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Monitoring of potential gas seepage for CO2 sequestration and CO2-EOR (Enhanced Oil Recovery) in geologic storage will involve geophysical and geochemical measurements of parameters at depth and at, or near the surface. The appropriate methods for MVA (Monitoring, Verification, Accounting) are needed for both cost and technical effectiveness. This work provides an overview of some of the geochemical methods that have been demonstrated to be effective for an existing CO2-EOR (Rangely, CA, USA) and a proposed project at Teapot Dome, WY, USA. Carbon dioxide and CH4 fluxes and shallow soil gas concentrations were measured, followed by nested completions of 10-m deep holes to obtain concentration gradients. The focus at Teapot Dome was the evaluation of faults as pathways for gas seepage in an under-pressured reservoir system. The measurements were supplemented by stable carbon and oxygen isotopic measurements, carbon-14, and limited use of inert gases. The work clearly demonstrates the superiority of CH4 over measurements of CO2 in early detection and quantification of gas seepage. Stable carbon isotopes, carbon-14, and inert gas measurements add to the verification of the deep source. A preliminary accounting at Rangely confirms the importance of CH4 measurements in the MVA application [ABSTRACT FROM AUTHOR]

Although the first petroleum fields in the Mozambique basin were discovered more than 60 years ago, the composition and origin of petroleum fluids in this basin are largely unknown. We studied the geochemical composition of petroleum gases and liquids from the Inhassoro, Pande and Temane fields located onshore Mozambique. The gases are relatively dry (methane-dominated, average C1/(C1-C5) ratio is ~0.96), have pure thermogenic origin, originate predominantly from marine shale source organofacies and show no evidence of primary microbial gas or biodegradation. Most condensates have relatively high API gravity up to 76 degrees, are very mature and contain only traces of biomarkers, likely from migration contamination. However, biomarkers in the light oil from the Inhassoro field indicate that the oil derived from sub-oxic marine shales of the Late Cretaceous age. We suggest that the Aptian-Coniacian Domo Shale is the likely source rock for petroleum gases and liquids in the studied fields. Our geochemical data, including gas isotopes, as well as source-specific and age-specific biomarkers, exclude coals in the Late Carboniferous—Early Jurassic Karoo Supergroup as effective source rocks for the studied fields. [ABSTRACT FROM AUTHOR]

Karstic aquifers play an important role for drinking and irrigation supply in Morocco. However, in some areas, a deeper understanding is needed in order to improve their sustainable management under global changes. Our study, based on chemical and isotopic investigation of 67 groundwater samples from the karst aquifer in the Rif Mountains, provides crucial information about the principal factors and processes influencing groundwater recharge and residence time. The δ18O and δ2H isotopic values indicate that the recharge is derived from meteoric water at high, intermediate, and low elevations for Lakraa Mountain, North of Lao River, and Haouz and Dersa Mountain aquifers, respectively. All samples show an isotopic signature from Atlantic Ocean except for those from the Lakraa Mountain aquifer, which shows Mediterranean Sea influence. Groundwater age determined by radiocarbon dating using the IAEA model indicates that the ages range from modern to 1460 years. This short residence time is consistent with the detectable tritium values (>2.7 TU) measured in groundwater. These values are similar to those of precipitation at the nearest GNIP stations of Gibraltar and Fez-Saiss, situated around 100 km north and 250 km south of the study area, respectively. This evidence indicates that groundwater in the Rif Mountains contains modern recharge (<60 years), testifying to significant renewability and the vulnerability of the hydrological system to climate variability and human activities. The results also indicate the efficiency of isotopic tracing in mountainous springs and would be helpful to decision makers for water in this karstic zone. [ABSTRACT FROM AUTHOR]

In metamorphic rocks, mineral species react over a range of pressure–temperature conditions that do not necessarily overlap. Mineral equilibration can occur at varied points along the metamorphic pressure–temperature (PT) path, and thus at different times. The sole or dominant use of zircon isotopic compositions to constrain the evolution of metamorphic rocks might then inadvertently skew geological interpretations towards one aspect or one moment of a rock's history. Here, we present in-situ U–Pb/Sm–Nd isotope analyses of the apatite crystals extracted from two meta-igneous rocks exposed in the Saglek Block (North Atlantic craton, Canada), an Archean metamorphic terrane, with the aim of examining the various signatures and events that they record. The data are combined with published U–Pb/Hf/O isotope compositions of zircon extracted from the same hand-specimens. We found an offset of nearly ca. 1.5 Gyr between U-Pb ages derived from the oldest zircon cores and apatite U–Pb/Sm–Nd isotopic ages, and an offset of ca. 200 Ma between the youngest zircon metamorphic overgrowths and apatite. These differences in metamorphic ages recorded by zircon and apatite mean that the redistribution of Hf isotopes (largely hosted in zircon) and Nd isotopes (largely hosted in apatite within these rocks), were not synchronous at the hand-specimen scale (≤~0.001 m3). We propose that the diachronous redistribution of Hf and Nd isotopes and their parent isotopes was caused by the different PT conditions of growth equilibration between zircon and apatite during metamorphism. These findings document the latest metamorphic evolution of the Saglek Block, highlighting the role played by intra-crustal reworking during the late-Archean regional metamorphic event. [ABSTRACT FROM AUTHOR]

