Vienna Pee Dee Belemnite Research Articles

Mineralization of autochthonous particulate organic carbon is a fast channel of organic matter turnover in Germany's largest drinking water reservoir

Abstract. Turnover of organic matter (OM) is an essential ecological function in inland water bodies and relevant for water quality. This is especially important for the potential of dissolved organic carbon (DOC) removal as well as for emissions of CO2. In this study, we investigated various phases of OM including DOC, autochthonous particulate organic carbon (auto-POC), allochthonous particulate organic carbon (allo-POC), and sedimentary matter (SED) in a temperate drinking water reservoir (Rappbode Reservoir, Germany) by means of dissolved inorganic carbon (DIC) concentrations and carbon stable isotope ratios. In order to best outline carbon turnover, we focused on the metalimnion and the hypolimnion of the reservoir, where respiration is expected to be dominant and hardly disturbed by atmospheric exchange or photosynthesis. DIC concentrations ranged between 0.30 and 0.53 mmol L−1, while δ13CDIC values ranged between −15.1 ‰ and −7.2 ‰ versus the VPDB (Vienna PeeDee Belemnite) standard. Values of δ13CDOC and δ13Cauto-POC ranged between −28.8 ‰ and −27.6 ‰ and between −35.2 ‰ and −26.8 ‰, respectively. Isotope compositions of sedimentary material and allochthonous POC were inferred from the literature and from measurements from previous studies with δ13CSED=-31.1 ‰ and δ13Callo-POC ranging from −31.8 ‰ to −28.6 ‰. Comparison of DIC concentration gains and stable isotope mass balances showed that auto-POC from primary producers was the main contributor to increases in the DIC pool. Calculated OM turnover rates (0.01 to 1.3 µmol L−1 d−1) were within the range for oligotrophic water bodies. Some higher values in the metalimnion are likely due to increased availability of settling auto-POC from the photic zone. Samples from a metalimnetic oxygen minimum (MOM) also showed dominance of respiration over photosynthesis. Our work shows that respiration in temperate lentic water bodies largely depends on auto-POC production as a major carbon source. Such dependencies can influence the vulnerabilities of these aqueous systems.

Geochemistry of the Neoarchean Dodguni carbonates of Chitradurga greenstone belt, Dharwar Craton, India: Implications on depositional environment

The carbonates of the Dodguni area of the Chitradurga greenstone belt, Dharwar Craton, India were studied to understand the Archean diagenetic and palaeo‐depositional conditions using carbon and oxygen isotopes along with whole‐rock geochemistry. These carbonates show significant variation in δ13C and δ18O (−1.73‰ Vienna Peedee Belemnite [VPDB] to −0.45‰ VPDB and δ18O vary from −13.51‰ VPDB to −8.46‰ VPDB, respectively). The rare earth element (REE) + Y (rare earth elements and yttrium) of the studied carbonate rocks exhibit flat and uniform patterns (PrSN/YbSN = 0.4–1), slight positive La, Eu and Gd anomalies (CeSN/CeSN* = 0.8–0.9; EuSN/EuSN* = 0.7–1.4 and GdSN/GdSN* = 2–2.3, respectively) with slight positive Ce anomalies (PrSN/PrSN* = 0.84–0.86) and superchondritic Y/Ho ratios (Y/Ho = 29–45; chondritic Y/Ho = 28). Their negative δ13C (−1.75‰ to −0.45‰) values are attributed to the influence of higher bio‐productivity during their deposition and oxidation of organic carbon. The geochemical and isotopic systematics suggest that the Dodguni limestones are not affected by the diagenetic and metamorphic processes and record the REE geochemistry of the ancient seawater in which they were precipitated. The comprehensive geochemical including the isotopic studies of the Archean carbonate rocks of the Dharwar Craton, indicate their deposition in shallow marine conditions, precipitation in high temperatures with significant hydrothermal input under the influence of high bio‐productivity, thereby providing valuable constraints on the palaeoceanography and geochemical evolution of the Archean sea.

Characterization of vanillin carbon isotope delta reference materials

Stable carbon isotope ratio measurements are used to investigate the provenance of vanillin. In this study, a variety of commercial vanillin samples and vanilla products were analyzed to provide a frame of reference for the variability of carbon isotope delta values in various vanillin samples, with the results ranging from −20.6 to −36.7‰ relative to the Vienna Peedee Belemnite (VPDB). We present information on the development of two synthetic vanillin reference materials, VANA-1 and VANB-1, prepared in 0.75 g units in glass vials, to be used for the calibration of carbon isotope delta measurements of vanillin and other easily combustible organic materials. Characterization of 40 vials each of VANA-1 and VANB-1 was performed by three laboratories over several measurement sequences. The certified carbon isotope delta values are −31.30 ± 0.06‰ (VANA-1) and −25.85 ± 0.05‰ (VANB-1). These uncertainties, for the 95% confidence level, include considerations for measurement uncertainty, coherence of the reference materials used for calibration, batch homogeneity, and stability during storage and transportation. The results are traceable to the VPDB through a set of nine reference materials (IAEA-CH-6, USGS65, IAEA-600, NBS22, USGS61, IAEA-603, IAEA-610, IAEA-611, and IAEA-612). For up to date certified values, users should refer to doi.org/10.4224/crm.2022.vana-1 and doi.org/10.4224/crm.2022.vanb-1.

