CO2 Isotope Research Articles

CO2 and Rn degassing from the natural analog of Campo de Calatrava (Spain): Implications for monitoring of CO2 storage sites

Natural analogs offer a valuable opportunity to investigate the long-term impacts associated with the potential leakage in geological storage of CO2.Degassing of CO2 and radon isotopes (222Rn–220Rn) from soil, gas vents and thermal water discharges was investigated in the natural analog of Campo de Calatrava Volcanic Field (CCVF; Central Spain) to determine the CO2–Rn relationships and to assess the role of CO2 as carrier gas for radon. Furthermore, radon measurements to discriminate between shallow and deep gas sources were evaluated under the perspective of their applicability in monitoring programs of carbon storage projects.CO2 flux as high as 5000gm−2d−1 and 222Rn activities up to 430kBqm−3 were measured; 220Rn activities were one order of magnitude lower than those of 222Rn. The 222Rn/220Rn ratios were used to constrain the source of the Campo de Calatrava soil gases since a positive correlation between radon isotopic ratios and CO2 fluxes was observed. Thus, in agreement with previous studies, our results indicate a deep mantle-related origin of CO2 for both free and soil gases, suggesting that carbon dioxide is an efficient carrier for Rn. Furthermore, it was ascertained that the increase of 222Rn in the soil gases was likely produced by two main processes: (i) direct transport by a carrier gas, i.e., CO2 and (ii) generation at shallow level due to the presence of relatively high concentrations of dissolved U and Ra in the thermal aquifer of Campo de Calatrava.The diffuse CO2 soil flux and radon isotopic surveys carried out in the Campo de Calatrava Volcanic Fields can also be applicable to geochemical monitoring programs in CCS (Carbon Capture and Storage) areas as these parameters are useful to: (i) constrain CO2 leakages once detected and (ii) monitor both the evolution of the leakages and the effectiveness of subsequent remediation activities. These measurements can also conveniently be used to detect diffuse leakages.

Structural characterization of CO-inhibited Mo-nitrogenase by combined application of nuclear resonance vibrational spectroscopy, extended X-ray absorption fine structure, and density functional theory: new insights into the effects of CO binding and the role of the interstitial atom.

The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm–1 mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N2ase variant. In the frequency region above 450 cm–1, additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by 13CO isotope shifts). The EXAFS for wild-type N2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal −CO and a partially reduced −CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational “shake” modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N2 reactivity of N2ase are discussed.

Systematic variation of the 12CO/13CO ratio as a function of star formation rate surface density

We show that the12CO/13CO intensity ratio in nearby galaxies varies systematically as a function of the star formation rate surface density and gas surface density. The same effect is observed in different transitions, and in the 12CO/C18O ratio, while the 13CO/C18O ratio appears to remain constant as a function of the star formation rate surface density. We discuss the cause of these variations, considering both changes in the physical state of the gas, and chemical changes that lead to abundance variations. We used the observed correlations with C18O to suggest that abundance variations are unlikely to be causing the systematic trend observed with the star formation rate surface density, and thus that the mean gas temperature and/or velocity dispersion are systematically higher in higher star-formation rate surface density regions. We present the best fitting relations between the star formation rate surface density and the 12CO/13CO and 12CO/C18O ratios, and discuss how this effect can help us predict CO isotope emission from galaxies across the known universe.

Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial–brine–rock–CO2 interactions

The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2 appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

Improved repetition rate mixed isotope CO₂ TEA laser.

A compact CO2 TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the (12)C(16)O2 isotope. With mixed (12)C(16)O2 plus (13)C(16)O2 isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

SPATIALLY RESOLVED HCN J = 4-3 AND CS J = 7-6 EMISSION FROM THE DISK AROUND HD 142527

The disk around HD 142527 attracts a lot of attention, amongst others because of its resolved (sub) mm dust continuum that is concentrated into a horseshoe-shape towards the north of the star. In this manuscript we present spatially resolved ALMA detections of the HCN J=4-3 and CS J=7-6 emission lines. These lines give us a view deeper into the disk compared to the (optically thicker) CO isotopes. This is the first detection of CS J=7-6 coming from a protoplanetary disk. Both emission lines are azimuthally asymmetric and are suppressed under the horseshoe-shaped continuum emission peak. A possible mechanism to explain the decrease under the horseshoe-shaped continuum is the increased opacity coming from the higher dust concentration at the continuum peak. Lower {\gr dust and/or gas} temperatures and an optically thick radio-continuum reduce line emission by freeze-out and shielding of emission from the far side of the disk.