Over 100 new Nd isotope analyses for the central Grenville Province in the Parent-Clova region of Quebec help fill a major gap in understanding the crustal accretion history of the province. Nd model ages show that the Parent-Clova region consists of three crustal blocks: the Archean parautochthon in the north; a central block with mixed ages interpreted as an ensialic arc; and a southerly block forming an extension of the Mesoproterozoic Quebecia arc terrane. The Allochthon Boundary Thrust is believed to define the edge of the Archean parautochthon, which is bordered for a distance of 300 km by the ensialic arc block, within which model ages decrease consistently away from the craton. A similar negative correlation between Nd model age and distance from the craton is seen in published data for the Algonquin terrane in Ontario, but with a lower range of model ages. These comparisons show that in the Parent-Clova region, a Mesoproterozoic ensialic arc was established directly on the Archean margin, but further west, the Mesoproterozoic arc was built on a younger margin consisting of accreted Palaeoproterozoic arc crust. The use of large Nd data sets allows these distinct regional growth patterns to become clear and, hence, allows an understanding of Mesoproterozoic crustal evolution in the province as a whole. [ABSTRACT FROM AUTHOR]

This study investigates the magnitude and direction of stable C and H isotope shifts of n-C15–30 alkanes from biodegraded oils sourced from Type II (Oil suite S) and Type II/III (Oil suite H) kerogens. Compound-specific isotope data show a 2.0‰ 13C-enrichment and no D-enrichment of n-alkanes in the most biodegraded oil from sample suite S. Similarly, there is a 1.5–2.5‰ 13C-enrichment and no D-enrichment in Oil suite H. Overall, there is a <2.5‰ δ13C and <20‰ δD variability among individual n-alkanes in the whole sequence of biodegradation. N-alkanes from the least biodegraded Oil H samples are 2–4‰ 13C-enriched in comparison with the least biodegraded Oil S. However, there are no differences in the δD values of n-alkanes in these samples. Our indirect isotopic evidence suggests (1) a site-specific biodegradation process, most likely at position C-2 and/or C-3 or another site-specific process, and (2) a significant D/H exchange between organic compounds in the source rock and isotopically similar marine formation waters. We conclude that, unlike δD methodology, investigation of δ13C composition of n-alkanes has strong potential as a supplementary tool for oil–oil and oil–source-rock correlation even in biodegraded oils when n-alkanes are present. [ABSTRACT FROM AUTHOR]

Martian meteorites provide the only direct constraints on the timing of Martian accretion, core formation, magmatic differentiation, and ongoing volcanism. While many radiogenic isotope chronometers have been applied to a wide variety of Martian samples, few, if any, techniques are immune to secondary effects from alteration and terrestrial weathering. This short review focuses on the most robust geochronometers that have been used to date Martian meteorites and geochemically model the differentiation of the planet, including 147Sm/143Nd, 146Sm/142Nd, 176Lu/176Hf, 182Hf/182W, and U-Th-Pb systematics. [ABSTRACT FROM AUTHOR]

Loess-paleosol series are well preserved in the south part of the Russian Plain. However, these sequences have a low number of studies on their organic matter, such as researches of isotope composition, n-alkane and other biomarkers. Thus, the purpose of the study was to reconstruct vegetation conditions from the Late Glacial to Late Holocene. We used the leaf wax-derived n-alkanes to detect vegetation evolution of the Bryansk Region. The stable carbon isotope composition of organic matter and pedogenic carbonates was carried out for the same aim. Three paleosols (of Lasko, Bølling-Allerød warmings and Holocene second humus horizons) and modern soils of different relief positions were investigated. n-Alkane distribution, as well as isotope composition indicates changes from grassy to woody vegetation during this period. The use of biomarkers such as n-alkanes helps to more clearly interpret isotopic data. [ABSTRACT FROM AUTHOR]