Nature and evolution of diagenetic fluids in the deeply buried Cambrian Xiaoerbulake Formation, Tarim Basin, China

Significant amounts of petroleum are found in the deeply buried Cambrian Xiaoerbulake Formation in the Tarim Basin. However, limited understanding of origin of diagenetic fluids hampers petroleum exploration. In this study, petrological and high-resolution geochemical methods have been performed to understand the origin and evolution of diagenetic fluids, and their effects on the formation of dolostone reservoir. The Xiaoerbulake Formation is characterised by microbialites. The matrix is characterised by modern seawater-like rare earth element and yttrium (REY) patterns and δ18O values of −6.02 ± 2.11‰ Vienna Pee Dee Belemnite (VPDB). Fine-crystalline dolomite cements have similar δ13C values and heavy rare earth element enrichment patterns to that of matrix dolomite, yet with lower δ18O values of −7.47 ± 1.2‰ VPDB. In the deep-burial regimes, medium- to coarse-crystalline dolomite cements and saddle dolomites were precipitated at temperatures of 90–120 and 130–190 °C, respectively, lower δ18O values, distinct middle rare earth element enrichment, and high Fe and Mn contents compared with matrix and fine-crystalline dolomite cements. These imply thermochemical reduction of Fe- or Mn-rich oxides and/or hydrothermal fluids. Compared with other types of dolomite cements, calcite cements are characterised by low δ13C values (as low as −6‰ VPDB), light rare earth elements enrichment and significantly elevated Y/Ho ratios (86 ± 59.3), likely related to the oxidation of organic matter during thermochemical sulfate reduction (TSR). Consequently, diagenetic fluid may have evolved from: Cambrian seawater, meteoric water, shallow-buried seawater-dominated pore water, medium-deep-buried ferrous-rich pore water, lately high-salinity hydrothermal fluid-dominated pore water and finally to acidic fluids related to TSR dissolution. Reservoir quality is enhanced by hydrothermal pulses and TSR in deep-burial settings. This study is significant for those concerned with the formation of deep-buried carbonate reservoirs.

Site-specific carbon isotope measurements of vanillin reference materials by nuclear magnetic resonance spectrometry

Vanillin, one of the world’s most popular flavor used in food and pharmaceutical industries, is extracted from vanilla beans or obtained (bio)-synthetically. The price of natural vanillin is considerably higher than that of its synthetic alternative which leads increasingly to counterfeit vanillin. Here, we describe the workflow of combining carbon isotope ratio combustion mass spectrometry with quantitative carbon nuclear magnetic resonance spectrometry (13C-qNMR) to obtain carbon isotope measurements traceable to the Vienna Peedee Belemnite (VPDB) with 0.7‰ combined standard uncertainty (or expanded uncertainty of 1.4‰ at 95% confidence level). We perform these measurements on qualified Bruker 400 MHz instruments to certify site-specific carbon isotope delta values in two vanillin materials, VANA-1 and VANB-1, believed to be the first intramolecular isotopic certified reference material (CRMs).Graphical abstract

Ames-2021 CO2 Dipole Moment Surface and IR Line Lists: Toward 0.1% Uncertainty for CO2 IR Intensities.