High-precision quasi-continuous atmospheric greenhouse gas measurements at Trainou tower (Orléans forest, France)

Abstract. Results from the Trainou tall tower measurement station installed in 2006 are presented for atmospheric measurements of CO2, CH4, N2O, SF6, CO, H2 mole fractions and radon-222 activity. Air is sampled from four sampling heights (180, 100, 50 and 5 m) of the Trainou 200 m television tower in the Orléans forest in France (47°57'53" N, 2°06'45" E, 131 m a.s.l.). The station is equipped with a custom-built CO2 analyser (CARIBOU), which is based on a commercial non-dispersive, infrared (NDIR) analyser (Licor 6252), and a coupled gas chromatography (GC) system equipped with an electron capture detector (ECD) and a flame ionization detector (FID) (HP6890N, Agilent) and a reduction gas detector (PP1, Peak Performer). Air intakes, pumping and air drying system are shared between the CARIBOU and the GC systems. The ultimately achieved short-term repeatability (1 sigma, over several days) for the GC system is 0.05 ppm for CO2, 1.4 ppb for CH4, 0.25 ppb for N2O, 0.08 ppb for SF6, 0.88 ppb for CO and 3.8 for H2. The repeatability of the CARIBOU CO2 analyser is 0.06 ppm. In addition to the in situ measurements, weekly flask sampling is performed, and flask air samples are analysed at the Laboratoire des Sciences du Climat et de l'Environnement (LSCE) central laboratory for the same species as well for stable isotopes of CO2. The comparison between in situ measurements and the flask sampling showed averaged differences of 0.08 ± 1.40 ppm for CO2, 0.7 ± 7.3 ppb for CH4, 0.6 ± 0.6 ppb for N2O, 0.01 ± 0.10 ppt for SF6, 1.5± 5.3 ppb for CO and 4.8± 6.9 ppb for H2 for the years 2008–2012. At Trainou station, the mean annual increase rates from 2007 to 2011 at the 180 m sampling height were 2.2 ppm yr−1 for CO2, 4 ppb yr−1 for CH4, 0.78 ppb yr−1 for N2O and 0.29 ppt yr−1 for SF6. For all species, the 180 m sampling level showed the smallest diurnal variation. Mean diurnal gradients between the 50 m and the 180 m sampling level reached up to 30 ppm CO2, 15 ppm CH4 or 0.5 ppb N2O during nighttime whereas the mean gradients are smaller than 0.5 ppm for CO2 and 1.5 ppb for CH4 during afternoon.

Diagnosis of small intestinal bacterial overgrowth in irritable bowel syndrome patients using high-precision stable13CO2/12CO2isotope ratios in exhaled breath

Hydrogen breath tests (HBT) are widely used for the diagnosis of small intestinal bacterial overgrowth (SIBO) in patients with irritable bowel syndrome (IBS). However, the conclusions drawn from these studies are highly controversial, and several discrepancies exist in the results. The aim of our study is to develop an alternative 13C-glucose breath test (13C-GBT) methodology by measuring high-precision 13CO2/12CO2 isotope ratios in exhaled breath to accurately diagnose SIBO using an optical cavity-enhanced CO2 isotope analyzer. In all, 118 diarrhea-predominant (IBS-D) patients diagnosed according to ROME III criteria underwent 13C-GBT and HBT following the ingestion of a test meal containing 50 mg 13C-enriched glucose with 50 g glucose. The excretion of 13CO2 enrichments and a cumulative percentage dose of 13C-recovered (c-PDR) significantly depleted (p < 0.001) for the positive SIBO patients (n = 25) compared to the patients with negative SIBO (n = 53) as diagnosed by HBT. A cut-off value of 5.47‰ at 45 min was indicative of a positive SIBO syndrome. Subsequently, a portion of IBS-D individuals (n = 20) whose HBTs were negative but 13C-GBTs were positive, suggesting HBT often fails to diagnose SIBO when the patients may have “non-hydrogen-producing” bacteria. 13C-GBT also correctly diagnosed SIBO in patients (n = 20) within the “grey-zone” and during the preclinical phase of SIBO as opposed to HBT. The prevalence of SIBO with IBS-D in Indian population was estimated to be 45.7%. Our study demonstrates 13C-GBT, for the first time, as a clinically valid and sufficiently robust alternative diagnostic methodology for an accurate evaluation of SIBO in IBS-D patients and superior to HBT.

