ± magnetite ± bornite, and (II) chalcopyrite ± pyrite ± hematite/musketovite, related to early potassic-iron and late alteration, respectively. The Castanha deposit was formed from magmatic fluid (δ18O H2O = 9.5 ± 0.5‰ to 5.2 ± 1.0‰, at 500 to 400 °C) and sulfur (δ34S = 0.1–3‰) sources, with a limited contribution of externally-derived fluids during its evolution. Ore precipitation progressed under considerably low f S 2 and f O 2 conditions, at relatively high temperatures (>370 ± 50 °C). Fluid inclusion analyses indicate greater proximity of the Castanha deposit to the source of a hot overpressured magmatic fluid, suggesting its formation in a high-temperature hydrothermal center. Fluid-rock interaction coupled with increasing pH might have been the critical factors in destabilizing the metal-chloride complex in the Castanha deposit. The Bacaba deposit evolved from a fluid-mixing between hot (>450 °C) hypersaline CaCl 2 -NaCl-bearing magmatic brine (>30 mass % equivalent) and a less saline, colder, and 18O-depleted and D-enriched fluid (e.g., seawater or low-latitude meteoric water). Mixing resulted in an oxidizing environment, dilution (salinities between 35 and 4 mass % equivalent), and temperature drop (160–190 °C), triggering the ore precipitation. At Bacaba, the slightly higher δ34S values (1.3–5.4‰) may reflect an additional contribution of externally-derived sulfur through the thermochemical reduction of oxidized sulfur species. In the Southern Copper Belt, the regional spatial distribution of the sulfur isotope compositions shows the highest δ34S sulfide values close to the Paleoproterozoic Sossego Orebody and the Alvo 118 deposit. This might suggest significant involvement of externally-derived components (e.g., diluted fluids and sulfur) during late stages of a protracted hydrothermal evolution in the Carajás IOCG deposits. [ABSTRACT FROM AUTHOR]

Although emerald deposits are relatively rare, they can be formed in several different, but specific geologic settings and the classification systems and models currently used to describe emerald precipitation and predict its occurrence are too restrictive, leading to confusion as to the exact mode of formation for some emerald deposits. Generally speaking, emerald is beryl with sufficient concentrations of the chromophores, chromium and vanadium, to result in green and sometimes bluish green or yellowish green crystals. The limiting factor in the formation of emerald is geological conditions resulting in an environment rich in both beryllium and chromium or vanadium. Historically, emerald deposits have been classified into three broad types. The first and most abundant deposit type, in terms of production, is the desilicated pegmatite related type that formed via the interaction of metasomatic fluids with beryllium-rich pegmatites, or similar granitic bodies, that intruded into chromium- or vanadium-rich rocks, such as ultramafic and volcanic rocks, or shales derived from those rocks. A second deposit type, accounting for most of the emerald of gem quality, is the sedimentary type, which generally involves the interaction, along faults and fractures, of upper level crustal brines rich in Be from evaporite interaction with shales and other Cr- and/or V-bearing sedimentary rocks. The third, and comparatively most rare, deposit type is the metamorphic-metasomatic deposit. In this deposit model, deeper crustal fluids circulate along faults or shear zones and interact with metamorphosed shales, carbonates, and ultramafic rocks, and Be and Cr (±V) may either be transported to the deposition site via the fluids or already be present in the host metamorphic rocks intersected by the faults or shear zones. All three emerald deposit models require some level of tectonic activity and often continued tectonic activity can result in the metamorphism of an existing sedimentary or magmatic type deposit. In the extreme, at deeper crustal levels, high-grade metamorphism can result in the partial melting of metamorphic rocks, blurring the distinction between metamorphic and magmatic deposit types. In the present paper, we propose an enhanced classification for emerald deposits based on the geological environment, i.e., magmatic or metamorphic; host-rocks type, i.e., mafic-ultramafic rocks, sedimentary rocks, and granitoids; degree of metamorphism; styles of minerlization, i.e., veins, pods, metasomatites, shear zone; type of fluids and their temperature, pressure, composition. The new classification accounts for multi-stage formation of the deposits and ages of formation, as well as probable remobilization of previous beryllium mineralization, such as pegmatite intrusions in mafic-ultramafic rocks. Such new considerations use the concept of genetic models based on studies employing chemical, geochemical, radiogenic, and stable isotope, and fluid and solid inclusion fingerprints. The emerald occurrences and deposits are classified into two main types: (Type I) Tectonic magmatic-related with sub-types hosted in: (IA) Mafic-ultramafic rocks (Brazil, Zambia, Russia, and others); (IB) Sedimentary rocks (China, Canada, Norway, Kazakhstan, Australia); (IC) Granitic rocks (Nigeria). (Type II) Tectonic metamorphic-related with sub-types hosted in: (IIA) Mafic-ultramafic rocks (Brazil, Austria); (IIB) Sedimentary rocks-black shale (Colombia, Canada, USA); (IIC) Metamorphic rocks (China, Afghanistan, USA); (IID) Metamorphosed and remobilized either type I deposits or hidden granitic intrusion-related (Austria, Egypt, Australia, Pakistan), and some unclassified deposits. [ABSTRACT FROM AUTHOR]