A highly accurate CO2 ab initio dipole moment surface (DMS), Ames-2021, is reported along with 12C16O2 infrared (IR) intensity comparisons approaching a 1-4‰ level of agreement and uncertainty. The Ames-2021 DMS was accurately fitted from CCSD(T) finite-field dipoles computed with the aug-cc-pVXZ (X = T, Q, 5) basis for C atom and the d-aug-cc-pVXZ (X = T, Q, 5) basis for O atoms, and extrapolated to the one particle basis set limit. Fitting σrms is 3.8 × 10-7 au for 4443 geometries below 15 000 cm-1. The corresponding IR intensity, SAmes-2021, are computed using the Ames-2 potential energy surface (PES), which is the best PES available for CO2. Compared to high accuracy IR studies for 2001i-00001 and 3001i-00001 bands, SAmes-2021 matches NIST experiment-based intensities [SNIST-HIT16 or SHIT20] to -1.0 ± 1.3‰, or matches DLR experiment-based intensities [SDLR-HIT16/UCL/Ames] to 1.9 ± 3.7‰. This indicates the systematic deviations and uncertainties have been significantly reduced in SAmes-2021. The SUCL2015 (or SHITRAN2016) have larger deviations (vs SDLR) and uncertainties (vs SDLR, SNIST) which are attributed to the less accurate Ames-1 PES adopted in UCL-296 line list calculation. The SAmes-2021 intensity of 12C16O2 and 13C16O2 is utilized to derive new absolute 13C/12C ratios for Vienna PeeDee Belemnite (VPDB) with uncertainty reduced by 1/3 or 2/3. Further evaluation of SAmes-2021 intensities are carried out on those CO2 bands discussed in the HITRAN2020 update paper. Consistent improvements and better accuracies are found in band-by-band analysis, except for those bands strongly affected by Coriolis couplings, or very weak bands measured with relatively larger experimental uncertainties. The Ames-2021 296 K IR line lists are generated for 13 CO2 isotopologues, with 18 000 cm-1 and S296K > 1 × 10-31 cm/molecule cutoff and then combined with CDSD line positions (except 14C16O2). The Ames-2021 DMS and 296 K IR line lists represent a major improvement over previous CO2 theoretical IR intensity studies, including Ames-2016, UCL-296, and recent UCL DMS 2021 update. A real 1 permille level of agreement and uncertainty will definitely require both more accurate PES and more accurate DMS.

The Helium and Carbon Isotope Characteristics of the Andean Convergent Margin

Subduction zones represent the interface between Earth’s interior (crust and mantle) and exterior (atmosphere and oceans), where carbon and other volatile elements are actively cycled between Earth reservoirs by plate tectonics. Helium is a sensitive tracer of volatile sources and can be used to deconvolute mantle and crustal sources in arcs; however it is not thought to be recycled into the mantle by subduction processes. In contrast, carbon is readily recycled, mostly in the form of carbon-rich sediments, and can thus be used to understand volatile delivery via subduction. Further, carbon is chemically-reactive and isotope fractionation can be used to determine the main processes controlling volatile movements within arc systems. Here, we report helium isotope and abundance data for 42 deeply-sourced fluid and gas samples from the Central Volcanic Zone (CVZ) and Southern Volcanic Zone (SVZ) of the Andean Convergent Margin (ACM). Data are used to assess the influence of subduction parameters (e.g., crustal thickness, subduction inputs, and convergence rate) on the composition of volatiles in surface volcanic fluid and gas emissions. He isotopes from the CVZ backarc range from 0.1 to 2.6 RA (n = 23), with the highest values in the Puna and the lowest in the Sub-Andean foreland fold-and-thrust belt. Atmosphere-corrected He isotopes from the SVZ range from 0.7 to 5.0 RA (n = 19). Taken together, these data reveal a clear southeastward increase in 3He/4He, with the highest values (in the SVZ) falling below the nominal range associated with pure upper mantle helium (8 ± 1 RA), approaching the mean He isotope value for arc gases of (5.4 ± 1.9 RA). Notably, the lowest values are found in the CVZ, suggesting more significant crustal inputs (i.e., assimilation of 4He) to the helium budget. The crustal thickness in the CVZ (up to 70 km) is significantly larger than in the SVZ, where it is just ∼40 km. We suggest that crustal thickness exerts a primary control on the extent of fluid-crust interaction, as helium and other volatiles rise through the upper plate in the ACM. We also report carbon isotopes from (n = 11) sites in the CVZ, where δ13C varies between −15.3‰ and −1.2‰ [vs. Vienna Pee Dee Belemnite (VPDB)] and CO2/3He values that vary by over two orders of magnitude (6.9 × 108–1.7 × 1011). In the SVZ, carbon isotope ratios are also reported from (n = 13) sites and vary between −17.2‰ and −4.1‰. CO2/3He values vary by over four orders of magnitude (4.7 × 107–1.7 × 1012). Low δ13C and CO2/3He values are consistent with CO2 removal (e.g., calcite precipitation and gas dissolution) in shallow hydrothermal systems. Carbon isotope fractionation modeling suggests that calcite precipitation occurs at temperatures coincident with the upper temperature limit for life (122°C), suggesting that biology may play a role in C-He systematics of arc-related volcanic fluid and gas emissions.

