The presence of ^(146)Sm in the early solar system and implications for its nucleosynthesis

The presence of the p-process nucleus ^(146)Sm (mean life, r = 149 x 10^6 yr) in the early solar system and its in situ ɑ-decay into ^(142)Nd is demonstrated by the correlation of ^(142)Nd/^(144)Nd with ^(144)Sm/^(144)Nd in two meteorites which have a large range in ^(144)Sm/^(144)Nd in their constituent mineral phases. Clear excesses of ^(142)Nd/^(144)Nd, relative to the solar system value, are present in high Sm/Nd phases and a clear deficit of ^(142)Nd/^(144)Nd is observed in one sample with low Sm/Nd. The inferred abundance of ^(146)Sm/^(144)Sm is 0.008 at the time of the last equilibration of each meteorite at 4.47 AE ago, which yields ^(146)Sm/^(144)Sm ~0.015 at the time of formation of the solar system, 4.56 AE ago. These results confirm the presence of ^(146)Sm and provide a well defined initial abundance for ^(146)Sm. The abundance of ^(146)Sm is compatible with the p-process production rate estimates but not with the production rate for ^(146)Sm based on a photodisintegration model for the production of p-process nuclides

Monitoring Stray Natural Gas in Groundwater With Dissolved Nitrogen. An Example From Parker County, Texas

Concern that hydraulic fracturing and natural gas production contaminates groundwater requires techniques to attribute and estimate methane flux. Although dissolved alkane and noble gas chemistry may distinguish thermogenic and microbial methane, low solubility and concentration of methane in atmosphereâ equilibrated groundwater precludes the use of methane to differentiate locations affected by high and low flux of stray methane. We present a method to estimate stray gas infiltration into groundwater using dissolved nitrogen. Due to the high concentration of nitrogen in atmosphericâ recharged groundwater and low concentration in natural gas, dissolved nitrogen in groundwater is much less sensitive to change than dissolved methane and may differentiate groundwater affected high and low flux of stray natural gas. We report alkane and nitrogen chemistry from shallow groundwater wells and eight natural gas production wells in the Barnett Shale footprint to attribute methane and estimate mixing ratios of thermogenic natural gas to groundwater. Most groundwater wells have trace to nondetect concentrations of methane. A cluster of groundwater wells have greater than 10 mg/L dissolved methane concentrations with alkane chemistries similar to natural gas from the Barnett Shale and/or shallower Strawn Group suggesting that localized migration of natural gas occurred. Twoâ component mixing models constructed with dissolved nitrogen concentrations and isotope values identify three wells that were likely affected by a large influx of natural gas with gas:water mixing ratios approaching 1:5. Most groundwater wells, even those with greater than 10â mg/L methane, have dissolved nitrogen chemistry typical of atmosphereâ equilibrated groundwater suggesting natural gas:water mixing ratios smaller than 1:20.Plain Language SummaryHydraulic fracturing, horizontal drilling, and associated natural gas production have dramatically changed the energy landscape across America over the past 10 years. Along with this renaissance in the energy sector has come public concern that hydraulic fracturing may contaminate groundwater. In this study we measure the chemistry of dissolved gas from shallow groundwater wells located above the Barnett Shale natural gas play, a tight gas reservoir located west of the Dallasâ Fort Worth Metroplex. We compare groundwater chemistry results to natural gas chemistry results from nearby production wells. Most groundwater wells have trace to nondetectible concentrations of methane, consistent with no measurable infiltration of natural gas into shallow groundwater. A cluster of groundwater wells have greater than 10 mg/L dissolved methane concentrations with alkane chemistries similar to natural gas. Using dissolved nitrogen and alkane concentrations and their stable isotope ratios in combination with chemical mixing models, we conclude that natural gas transported from the shallower Strawn Group affected these groundwater wells rather than natural gas from the deeper Barnett Shale, which is the target of hydraulic fracturing in this area. These results suggest that hydraulic fracturing has not affected shallow groundwater drinking sources in this area.Key PointsDissolved nitrogen in groundwater provides a means to differentiate highâ and lowâ flux infiltration of stray gasNitrogen concentrations and isotope values may attribute natural gas sourcesPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/146362/1/wrcr23523.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/146362/2/wrcr23523_am.pd