The behaviour of bioavailable trace metals and their stable isotopes in the modern oceans is controlled by uptake into phototrophic organisms and adsorption on and incorporation into marine authigenic minerals. Among other bioessential metals, Cd and its stable isotopes have recently been used in carbonate lithologies as novel tracer for changes in the paleo primary productivity and (bio)geochemical cycling. However, many marine sediments that were deposited during geologically highly relevant episodes and which, thus, urgently require study for a better understanding of the paleo environment are rather composed of a mixture of organic matter (OM), and detrital and authigenic minerals. In this study, we present Cd concentrations and their isotopic compositions as well as trace metal concentrations from sequential leachates of OM-rich shales of the Cryogenian basal Datangpo Formation, Yangtze Platform (South China). Our study shows variable distribution of conservative and bioavailable trace metals as well as Cd isotope compositions between sequential leachates of carbonate, OM, sulphide, and silicate phases. We show that the Cd isotope compositions obtained from OM leachates can be used to calculate the ambient Cryogenian surface seawater of the restricted Nanhua Basin by applying mass balance calculations. By contrast, early diagenetic Mn carbonates and sulphides incorporated the residual Cd from dissolved organic matter that was in isotopic equilibrium with deep/pore waters of the Nanhua Basin. Our model suggests that the Cd isotopic composition of surface seawater at that time reached values of modern oxygenated surface oceans. However, the deep water Cd isotope composition was substantially heavier than that of modern fully oxygenated oceans and rather resembles deep waters with abundant sulphide precipitation typical for modern oxygen minimum zones. This argues for incomplete recycling of Cd and other bioavailable metals shortly after the Sturtian glaciation in the redox stratified Cryogenian Nanhua Basin. Our study highlights the importance of sequential leaching procedures when dealing with impure authigenic sediments such as OM-rich carbonates, mudstones, or shales to achieve reliable trace metal concentrations and Cd isotope compositions as proxies for (bio)geochemical metal cycling in past aquatic systems. [ABSTRACT FROM AUTHOR]

Mountain-block groundwater in the Southern Basin-and-Range Province shows a variety of patterns of δ18O and δ2H that indicate multiple recharge mechanisms. At 2420 m above sea level (masl) in Tucson Basin, seasonal amount-weighted means of δ18O and δ2H for summer are −8.3, −53‰, and for winter, −10.8 and −70‰, respectively. Elevation-effect coefficients for δ18O and δ2H are as follows: summer, −1.6 and −7.7 ‰ per km and winter, −1.1 and −8.9 ‰ per km. Little altitude effect exists in 25% of seasons studied. At 2420 masl, amount-weighted monthly averages of δ18O and δ2H decrease in summer but increase in winter as precipitation intensity increases. In snow-banks, δ18O and δ2H commonly plots close to the winter local meteoric water line (LMWL). Four principal patterns of (δ18O, δ2H) data have been identified: (1) data plotting along LMWLs for all precipitation at >1800 masl; (2) data plotting along modified LMWLs for the wettest 30% of months at <1700 masl; (3) evaporation trends at all elevations; (4) other patterns, including those affected by ancient groundwater. Young, tritiated groundwater predominates in studied mountain blocks. Ancient groundwater forms separate systems and mixes with young groundwater. Recharge mechanisms reflect a complex interplay of precipitation season, altitude, precipitation intensity, groundwater age and geology. Tucson Basin alluvium receives mountain-front recharge containing 50%–90% winter precipitation. [ABSTRACT FROM AUTHOR]

The thermal waters produced by wells and springs from the Buda Thermal Karst in Budapest and its surroundings are rich in dissolved sulphate. Radiocarbon ages indicate that waters of T >45 ℃ were infiltrated during the Ice Age (more than 11 thousand years ago), on the higher elevations of the Buda-Pilis Hills, whereas waters of lower temperatures were infiltrated during the Holocene. For the origin of dissolved sulphate, two hypotheses can be set up: (1) the dissolved sulphate originates from the oxidation of the sulphide (pyrite) of Oligocene Clay Formation; (2) it is the dissolution product of the sulphate minerals (gypsum and anhydrite) of older carbonaceous rocks (limestone and dolomite). The isotopically stable sulphur composition of the dissolved sulphate in the thermal water (δ34S = 9.7‰ to 17.7‰) indicates its marine origin, so likely it dissolved from the older Permian evaporites. [ABSTRACT FROM AUTHOR]

The cycling of copper (Cu) and its isotopes in the modern ocean is controlled by the interplay of biology, redox settings, and organic complexation. To help build a robust understanding of Cu cycling in the modern ocean and investigate the potential processes controlling its behavior in the geological past, this study presents Cu abundance and isotope data from modern Peru Margin sediments as well as from a suite of ancient, mostly organic-rich, shales. Analyses of an organic-pyrite fraction extracted from bulk modern sediments suggest that sulphidation is the main control on authigenic Cu enrichments in this setting. This organic-pyrite fraction contains, in most cases, >50% of the bulk Cu reservoir. This is in contrast to ancient samples, for which a hydrogen fluoride (HF)-dissolvable fraction dominates the total Cu reservoir. With <20% of Cu found in the organic-pyrite fraction of most ancient sediments, interpretation of the associated Cu isotope composition is challenging, as primary signatures may be masked by secondary processes. But the Cu isotope composition of the organic-pyrite fraction in ancient sediments hints at the potential importance of a significant Cu(I) reservoir in ancient seawater, perhaps suggesting that the ancient ocean was characterized by different redox conditions and a different Cu isotope composition to that of the modern ocean. [ABSTRACT FROM AUTHOR]