Kinetic fractionation of carbon and oxygen isotopes during hydration of carbon dioxide

Kinetic isotope effects (KIEs) during the inorganic hydration of carbon dioxide (CO2) in aqueous solution cause reduced stable carbon and oxygen isotope ratios (13C/12C and 18O/16O) in the reaction product carbonic acid (H2CO3) or bicarbonate ion (HCO3-), relative to CO2. While such KIEs are of importance in various physicochemical, geochemical, and biological systems, very few experimental and theoretical studies have attempted to determine the magnitude of the carbon and oxygen kinetic isotope fractionation (KIF) during hydration of CO2. Here I use transition state theory (TST) and quantum chemistry calculations to investigate the reaction rates of isotopic reactants CO2+nH2O (n=1–8) along the hydration pathway to H2CO3 or HCO3-. Locating transition states is difficult and the quantum chemistry calculations time-consuming at large n. My results suggest that the hydration mechanism for n=1–3 is unlikely to be the dominant pathway producing KIFs during CO2 hydration in aqueous solution; hydration mechanisms for n⩾4 appear more likely. For n=4–8, the predicted KIF based on MP2/aug-cc-pVDZ calculations at 25°C is ∼1.023–1.033 and ∼1.013–1.015, for carbon and oxygen, respectively. However, these values are uncertain and the results of the present study suggest that new experimental work is required to accurately determine the KIF of carbon and oxygen during CO2 hydration.

High-resolution stable carbon isotope monitoring indicates variable flow dynamic patterns in a deep saline aquifer at the Ketzin pilot site (Germany)

Stable isotopes of injected CO2 act as useful tracers in carbon capture and storage (CCS) because the CO2 itself is the carrier of the tracer signal and remains unaffected by sorption or partitioning effects. At the Ketzin pilot site (Germany), carbon stable isotope composition (δ13C) of injected CO2 at the injection well was analyzed over a time period of 4months. Occurring isotope variances resulted from the injection of CO2 from two different sources (an oil refinery and a natural gas-reservoir). The two gases differed in their carbon isotope composition by more than 27‰. In order to find identifiable patterns of these variances in the reservoir, more than 250 CO2-samples were collected and analyzed for their carbon isotope ratios at an observation well 100m distant from the injection well. An isotope ratio mass spectrometer connected to a modified Thermo Gasbench system allowed quick and cost effective isotope analyses of a high number of CO2 gas specimens. CO2 gas from the oil refinery (δ13C=−30.9‰, source A) was most frequently injected and dominated the reservoir δ13C values at the injection site. Sporadic injection of the CO2 from the natural gas-reservoir (δ13C=−3.5‰, source B) caused isotope shifts of up to +5‰ at the injection well. These variances provided a potential ideal tracer for CO2 migration behavior. Based on these findings, tracer input signals that were injected during the last 2years of injection could be reconstructed with the aid of an isotope mixing model and CO2 delivery schedules. However, in contrast to the injection well, δ13C values at the observation well showed no variances and a constant value of −28.5‰ was measured at 600m depth. This is in disagreement with signals that would be expected if the input signals from the injection would arrive at the observation well. The lack of isotope signals at the observation well suggests that parts of the reservoir are filled with CO2 that is immobilized.