Nicoya Peninsula, Costa Rica: A single suite of Caribbean oceanic plateau magmas

The pre‐Tertiary oceanic crust exposed on the west coast of Costa Rica has been broadly referred to as the Nicoya Complex. This study was designed to determine the age of the Nicoya Complex in the Nicoya Peninsula, Playa Jacó, and the Quepos Peninsula using 40Ar‐39Ar radiometric dating and to assess the petrologic relationships between the different localities using major element, trace element, and Sr, Nd, Pb isotopic data. Radiometric ages of basalts and diabases from the Nicoya Peninsula are 88–90 Ma (with a weighted mean of 88.5 Ma), and those of two intrusive rocks (a gabbro and plagiogranite) are both 83–84 Ma. The combined geochemical data indicate that the sampled Nicoya Peninsula rocks belong to a single suite related by fractional crystallization of similar parental magmas. Nd and Pb isotopic ratios indicate a common mantle source distinct from that of mid‐ocean ridge basalts. Both the age and composition of the Nicoya rocks are consistent with the idea that they are a part of the Caribbean Cretaceous oceanic plateau [Donnelly, 1994]. The Jacó lavas are geochemically similar to the Nicoya Peninsula suite, and a single age of 84 Ma is identical to the age of the Nicoya Peninsula intrusives. The one analyzed Quepos basalt has a radiometric age of ∼64 Ma, and it is enriched in incompatible elements relative to the Nicoya rocks. Similarities in Nd and Pb isotopic ratios indicate that the Quepos and Nicoya/Jacó lavas were derived from a similar mantle source to that which produced the Nicoya rocks, possibly the Galapagos plume

A Critical Review of State-of-the-Art and Emerging Approaches to Identify Fracking-Derived Gases and Associated Contaminants in Aquifers

High-volume, hydraulic fracturing (HVHF) is widely applied for natural gas and oil production from shales, coals, or tight sandstone formations in the United States, Canada, and Australia, and is being widely considered by other countries with similar unconventional energy resources. Secure retention of fluids (natural gas, saline formation waters, oil, HVHF fluids) during and after well stimulation is important to prevent unintended environmental contamination, and release of greenhouse gases to the atmosphere. Here, we critically review state-of-the-art techniques and promising new approaches for identifying oil and gas production from unconventional reservoirs to resolve whether they are the source of fugitive methane and associated contaminants into shallow aquifers. We highlight future research needs and propose a phased program, from generic baseline to highly specific analyses, to inform HVHF and unconventional oil and gas production and impact assessment studies. These approaches may also be applied to broader subsurface exploration and development issues (e.g., groundwater resources), or new frontiers of low-carbon energy alternatives (e.g., subsurface H2 storage, nuclear waste isolation, geologic CO2 sequestration)

Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism

Insights into mantle composition and mantle melting beneath mid-ocean ridges from postspreading volcanism on the fossil Galapagos Rise

New major and trace element and Sr, Nd, and Pb isotope data, together with 39Ar-40Ar ages for lavas from the extinct Galapagos Rise spreading center in the eastern Pacific reveal the evolution in magma compositions erupted during slowdown and after the end of active spreading at a mid-ocean ridge. Lavas erupted at 9.2 Ma, immediately prior to the end of spreading are incompatible element depleted mid-ocean ridge tholeiitic basalts, whereas progressively younger (7.5 to 5.7 Ma) postspreading lavas are increasingly alkalic, have higher concentrations of incompatible elements, higher La/Yb, K/Ti, 87Sr/86Sr, and lower 143Nd/144Nd ratios and were produced by smaller degrees of mantle melting. The large, correlated variations in trace element and isotope compositions can only be explained by melting of heterogenous mantle, in which incompatible trace element enriched lithologies preferentially contribute to smaller degree mantle melts. The effects of variable degrees of melting of heterogeneous mantle on lava compositions must be taken into account when using mid-ocean ridge basalt (MORB) to infer the conditions of melting beneath active spreading ridges. For example, the stronger “garnet signature” inferred from Sm/Nd and 143Nd/144Nd ratios for postspreading lavas from the Galapagos Rise results from a larger contribution from enriched lithologies with high La/Yb and Sm/Yb, rather than from a greater proportion of melting in the stability field of garnet peridotite. Correlations between ridge depth and Sm/Yb and fractionation-corrected Na concentrations in MORB worldwide could result from variations in mantle fertility and/or variations in the average degree of melting, rather than from large variations in mantle temperature. If more fertile mantle lithologies are preferentially melted beneath active spreading ridges, then the upper mantle may be significantly more “depleted” than is generally inferred from the compositions of MORB