Carbonatite-melilitite-phosphate immiscible melts from the aragonite stability field entrained from the mantle by a Pliocene basalt

A plagioclase megacryst containing composite crystal-glass inclusions was ejected in a Pliocene basaltic diatreme in the Carpathian back-arc basin (Pannonian Basin). The megacryst grew from phonolitic melt, relics of which are preserved in the crystal-glass inclusions. Most of the pristine melt has undergone substantial compositional resetting by interaction with several batches of a low-viscosity carbonated, P-rich melilitite melt, which infiltrated and largely replaced the original inclusion content. The melilitite melt also caused partial resorption of the host megacryst and crystallisation of new calcic plagioclase forming stringers and palisades. A P-rich calcic carbonatite melt exsolved from the melilitite and later crystallised to aragonite at ~ 800 °C and 1.9 GPa. The phosphate melt fraction exsolved from the carbonatite and solidified as CO32−-rich A-B type apatite. At a very late evolutionary stage, K- and Si-rich fluids caused potassic and silicic alteration of the solidified melilitite glass along cracks and interfaces between calcic carbonate globules and glass at temperatures below 680 °C. The oxygen isotope composition of the plagioclase megacryst (6.2 ‰ V-SMOW; Vienna Standard Mean Ocean Water) and the 87Sr/86Sr isotope ratio of carbonates in the inclusions (0.7034) are consistent with a mantle-derived melt. 87Sr/86Sr isotope ratios (0.7047–0.7051) in interstitial carbonates from associated syenite and carbonatite xenoliths indicate a metasomatised mantle source contaminated with radiogenic crustal material or altered marine carbonate. The O-isotope ratios in the carbonates, 22.7 ± 0.6 ‰ V-SMOW in calcite and 23.6 ± 0.7 ‰ V-SMOW in aragonite, are also consistent with a sedimentary precursor. Contrasting δ13C values in the calcite, -12.7 ± 0.5 ‰ V-PDB (Vienna PeeDee Belemnite), and the aragonite (-4.6 ± 0.5 ‰ V-PDB) indicate low-temperature modification of calcite assisted by delta13C-depleted CO2 and preservation of primary magmatic delta13C values in aragonite. The microstructural and geochemical evidence points towards heterogeneous silicate-carbonate melt fractions generated during the metasomatism and partial melting of a supra-subduction mantle wedge.

Absolute Carbon Stable Isotope Ratio in the Vienna Peedee Belemnite Isotope Reference Determined by 1H NMR Spectroscopy.

The Vienna Peedee Belemnite (VPDB) isotope reference defines the zero point of the carbon stable isotope scale that is used to describe the relative abundance of 13C and 12C. An accurate and precise characterization of this isotope reference is valuable for interlaboratory comparisons and conducting robust carbon stable isotope analyses in a vast array of fields, such as chemical forensics, (bio)geochemistry, ecology, or (astro)biology. Here, we report an absolute 13C/12C ratio for VPDB that has been obtained, for the first time, using proton nuclear magnetic resonance spectroscopy (1H NMR). Four different NMR instruments were used to determine 13C/12C ratios in a set of glycine reference materials from the US Geological Survey (USGS64, USGS65, and USGS66) and a set of formate samples that were characterized by isotope ratios mass spectrometry (IRMS). Intercalibration of the NMR-derived 13C/12C ratios with relative abundance (δ13CVPDB) measurements from IRMS yields a value of 0.011100 for the absolute 13C/12C ratio in VPDB, with an expanded uncertainty of ±0.000026 (2σ, n = 114). This is significantly different from the value of 0.011180 that is commonly used but falls within the range of values recently revised using IRMS and infrared absorption measurements. 1H NMR was found to be an effective method for measuring absolute 13C/12C ratios due to its ability to simultaneously detect signals associated with 12C and 13C. Results provide a new and independent measure of the carbon isotope composition of VPDB, improving our understanding of this important isotope reference.

Extensive recrystallization of Cenozoic dolomite during shallow burial: A case study from the Palaeocene–Eocene Umm er Radhuma formation and a global meta‐analysis

AbstractRecrystallization of dolomite can alter textural, mineralogical and geochemical attributes used to infer environmental conditions of initial dolomitization. A meta‐analysis of the published literature shows that extensive recrystallization is most common in old and deeply buried dolomites, but data from the Palaeocene–Eocene Umm er Radhuma Formation in Qatar show that this can also happen in geologically young carbonates that have never been deeply buried. Evidence of extensive recrystallization comes from a principal component analysis of published mineralogical and geochemical data that are integrated with new clumped isotope (∆47) measurements and cathodoluminescence petrography. The observations indicate that dolomite stoichiometry and cation ordering correlate with dolomite texture and depth: shallow mimetic dolomites are less stoichiometric and poorly‐ordered whereas coarser and deeper planar‐e and planar‐s to nonplanar dolomites with mottled cathodoluminescence signatures are more stoichiometric and well‐ordered, suggesting they have recrystallized. Dolomite δ18O data (Vienna Pee Dee Belemnite) also covary with texture, as mimetic dolomites have the narrowest range (−0.45‰ to +0.38‰), planar‐e dolomites are generally ≤0‰ (−2.4‰ to +0.68‰) and planar‐s to nonplanar dolomites exhibit the widest range (−2.3‰ to +1.4‰). The principal component analysis results indicate one component with positive loadings for dolomite stoichiometry (+0.752) and cation ordering (+0.813), and negative loading for δ18O (−0.833), trends predicted in recrystallized dolomites. The ∆47‐derived temperatures (32 to 46°C) and δ18Ow (+0.18 to +2.6‰ Vienna Standard Mean Ocean Water) reflect recrystallization by warm, slightly evaporated seawater at shallow depths. In the context of a meta‐analysis of recrystallized dolomites in the literature, this study implies that extensive dolomite recrystallization in Cenozoic dolomites and shallow‐burial conditions is an under‐appreciated phenomenon. The results of this study also demonstrate that initial petrological attributes can be significantly altered after dolomitization, hindering interpretations of past seawater chemistry and environmental conditions of dolomitization.