In this study, the oxygen isotope (δ18O) composition of pink to red gem-quality rubies from Paranesti, Greece was investigated using in-situ secondary ionization mass spectrometry (SIMS) and laser-fluorination techniques. Paranesti rubies have a narrow range of δ18O values between ~0 and +1‰ and represent one of only a few cases worldwide where δ18O signatures can be used to distinguish them from other localities. SIMS analyses from this study and previous work by the authors suggests that the rubies formed under metamorphic/metasomatic conditions involving deeply penetrating meteoric waters along major crustal structures associated with the Nestos Shear Zone. SIMS analyses also revealed slight variations in δ18O composition for two outcrops located just ~500 m apart: PAR-1 with a mean value of 1.0‰ ± 0.42‰ and PAR-5 with a mean value of 0.14‰ ± 0.24‰. This work adds to the growing use of in-situ methods to determine the origin of gem-quality corundum and re-confirms its usefulness in geographic "fingerprinting". [ABSTRACT FROM AUTHOR]

Greece contains several gem corundum deposits set within diverse geological settings, mostly within the Rhodope (Xanthi and Drama areas) and Attico-Cycladic (Naxos and Ikaria islands) tectono-metamorphic units. In the Xanthi area, the sapphire (pink, blue to purple) deposits are stratiform, occurring within marble layers alternating with amphibolites. Deep red rubies in the Paranesti-Drama area are restricted to boudinaged lenses of Al-rich metapyroxenites alternating with amphibolites and gneisses. Both occurrences are oriented parallel to the ultra-high pressure/high pressure (UHP/HP) Nestos suture zone. On central Naxos Island, colored sapphires are associated with desilicated granite pegmatites intruding ultramafic lithologies (plumasites), occurring either within the pegmatites themselves or associated metasomatic reaction zones. In contrast, on southern Naxos and Ikaria Islands, blue sapphires occur in extensional fissures within Mesozoic metabauxites hosted in marbles. Mineral inclusions in corundums are in equilibrium and/or postdate corundum crystallization and comprise: spinel and pargasite (Paranesti), spinel, zircon (Xanthi), margarite, zircon, apatite, diaspore, phlogopite and chlorite (Naxos) and chloritoid, ilmenite, hematite, ulvospinel, rutile and zircon (Ikaria). The main chromophore elements within the Greek corundums show a wide range in concentration: the Fe contents vary from (average values) 1099 ppm in the blue sapphires of Xanthi, 424 ppm in the pink sapphires of Xanthi, 2654 ppm for Paranesti rubies, 4326 ppm for the Ikaria sapphires, 3706 for southern Naxos blue sapphires, 4777 for purple and 3301 for pink sapphire from Naxos plumasite, and finally 4677 to 1532 for blue to colorless sapphires from Naxos plumasites, respectively. The Ti concentrations (average values) are very low in rubies from Paranesti (41 ppm), with values of 2871 ppm and 509 in the blue and pink sapphires of Xanthi, respectively, of 1263 ppm for the Ikaria blue sapphires, and 520 ppm, 181 ppm in Naxos purple, pink sapphires, respectively. The blue to colorless sapphires from Naxos plumasites contain 1944 to 264 ppm Ti, respectively. The very high Ti contents of the Xanthi blue sapphires may reflect submicroscopic rutile inclusions. The Cr (average values) ranges from 4 to 691 ppm in the blue, purple and pink colored corundums from Naxos plumasite, is quite fixed (222 ppm) for Ikaria sapphires, ranges from 90 to 297 ppm in the blue and pink sapphires from Xanthi, reaches 9142 ppm in the corundums of Paranesti, with highest values of 15,347 ppm in deep red colored varieties. Each occurrence has both unique mineral assemblage and trace element chemistry (with variable Fe/Mg, Ga/Mg, Ga/Cr and Fe/Ti ratios). Additionally, oxygen isotope compositions confirm their geological typology, i.e., with, respectively δ18O of 4.9 ± 0.2‰ for sapphire in plumasite, 20.5‰ for sapphire in marble and 1‰ for ruby in mafics. The fluid inclusions study evidenced water free CO2 dominant fluids with traces of CH4 or N2, and low CO2 densities (0.46 and 0.67 g/cm3), which were probably trapped after the metamorphic peak. The Paranesti, Xanthi and central Naxos corundum deposits can be classified as metamorphic sensu stricto (s.s.) and metasomatic, respectively, those from southern Naxos and Ikaria display atypical magmatic signature indicating a hydrothermal origin. Greek corundums are characterized by wide color variation, homogeneity of the color hues, and transparency, and can be considered as potential gemstones. [ABSTRACT FROM AUTHOR]