Enhanced Raman multigas sensing – a novel tool for control and analysis of13CO2labeling experiments in environmental research

Cavity-enhanced Raman multigas spectrometry is introduced as a versatile technique for monitoring of (13)CO2 isotope labeling experiments, while simultaneously quantifying the fluxes of O2 and other relevant gases across a wide range of concentrations. The multigas analysis was performed in a closed cycle; no gas was consumed, and the gas composition was not altered by the measurement. Isotope labeling of plant metabolites via photosynthetic uptake of (13)CO2 enables the investigation of resource flows in plants and is now an important tool in ecophysiological studies. In this experiment the (13)C labeling of monoclonal cuttings of Populus trichocarpa was undertaken. The high time resolution of the online multigas analysis allowed precise control of the pulse labeling and was exploited to calculate the kinetics of photosynthetic (13)CO2 uptake and to extrapolate the exact value of the (13)CO2 peak concentration in the labeling chamber. Further, the leaf dark respiration of immature and mature leaves was analyzed. The quantification of the photosynthetic O2 production rate as a byproduct of the (13)CO2 uptake correlated with the amount of available light and the leaf area of the plants in the labeling chamber. The ability to acquire CO2 and O2 respiration rates simultaneously also simplifies the determination of respiratory quotients (rate of O2 uptake compared to CO2 release) and thus indicates the type of combusted substrate. By combining quantification of respiration quotients with the tracing of (13)C in plants, cavity enhanced Raman spectroscopy adds a valuable new tool for studies of metabolism at the organismal to ecosystem scale.

Carbon isotope discrimination as a tool to explore C4 photosynthesis

Photosynthetic carbon isotope discrimination is a non-destructive tool for investigating C4 metabolism. Tuneable diode laser absorption spectroscopy provides new opportunities for making rapid, concurrent measurements of carbon isotope discrimination and CO2 assimilation over a range of environmental conditions, and this has facilitated the use of carbon isotope discrimination as a probe of C4 metabolism. In spite of the significant progress made in recent years, understanding how photosynthetic carbon isotope discrimination measured concurrently with gas exchange relates to carbon isotope composition of leaf and plant dry matter remains a challenge that requires resolution if this technique is to be successfully applied as a screening tool in crop breeding and phylogenetic research. In this review, we update our understanding of the factors and assumptions that underlie variations in photosynthetic carbon isotope discrimination in C4 leaves. Closing the main gaps in our understanding of carbon isotope discrimination during C4 photosynthesis may help advance research aimed at developing higher productivity and efficiency in key C4 food, feed, and biofuel crops.

Photodissociation of CO isotopologues: Models of laboratory experiments and implications for the solar nebula

AbstractCO photodissociation in the solar nebula and/or parent cloud has been proposed to be the mechanism responsible for forming the 16O‐poor reservoir of the calcium‐aluminum‐rich inclusion (CAI) mixing line. However, laboratory experiments on CO photolysis found a wavelength dependence in the oxygen isotope ratios of the product O atoms, which was interpreted as proof that CO photolysis was not a viable mechanism. Here, I report photochemical simulations of these experiments using line‐by‐line CO spectra to identify the origin of the wavelength dependence. At long wavelengths (&gt;105 nm), the line‐by‐line spectra for isotopic CO can explain the experimental data with a combination of C16O self‐shielding and reduced dissociation probabilities for C18O. At short wavelengths, the greater number of diffuse bands increases the importance of mass‐dependent fractionation, lowering the slope to below unity. The line‐by‐line isotopic spectra are then applied to CO photodissociation in a model solar nebula. Three FUV sources are considered (1) HD 303308, an O4 star in Carina; (2) HD 36981, a B5 star in Orion; and (3) TW Hydrae, a T Tauri star of 10 Myr age. Using reduced dissociation probabilities for C18O based on the photolysis experiments yields nebular water slopes approximately 0.95–1.0 for HD 303308 and TW Hya, and approximately 0.8–1.5 for HD 36981. For the central protostar case (TW Hya) with a simplified treatment of the 2‐D radiative transfer, slopes approximately 0.95–1.0 are obtained, independent of the C18O dissociation probability. Greatly improved measurements of the C17O and C18O cross sections and dissociation probabilities are in progress.