Oxygen isotope fractionation in otoliths: experimental results from four North Pacific and Arctic gadid species

High-latitude climate warming is expected to have wide-ranging effects on habitats, ecosystems, and the fish species that occupy them. Not all fish species will be able to adapt to increasing temperatures. We investigated oxygen isotope fractionation in fish otoliths and its relationship to environmental temperature and thermal histories of individual fish. Fish from 4 gadid species, Gadus macrocephalus, Boreogadus saida, Eleginus gracilis, and G. chalcogrammus, representing North Pacific and Arctic regions, were reared in a range of controlled temperatures (0-20°C). We estimated 4 new species-specific otolith oxygen isotope fractionation equations, a relationship between otolith δ18O and temperature (T) in the form δ18Oo - δ18Ow = m × T°C + b and also in a second form using the fractionation factor α: 1000 ln α = a × (1000 TK-1) + c, where o is otolith, w is water, and m, b, a and c are regression coefficients. In using the first form, B. saida was the most unique among the 4 species, with the steepest slope (-0.23) and the highest intercept (32.99‰ Vienna PeeDee Belemnite [VPDB]). G. macrocephalus had the lowest slope (-0.17) and the lowest intercept (31.76‰ [VPDB]). Results of an ANCOVA test indicated that the 4 fractionation equations were not statistically different (F = 2.25, p > 0.087). However, when we applied the 4 new fractionation equations to δ18Oo measured in wild-caught B. saida otoliths, the species-�specific fractionation equation resulted in the closest match between measured and predicted water temperatures. These new fractionation equations represent new tools for investigating temperature effects on fish biota and will also improve paleotemperature reconstruction, especially for high-latitude species.

Geochemical comparison of ikaite and methane-derived authigenic carbonates recovered from Echigo Bank in the Sea of Japan

This study compares the geochemistry of ikaite (CaCO3·6H2O) with that of nearby (< 500 m in distance) recovered methane-derived authigenic carbonates (MDACs) of ~10 mol% Mg-calcite. The carbon isotopic composition (δ13C) of MDACs (lower than −49‰ Vienna Pee Dee Belemnite or VPDB) suggests a more prominent influence of anaerobic oxidation of methane (AOM) than that of ikaite (approximately −35‰ VPDB). The higher δ13C value of ikaite is attributed to its growth at sediment depths closer to the seafloor, where the proportion of seawater HCO3− relative to methane-derived HCO3− was higher. Assuming that seawater and AOM are the major sources of HCO3− for ikaite growth, the actual 14C age was estimated to be ~14 cal ky before present, close to the age of the sediments observed around the ikaite. For alkalinity increase at shallower sediment depths by the AOM, a higher methane flux is necessary. However, attributing the ikaite growth at shallower sediment depths to higher methane flux alone posed an issue, as no traces of gas hydrate growth were found in the laminated sediments. The oxygen isotopic composition (δ18O) of the freeze-dried ikaite (ikaite-CO3) was ~2‐3‰ VPDB, which is lower than the corresponding value of ~4.0‰ VPDB for the Mg-calibrated MDACs. It is characteristic of ikaite-CO3 to exhibit such low δ18O values, indicating a unique oxygen isotope fractionation factor for ikaite. The preferential H218O uptake of ikaite for growth also influenced the δ18O value of ikaite-CO3. Hence, owing to H218O depletion in the ambient interstitial water, the δ18O value of the ikaite-CO3 tended to decrease from the interior to the margin. The δ18O values of the ikaite-CO3 were archived in yellowish calcite grains that were formed in the pores after patchy dissociation of the ikaite. The δ18O values of the grains were close to those of ikaite-CO3. Therefore, the δ18O-temperature equation for ikaite is necessary for geochemical interpretation of the calcite δ18O values.