Gas Isotopes Tracing: an Important Tool for Hydrocarbons Exploration

Gas may be considered today both as a reliable tracer for the understanding of associated liquid hydrocarbons and as an economic target. Isotopic measurements of stables isotopes and noble gases give important clues to reconstruct the geological history of hydrocarbons from their generation to their accumulation. Recent analytical advances in carbon isotopes of natural gases (methane to butane and carbon dioxide) duemainly to the development of GC-C-IRMS (Gas Chromatograph-Combustion-Isotopic ratios mass spectrometer) have allowed to reconstruct some of the physico-chemical processes which affect naturalgas chemical signatures, instead of using these signatures as simple fingerprinting of origins as it was the case some time ago. These reconstructions provide important information on both the origins and the dynamic behavior of hydrocarbon fluids between the source rocks and the accumulations in reservoirs. Correlating this methodology with other natural tracers increases the understanding of hydrocarbon history in sedimentary basins. Among other new potential methodologies, noble gas coupled to stable isotopes are the new frontier tool, as their chemical inertia enables their use as precise tracers of sources and of associated physical processes (state of the phases, migration and leakage). Moreover, because some isotopes (4He, 40Ar for example) are produced by natural radioactivity, they may very well represent geological "clocks", giving potentially a quantification of the residence times of hydrocarbons in a reservoir. Several new applications of this association of stable isotopes and noble gases are presented in this paper: a new way for distinguishing bacterial and thermogenic gas origins, and the characterization of the parameters related to the genesis of thermogenic gas (primary versus secondary cracking, openness of the system, relations between gas isotope signatures and biodegradation). At last is presented a tentative quantification of the proportion of hydrocarbon gases leaked from a reservoir, and a quantitative relative residence times of hydrocarbons in heterogeneous reservoirs

Reconsideration of Methane Isotope Signature As a Criterion for the Genesis of Natural Gas: Influence of Migration on Isotopic Signatures Reconsidération de la signature isotopique du méthane comme critère pour la genèse du gaz naturel : influence de la migration sur les signatures isotopiques

Experiments were performed in the purpose of studying the isotopic consequences of the diffusional transport of hydrocarbon gases through sediment rocks. Linked to a numerical model, these gas diffusion experiments through a shale porous plug allowed us to correlate porosity and diffusivity of the migration medium. Significant isotopic fractionations (carbon and hydrogen) of methane, and ethane at a lesser degree were observed. This is in contradiction with the actual dogma of isotope geochemistry of natural gases which claims that no fractionation occurs during gas migration. The genetic characterization of natural gases by using the isotopic signature of methane appears as an ambiguous method. Plusieurs expériences ont été réalisées dans le but d'étudier les conséquences isotopiques du transport par diffusion des gaz hydrocarbures au travers des roches sédimentaires. Associées à un modèle numérique, ces expériences de diffusion au travers d'une membrane d'argile reconstituée nous ont permis de corréler deux paramètres pétrophysiques du milieu de migration : la porosité et la diffusivité. D'importants fractionnements isotopiques ont été observés au cours de la diffusion du méthane et, à plus petite échelle, lors de la diffusion de l'éthane. Ces résultats remettent en cause le dogme actuel de la géochimie isotopique des gaz naturels qui stipule que la migration des gaz ne peut induire de fractionnements isotopiques. En conséquence, les méthodes de caractérisation génétique des gaz naturels utilisant la signature isotopique du méthane apparaissent comme insuffisantes

Identification and Quantification of Carbonate Species Using Rock-Eval Pyrolysis

This paper presents a new reliable and rapid method to characterise and quantify carbonates in solid samples based on monitoring the CO2 flux emitted by progressive thermal decomposition of carbonates during a programmed heating. The different peaks of destabilisation allow determining the different types of carbonates present in the analysed sample. The quantification of each peak gives the respective proportions of these different types of carbonates in the sample. In addition to the chosen procedure presented in this paper, using a standard Rock-Eval 6 pyrolyser, calibration characteristic profiles are also presented for the most common carbonates in nature. This method should allow different types of application for different disciplines, either academic or industrial