Integrating palaeoclimatological proxies and historical records, which is necessary to achieve a more complete understanding of climate impacts on past societies, is a challenging task, often leading to unsatisfactory and even contradictory conclusions. This has until recently been the case for Italy, the heart of the Roman Empire, during the transition between Antiquity and the Middle Ages. In this paper, we present new high-resolution speleothem data from the Apuan Alps (Central Italy). The data document a period of very wet conditions in the sixth c. AD, probably related to synoptic atmospheric conditions similar to a negative phase of the North Atlantic Oscillation. For this century, there also exist a significant number of historical records of extreme hydroclimatic events, previously discarded as anecdotal. We show that this varied evidence reflects the increased frequency of floods and extreme rainfall events in Central and Northern Italy at the time. Moreover, we also show that these unusual hydroclimatic conditions overlapped with the increased presence of "water miracles" in Italian hagiographical accounts and social imagination. The miracles, performed by local Church leaders, strengthened the already growing authority of holy bishops and monks in Italian society during the crucial centuries that followed the "Fall of the Roman Empire". Thus, the combination of natural and historical data allows us to show the degree to which the impact of climate variability on historical societies is determined not by the nature of the climatic phenomena per se, but by the culture and the structure of the society that experienced it., Supplementary Information: The online version contains supplementary material available at 10.1007/s10584-021-03043-x., Competing Interests: Conflict of interestThe authors declare no competing interests., (© The Author(s) 2021, corrected publication 2021.)

Our study focuses on pyrite nodules developed in the Brent Group sandstones, which host the Brent Oilfield, one of the North Sea's greatest oil and gas producers. Timing of nodule formation is equivocal, but due to the forceful, penetrative textures that abound, it is considered late. This pyrite offers a research opportunity because it records the development of the supply of H(2)S in a hydrocarbon reservoir and its sulphur isotopic composition. Laser-based analysis of δ(34)S reveals an extraordinary diversity in values and patterns. The values range from-27 to+72‰, covering half the terrestrial range, with large variations at the submillimetre scale. Isotopically heavy (δ(34)S ∼+30‰ or higher) sulphide is endemic, but low δ(34)S pyrite is also present and appears to represent a temporally though not spatially (on the ∼cm scale) distinct pyritisation event. The distribution of δ(34)S values within individual concretions can be normal (Gaussian), but in some cases may reflect progressive isotope fractionation process(es), conceivably of Rayleigh type. The source of the sulphur and the identity of the isotope fractionation process(es) remain enigmatic.