Helium-carbon systematics of groundwaters in the Lassen Peak Region

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium (3He, 4He) and carbon (12C, 13C, 14C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3He/4He values between 0.19 and 7.44 RA (where RA = air 3He/4He = 1.39 × 10−6), all in excess of the radiogenic production value (~0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ13C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/3He values fall in the range of 2.2 × 1010 to 1.1 × 1012. Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO214C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ13C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/3He between 7.0 × 109 and 1.0 × 1012. These apparent δ13C and C/3He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ13C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 106 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region (Rose and Davisson, 1996). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO2 degassing flux (estimated to be ~3.5 × 107 kg/yr Rose and Davisson, 1996; Gerlach et al., 2008), which is still more than an order of magnitude smaller than soil gas CO2 flux estimates (7.3–11 × 107 kg/yr) for nearby volcanoes (Sorey et al., 1998; Gerlach et al., 1999; Evans et al., 2002; Werner et al., 2014). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ13C and 14C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

Methane (CH&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt;) sources in Krakow, Poland: insights from isotope analysis

Abstract. Methane (CH4) emissions from human activities are a threat to the resilience of our current climate system. The stable isotopic composition of methane (δ13C and δ2H) allows us to distinguish between the different CH4 origins. A significant part of the European CH4 emissions, 3.6 % in 2018, comes from coal extraction in Poland, the Upper Silesian Coal Basin (USCB) being the main hotspot. Measurements of CH4 mole fraction (χ(CH4)), δ13C, and δ2H in CH4 in ambient air were performed continuously during 6 months in 2018 and 2019 at Krakow, Poland, in the east of the USCB. In addition, air samples were collected during parallel mobile campaigns, from multiple CH4 sources in the footprint area of the continuous measurements. The resulting isotopic signatures from sampled plumes allowed us to distinguish between natural gas leaks, coal mine fugitive emissions, landfill and sewage, and ruminants. The use of δ2H in CH4 is crucial to distinguish the fossil fuel emissions in the case of Krakow because their relatively depleted δ13C values overlap with the ones of microbial sources. The observed χ(CH4) time series showed regular daily night-time accumulations, sometimes combined with irregular pollution events during the day. The isotopic signatures of each peak were obtained using the Keeling plot method and generally fall in the range of thermogenic CH4 formation – with δ13C between −59.3 ‰ and −37.4 ‰ Vienna Pee Dee Belemnite (V-PDB) and δ2H between −291 ‰ and −137 ‰ Vienna Standard Mean Ocean Water (V-SMOW). They compare well with the signatures measured for gas leaks in Krakow and USCB mines. The CHIMERE transport model was used to compute the CH4 and isotopic composition time series in Krakow, based on two emission inventories. The magnitude of the pollution events is generally underestimated in the model, which suggests that emission rates in the inventories are too low. The simulated isotopic source signatures, obtained with Keeling plots on each simulated peak, indicate that a higher contribution from fuel combustion sources in the EDGAR v5.0 inventory would lead to a better agreement than when using CAMS-REG-GHG v4.2 (Copernicus Atmosphere Monitoring Service REGional inventory for Air Pollutants and GreenHouse Gases). The isotopic mismatches between model and observations are mainly caused by uncertainties in the assigned isotopic signatures for each source category and the way they are classified in the inventory. These uncertainties are larger for emissions close to the study site, which are more heterogenous than the ones advected from the USCB coal mines. Our isotope approach proves to be very sensitive in this region, thus helping to evaluate emission estimates.

Precise timing of MIS 7 substages from the Austrian Alps

Abstract. Investigating the precise timing of regional-scale climate changes during glacial terminations and the interglacial periods that follow is key to unraveling the mechanisms behind these global climate shifts. Here, we present a high-precision time series of climate changes in the Austrian Alps that coincide with the later portion of Termination III (TIII), the entire penultimate interglacial (Marine Isotope Stage (MIS) 7), Termination IIIa (TIIIa), and the penultimate glacial inception (MIS 7–6 transition). Using state-of-the-art mass spectrometry techniques, we have constructed a uranium-series chronology with relative age uncertainties averaging 1.7 ‰ (2σ) for our study period (247 to 191 thousand years before present, ka). Results reveal the onset of warming in the Austrian Alps associated with TIII at 242.5 ± 0.2 ka and the duration of MIS 7e warming between 241.8 and 236.7 (±0.6) ka. An abrupt shift towards higher δ18O values at 216.8 ka marks the onset of regional warming associated with TIIIa. Two periods of high δ18O values (greater than −10 ‰ Vienna Pee Dee Belemnite (VPDB)) between 215.9–213.3 and 204.3–197.5 (±0.4) ka coincide with interglacial substages MIS 7c and 7a, respectively. Multiple fluorescent inclusions suggest a partial retreat of the local Alpine glacier during peak obliquity forcings at 214.3 ± 0.4 ka. Two newly collected stalagmites from Spannagel Cave (SPA146 and 183) provide high-resolution replications of the latter portion of the MIS 7a-to-6e transition. The resulting multi-stalagmite record reveals important chronological constraints on climate shifts in the Austrian Alps associated with MIS 7 while offering new insight into the timing of millennial-scale changes in the North Atlantic realm leading up to TIII and TIIIa.