Ångström (B1Σ+ →A1Π) 0–1 and 1–1 bands in isotopic CO molecules: further investigations

In the emission spectrum of six 12C16O, 13C16O, 12C18O, 14C16O, 13C18O and 14C18O isotopologues of the carbon monoxide molecule, new recordings and analyses or new reanalyses of the selected and strongest bands belonging to the Ångström (B1Σ+ − A1Π) system were carried out. Under high resolution, emission spectra of the 0–1 and 1–1 bands were recorded and reanalysed, representing both the 0 − v″ and 1 − v″ progressions of this system. Unobserved so far, new spectral lines were identified, and for the 12C16O, 13C16O, 12C18O, 14C16O and 14C18O molecules new parameters of the rovibronic structure B0, B1, D0 and D1 of the v = 0 and v = 1 levels of the B1Σ+ state and band origins ν0 of the 0–1 and 1–1 bands of the B − A transition were determined. A detailed analysis included the predissociation regions of the spectra observed in all analysed bands and isotopologues. The values of rotational quantum numbers and rovibronic terms of the highest nonpredissociated Jh as well as the first, already predissociated Jf levels were determined. On that basis, a new and more precise value of dissociation energy of the CO molecule was determined: cm−1. Also, atomic states of the dissociation products of this molecule, which correspond to this energy, were identified as C(3P0) + O(3P2) i.e. as both triplet ground atomic sublevels.

Single‐cell C4 photosynthesis: efficiency and acclimation of Bienertia sinuspersici to growth under low light

Traditionally, it was believed that C(4) photosynthesis required two types of chlorenchyma cells to concentrate CO(2) within the leaf. However, several species have been identified that perform C(4) photosynthesis using dimorphic chloroplasts within an individual cell. The goal of this research was to determine how growth under limited light affects leaf structure, biochemistry and efficiency of the single-cell CO(2) -concentrating mechanism in Bienertia sinuspersici. Measurements of rates of CO(2) assimilation and CO(2) isotope exchange in response to light intensity and O(2) were used to determine the efficiency of the CO(2) -concentrating mechanism in plants grown under moderate and low light. In addition, enzyme assays, chlorophyll content and light microscopy of leaves were used to characterize acclimation to light-limited growth conditions. There was acclimation to growth under low light with a decrease in capacity for photosynthesis when exposed to high light. This was associated with a decreased investment in biochemistry for carbon assimilation with only subtle changes in leaf structure and anatomy. The capture and assimilation of CO(2) delivered by the C(4) cycle was lower in low-light-grown plants. Low-light-grown plants were able to acclimate to maintain structural and functional features for the performance of efficient single-cell C(4) photosynthesis.

QUANTIFYING OBSERVATIONAL PROJECTION EFFECTS USING MOLECULAR CLOUD SIMULATIONS

The physical properties of molecular clouds are often measured using spectral-line observations, which provide the only probes of the clouds' velocity structure. It is hard, though, to assess whether and to what extent intensity features in position-position-velocity (PPV) space correspond to "real" density structures in position-position-position (PPP) space. In this paper, we create synthetic molecular cloud spectral-line maps of simulated molecular clouds, and present a new technique for measuring the reality of individual PPV structures. Our procedure projects density structures identified in PPP space into corresponding intensity structures in PPV space and then measures the geometric overlap of the projected structures with structures identified from the synthetic observation. The fractional overlap between a PPP and PPV structure quantifies how well the synthetic observation recovers information about the 3D structure. Applying this machinery to a set of synthetic observations of CO isotopes, we measure how well spectral-line measurements recover mass, size, velocity dispersion, and virial parameter for a simulated star-forming region. By disabling various steps of our analysis, we investigate how much opacity, chemistry, and gravity affect measurements of physical properties extracted from PPV cubes. For the simulations used here, our results suggest that superposition induces a ~40% uncertainty in masses, sizes, and velocity dispersions derived from 13CO. The virial parameter is most affected by superposition, such that estimates of the virial parameter derived from PPV and PPP information typically disagree by a factor of ~2. This uncertainty makes it particularly difficult to judge whether gravitational or kinetic energy dominate a given region, since the majority of virial parameter measurements fall within a factor of 2 of the equipartition level alpha ~ 2.