Conversion of native grasslands to agricultural sites has resulted in remarkable changes in soil carbon at depth, but its impact on soil diagnostic horizons is unknown. This study was conducted to radiocarbon date the soil organic carbon (SOC) and quantify pedogenic carbonates in the Russian Chernozem at depth at three sites: a native grassland field (not cultivated for at least 300 years), an adjacent 50-year continuous fallow field in the V.V. Alekhin Central-Chernozem Biosphere State Reserve in the Kursk region of Russia (UNESCO—MAB Biosphere Reserve), and a cropland in the Experimental Station of the Kursk Institute of Agronomy and Soil Erosion Control. All sampled soils were classified as Fine-silty, mixed, frigid Pachic Hapludolls (Haplic Chernozem). The radiocarbon age (14C date, y BP) of SOC was highly variable: in the native grassland field, it varied from post-bomb (A-horizon) to 8011 ± 54 y BP (C-horizon); in the continuous fallow, it varied from 1569 ± 41 y BP (Ap-horizon) to 11,380 ± 180 y BP (C1-horizon); and in the cropland, it varied from 1055 ± 38 y BP (Ap-horizon) to 11,805 ± 68 y BP (Ck-horizon). Cultivation resulted in morphological/diagnostic changes in the soil profile (conversion of A to Ap; conversion of Bw to Bk horizon) over a 50-year period. These changes are supported by radiocarbon dating of SOC and pedogenic carbonate distribution within the soil profile. The proportion of pedogenic carbonates was highly variable: in the native grassland, it was 27% (C-horizon); in the continuous fallow, it varied from 53% (Bk1-horizon) to 72% (C2-horizon); and in the cropland, it varied from 85% (A-horizon) to 10% (Ck-horizon). The radiocarbon age differences with depth among the soils reflect changes in the soil carbon dynamics resulting from cultivation. [ABSTRACT FROM AUTHOR]

The Hf-Nd isotope systems are coupled in magmatic systems, but incongruent Hf weathering (‘zircon effect’) of the continental crust leads to a decoupling of the Hf-Nd isotope systems in low-temperature environments during weathering and erosion processes. The Hf-Nd isotope record was recently dated back from the Cenozoic oceans until the Archean, showing that both isotope systems were already decoupled in seawater 2.7 Ga ago and potentially 3.4 Ga and 3.7 Ga ago. While there might have existed a hydrothermal pathway for Hf into Archean seawater, incongruent Hf weathering of more evolved, zircon-bearing uppermost continental crust that was emerged and available for subaerial weathering accounts for a significant decoupling of Hf-Nd isotopes in the dissolved (<0.2 µm) and suspended (>0.2 µm) fractions of Early Earth’s seawater. These findings contradict the consensus that uppermost Archean continental crust was (ultra)mafic in composition and predominantly submerged. Hence, Hf-Nd isotopes in Archean marine chemical sediments provide the unique potential for future research to trace the emergence of evolved continental crust, which in turn has major implications for the geodynamical evolution of Early Earth and the nutrient flux into the earliest marine habitats on Earth. [ABSTRACT FROM AUTHOR]

New whole-rock lead (Pb) isotope analyses are presented in this study for granitoid orthogneisses from the Southwest Grenville Province in Ontario and Western Quebec. These data are used to test the location of a cryptic Archean-Proterozoic suture proposed on the basis of neodymium (Nd) isotope mapping. Immediately south of the inferred suture boundary, Pb isotope results show a crustal component derived solely from a juvenile Paleoproterozoic mantle source. These data are distinctly different from the reworked Archean craton to the northwest and strongly support the boundary derived from Nd isotope data. Pb signatures in the Paleoproterozoic crust suggest a southerly increase in magmatic reworking due to intensive plutonism during the late Paleoproterozoic and early Mesoproterozoic periods. The accretion of a juvenile arc to the Archean margin during the Penokean event (ca. 1.85 Ga) would have triggered subduction-zone reversal and the development of a long-lived ensialic arc on the composite margin. This was expressed as a 1.75 Ga Killarnian magmatic event and subsequent early Mesoproterozoic magmatism. This tectonic model for the Southwest Grenville Province shows that its crustal evolution is consistent with the Paleoproterozoic Makkovik-Ketilidian Orogen of Labrador and Southern Greenland. Hence, the application of whole-rock Pb isotope data in conjunction with Nd model ages provides data useful for mapping the extent of crustal terranes of differing age, which is essential for modeling the tectonic evolution of complex ancient accretionary orogens. [ABSTRACT FROM AUTHOR]