Author Correction: Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy

Author Correction: Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy

Dissolution of ooids in seawater‐derived fluids – an example from Lower Permian re‐sedimented carbonates, West Texas, USA

Abstract Selective dissolution of metastable minerals and certain pore types, such as moldic and oomoldic pores, are widely accepted to indicate diagenesis by meteoric fluids in carbonate rocks. In this study, oomoldic‐rich re‐sedimented carbonates from the Happy Field in the Midland Basin, which contain no evidence of subaerial environments, indicate that such pores may form in other settings. Ooid dissolution in the reservoir was evaluated through petrography, scanning electron microscopy, stable isotopes (δ18O and δ13C), elemental geochemistry, and X‐ray diffraction of bioclasts, ooids and associated cements. Cements are primarily dogtooth and equant low‐magnesium calcite, poikilotopic celestine is present, and late‐stage low‐magnesium calcite occurs in lesser amounts. Equant low magnesium calcite cements are interpreted to reflect the initial stages of pore filling, synchronous with aragonitic ooid dissolution, thus implying that oomoldic pores and equant cements formed in similar fluids. Although the prominent equant low magnesium calcite cement textures mimic those often associated with meteoric fluids, geochemistry suggests a marine origin. The equant cements have δ18O (Vienna Pee Dee Belemnite) ratios between −2.0‰ and −3.5‰, and δ13C (Vienna Pee Dee Belemnite) ratios between 4‰ and 5‰. Magnesium/calcium ratios show values, ranging from 5 to 142 mmol/mol (n = 223, average 23.2 and SD = 20.1). Strontium/calcium ratios present values from 0.3 to 2.6 mmol/mol (n = 223, average 0.71 mmol/mol, SD = 0.35). Geochemical data coincide with typical low‐latitude Permian marine carbonate values and further signify diagenesis within the marine phreatic realm. To explain this process, the results indicate that the dissolution of aragonite ooids and precipitation of early cements occurred in environments ranging between the seafloor to shallow burial dominated by undersaturated marine fluids. Undersaturation was triggered by organic matter decomposition occurring at the seafloor and in the shallow subsurface immediately below. These findings have broader implications for marine and burial carbonate diagenesis as well as diagenesis of re‐sedimented deposits.

Simultaneous measurement of &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C, &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O and &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;17&amp;lt;/sup&amp;gt;O of atmospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; – performance assessment of a dual-laser absorption spectrometer

Abstract. Using laser absorption spectrometry for the measurement of stable isotopes of atmospheric CO2 instead of the traditional isotope ratio mass spectrometry method decreases sample preparation time significantly, and uncertainties in the measurement accuracy due to CO2 extraction and isobaric interferences are avoided. In this study we present the measurement performance of a new dual-laser instrument developed for the simultaneous measurement of the δ13C, δ18O and δ17O of atmospheric CO2 in discrete air samples, referred to as the Stable Isotopes of CO2 Absorption Spectrometer (SICAS). We compare two different calibration methods: the ratio method, based on the measured isotope ratio and a CO2 mole fraction dependency correction, and the isotopologue method, based on measured isotopologue abundances. Calibration with the ratio method and isotopologue method is based on three different assigned whole-air references calibrated on the VPDB (Vienna Pee Dee Belemnite) and the WMO 2007 (World Meteorological Organization) scale for their stable isotope compositions and their CO2 mole fractions, respectively. An additional quality control tank is included in both methods to follow long-term instrument performance. Measurements of the quality control tank show that the measurement precision and accuracy of both calibration methods is of similar quality for δ13C and δ18O measurements. During one specific measurement period the precision and accuracy of the quality control tank reach WMO compatibility requirements, being 0.01 ‰ for δ13C and 0.05 ‰ for δ18O. Uncertainty contributions of the scale uncertainties of the reference gases add another 0.03 ‰ and 0.05 ‰ to the combined uncertainty of the sample measurements. Hence, reaching WMO compatibility for sample measurements on the SICAS requires reduction of the scale uncertainty of the reference gases used for calibration. An intercomparison of flask samples over a wide range of CO2 mole fractions has been conducted with the Max Planck Institute for Biogeochemistry, resulting in a mean residual of 0.01 ‰ and −0.01 ‰ and a standard deviation of 0.05 ‰ and 0.07 ‰ for the δ13C measurements calibrated using the ratio method and the isotopologue method, respectively. The δ18O could not be compared due to depletion of the δ18O signal in our sample flasks because of storage times being too long. Finally, we evaluate the potential of our Δ17O measurements as a tracer for gross primary production by vegetation through photosynthesis. Here, a measurement precision of &lt;0.01 ‰ would be a prerequisite for capturing seasonal variations in the Δ17O signal. Lowest standard errors for the δ17O and Δ17O of the ratio method and the isotopologue method are 0.02 ‰ and 0.02 ‰ and 0.01 ‰ and 0.02 ‰, respectively. The accuracy results show consequently results that are too enriched for both the δ17O and Δ17O measurements for both methods. This is probably due to the fact that two of our reference gases were not measured directly but were determined indirectly. The ratio method shows residuals ranging from 0.06 ‰ to 0.08 ‰ and from 0.06 ‰ to 0.1 ‰ for the δ17O and Δ17O results, respectively. The isotopologue method shows residuals ranging from 0.04 ‰ to 0.1 ‰ and from 0.05 ‰ to 0.13 ‰ for the δ17O and Δ17O results, respectively. Direct determination of the δ17O of all reference gases would improve the accuracy of the δ17O and thereby of the Δ17O measurements.