Adélie penguin (Pygoscelis adeliae) modern and fossil eggshells and guano samples collected from ornithogenic soils in Terra Nova Bay (Victoria Land, Ross Sea) were processed for carbon and nitrogen isotopic ratios with the aim of detecting past penguin dietary changes. A detailed and greatly expanded Adélie penguin dietary record dated back to 7,200 years BP has been reconstructed for the investigated area. Our data indicate a significant dietary shift between fish and krill, with a gradual decrease from past to present time in the proportion of fish compared to krill in Adélie penguin diet. From 7,200 to 2,000 years BP, δ(13)C and δ(15)N values indicate fish as the most eaten prey. The dietary contribution of lower-trophic prey in penguin diet started becoming evident not earlier than 2,000 years BP, when the δ(13)C values reveal a change in the penguin feeding behavior. Modern eggshell and guano samples reveal a major dietary contribution of krill but not a krill-dominated diet, since δ(13)C values remain much too high if krill prevail in the diet. According to the Holocene environmental background attested for Victoria Land, Adélie penguin dietary shifts between fish and krill seem to reflect penguin paleoecological responses to different paleoenvironmental settings with different conditions of sea-ice extension and persistence. Furthermore, Adélie penguin diet appears to be particularly affected by environmental changes in a very specific period within the breeding season, namely the egg-laying period when penguin dietary and feeding habit shifts are clearly documented by the δ(13)C of eggshell carbonate.

The fossil record of the subsurface biosphere is sparse. Results obtained on subsurface filamentous fabrics (SFF) from >225 paleosubsurface sites in volcanics, oxidized ores, and paleokarst of subrecent to Proterozoic age are presented. SFF are mineral encrustations on filamentous or fibrous substrates that formed in subsurface environments. SFF occur in association with low-temperature aqueous mineral assemblages and consist of tubular, micron-thick (median 1.6 micron) filaments in high spatial density, which occur as irregular masses, matted fabrics, and vertically draped features that resemble stalactites. Micron-sized filamentous centers rule out a stalactitic origin. Morphometric analysis of SFF filamentous forms demonstrates that their shape more closely resembles microbial filaments than fibrous minerals. Abiogenic filament-like forms are considered unlikely precursors of most SFF, because abiogenic forms differ in the distribution of widths and have a lower degree of curvature and a lower number of direction changes. Elemental analyses of SFF show depletion in immobile elements (e.g., Al, Th) and a systematic enrichment in As and Sb, which demonstrates a relation to environments with high flows of water. Sulfur isotopic analyses are consistent with a biological origin of a SFF sample from a Mississippi Valley-Type deposit, which is consistent with data in the literature. Fe isotopes in SFF and active analogue systems, however, allow no discrimination between biogenic and abiogenic origins. The origin of most SFF is explained as permineralized remains of microbial filaments that possibly record rapid growth during phases of high water flow that released chemical energy. It is possible that some SFF formed due to encrustation of mineral fibers. SFF share similarities with Microcodium from soil environments. SFF are a logical target in the search for past life on Mars. The macroscopic nature of many SFF allows for their relatively easy in situ recognition and targeting for more detailed microstructural and geochemical analysis.

A preliminary evaluation of compound-specific isotope analysis (CSIA) as a novel, alternative method for identifying source correlation compounds in soils contaminated with residual heavy or weathered petroleum wastes is presented. Oil-contaminated soil microcosms were established using soil (sandy-loam, non-carbonaceous cley) amended with ballast-, crude- or No.6 fuel oil. Microcosms were periodically sampled over 256 days and delta(13)C values (which express the ratio of (13)C to (12)C) determined at each time point for five n-alkanes and the isoprenoid norpristane using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). Although some temporal variation was observed, no significant temporal shifts in the delta(13)C values for the five n-alkanes were measured in all three oils. Isoprenoid isotope ratios (delta(13)C) appeared to be least affected by biotransformation, especially in the No.6 fuel oil. The research suggests that the delta(13)C of isoprenoids such as norpristane, may be of use as source correlation parameters.

In grassland ecosystems, soil animals act as key soil engineers and architects. The diversity of soil animals is also a regulator of ecosystem carbon flow. However, our understanding of the link between soil animals, carbon fluxes and soil physical organisation remains poor. An integrated approach based on soil micromorphology and laser ablation stable isotope ratio mass spectrometry (LA-IRMS) was developed to provide spatially distributed data of pulse-derived (13)C tracer from roots in the soil environment. This paper describes the development and testing of a LA-IRMS (13)C/(12)C analytical method on soil thin sections as a means to determine the fate of root carbon derived from photosynthesis into soil. Results from this work demonstrated (1) that micro-scale delta(13)C (per thousand) analysis could be made on targeted features located within a soil thin section and (2) that LA-IRMS delta(13)C (per thousand) measurements made on samples obtained from (13)CO(2) pulse labelled plant-soil blocks confirmed the presence of recent photosynthates in the rhizosphere (1 and 4 weeks post-pulse)., (Copyright 2002 John Wiley & Sons, Ltd.)