Differentiating early from later diagenesis in a Cretaceous sandstone and petroleum reservoir of the Cedar Mountain Formation, Utah

ABSTRACT Previously published anomalous whole-rock stable isotopic values from the Poison Strip Sandstone Member of the Cretaceous Cedar Mountain Formation (CMF) of eastern Utah are of uncertain origins. This study investigated the diagenetic history and the processes responsible for these anomalous data. Accordingly, we integrated photomicroscopic techniques including polarized light microscopy, epifluorescence and cathodoluminescence (CL) imaging, micromilling of stable isotope samples, and fluid-inclusion heating and freezing measurements to this end. The key observations involved the microscopic mapping of calcite cement stratigraphy using CL imaging to permit the analysis of stable isotopes of calcite cements that crystallized during early and late diagenesis. The mapping of calcite cement zones of sufficient submillimeter size to mill out and isolate microgram-sized stable isotope samples enabled this discrimination. Early diagenetic calcite cements have the most positive δ18O values (-10 to -8.5‰ Vienna Pee Dee Belemnite [VPDB]) of all components. The pattern of δ13C and δ18O variation in this early diagenetic cement indicates affinities with early meteoric diagenesis previously documented in published literature on the CFM. The late diagenetic calcite cements yield the most negative δ18O values (-18 to -16‰ VPDB). We interpret the late diagenetic cements to be responsible for the anomalously low whole-rock δ18O values previously reported from the Poison Strip Sandstone Member. Our discoveries of bitumen in late-stage pore fillings and liquid petroleum in the fluid inclusions of late diagenetic calcite cements of the Poison Strip Sandstone Member explain the lower whole-rock organic matter δ13C values and anomalous Δ13C values reported from the unit. Comparatively lower carbonate δ18O and organic δ13C values originally derived from whole-rock analyses of samples from the Poison Strip Sandstone Member resulted from high-temperature basinal diagenesis (hydrothermal circulation and/or petroleum migration), rather than the alternative interpretation of early diagenesis related to a Cretaceous paleoclimatic perturbation. Our results are illustrative of methods to resolve the long-standing geologic problem of discriminating and characterizing products of early vs. late diagenesis in terrigenous clastic sedimentary strata.

Absolute 13C/12C Isotope Amount Ratio for Vienna Pee Dee Belemnite from Infrared Absorption Spectroscopy.

Measurements of isotope ratios are predominantly made with reference to standard specimens that have been characterized in the past. In the 1950s, the carbon isotope ratio was referenced to a belemnite sample collected by Heinz Lowenstam and Harold Urey1 in South Carolina's Pee Dee region. Due to the exhaustion of the sample since then, reference materials that are traceable to the original artefact are used to define the Vienna Pee Dee Belemnite (VPDB) scale for stable carbon isotope analysis2. However, these reference materials have also become exhausted or proven to exhibit unstable composition over time3, mirroring issues with the international prototype of the kilogram that led to a revised International System of Units4. A campaign to elucidate the stable carbon isotope ratio of VPDB is underway5, but independent measurement techniques are required to support it. Here we report an accurate value for the stable carbon isotope ratio inferred from infrared absorption spectroscopy, fulfilling the promise of this fundamentally accurate approach6. Our results agree with a value recently derived from mass spectrometry5, and therefore advance the prospects of SI-traceable isotope analysis. Further, our calibration-free method could improve mass balance calculations and enhance isotopic tracer studies in CO2 source apportionment.