Carbon and helium isotopes in thermal springs of La Soufrière volcano (Guadeloupe, Lesser Antilles): Implications for volcanological monitoring

La Soufrière (Guadeloupe, Lesser Antilles) is one of the most active and dangerous volcanoes of the Lesser Antilles arc. The renewal of the volcanic activity at La Soufrière requires replenishment of the volatile-poor andesitic stored magma with more primitive, volatile-rich basaltic magma. This event will trigger early release of large quantities of highly volatile species, like CO2 and helium, in the hydrothermal system. To use these precursors, first their baseline abundances and their behaviour in the hydrothermal system must be known during the current phase of dormancy. In this study, we have combined a previous systematic investigation of noble gases with carbon data of hydrothermal fluids flowing out of La Soufrière.The results for dissolved gases reveal that an intense interaction between rising magmatic volatiles and groundwaters currently takes place at La Soufrière. We show that the pristine magmatic composition, with a δ13CCO2 value of −3.19±0.03‰, a 3He/4He ratio of 8.1±0.2 Ra and a CO2/3He ratio of 1.03±0.18×1010, may vary during the ascent of magmatic fluids due to either fractionation or mixing processes with meteoric water and/or an organic component. Here, we provide a baseline for CO2 and helium isotopes at each monitored spring and describe the superficial processes affecting both elemental and isotopic ratios.

Multiple lines of evidence to demonstrate vinyl chloride aerobic biodegradation in the vadose zone, and factors controlling rates

A field-based investigation was conducted at a contaminated site where the vadose zone was contaminated with a range of chlorinated hydrocarbons. The investigation consisted of groundwater and multilevel soil-gas monitoring of a range of contaminants and gases, along with isotope measurements and microbiology studies. The investigation provided multiple lines of evidence that demonstrated aerobic biodegradation of vinyl chloride (VC) was occurring in the vadose zone (i) above the on-site source zone, and (ii) above the downgradient off-site groundwater plume location. Data from both the on-site and off-site locations were consistent in showing substantially greater (an order of magnitude greater) rates of VC removal from the aerobic vadose zone compared to more recalcitrant contaminants trichloroethene (TCE) and tetrachloroethene (PCE). Soil gas VC isotope analysis showed substantial isotopic enrichment of VC (δ¹³C -5.2 to -10.9‰) compared to groundwater (δ¹³C -39.5‰) at the on-site location. Soil gas CO₂ isotope analysis at both locations showed that CO₂ was highly isotopically depleted (δ¹³C -28.8 to -33.3‰), compared to soil gas CO₂ data originating from natural sediment organic matter (δ¹³C= -14.7 to -21.3‰). The soil gas CO2 δ¹³C values were consistent with near-water table VC groundwater δ¹³C values (-36.8 to -39.5‰), suggesting CO₂ originating from aerobic biodegradation of VC. Bacteria that had functional genes (ethene monooxygenase (etnC) and epoxyalkane transferase (etnE)) involved in ethene metabolism and VC oxidation were more abundant at the source zone where oxygen co-existed with VC. The distribution of VC and oxygen vadose zone vapour plumes, together with long-term changes in soil gas CO₂ concentrations and temperature, provided information to elucidate the factors controlling aerobic biodegradation of VC in the vadose zone. Based on the overlapping VC and oxygen vadose zone vapour plumes, aerobic vapour biodegradation rates were independent of substrate (VC and/or oxygen) concentration. The high correlation (R=0.962 to 0.975) between CO₂ concentrations and temperature suggested that aerobic biodegradation of VC was controlled by bacterial activity that was regulated by the temperature within the vadose zone. When assessing a contaminated site for possible vapour intrusion into buildings, accounting for environmental conditions for aerobic biodegradation of VC in the vadose zone should improve the assessment of environmental risk of VC intrusion into buildings, enabling better identification and prioritisation of contaminated sites to be remediated.

N2O as a tracer of mixing stratospheric and tropospheric air based on CARIBIC data with applications for CO2

Stratosphere–troposphere exchange (STE) affects distributions of trace gases, with ozone (O3) and CO being commonly used to study mixing process in the UTLS (Upper Troposphere and Lower Stratosphere) region. Here we explore the application of N2O as a tracer of stratosphere to troposphere flux for CO2 and its isotopes, using N2O and CO2 mixing ratios including a set of CO2 isotope data for CARIBIC aircraft samples and NOAA-Carbon Cycle flask samples. A frequency distribution of CARIBIC N2O data (mostly UTLS at mid- and high-latitudes) reveals a narrow distribution around a tropospheric maximum at nearly the same N2O mixing ratio as the distribution peak for the station Mauna Loa (MLO) however with a skewing due to STE. We demonstrate that upper-tropospheric and STE-affected air can be distinguished using a threshold value based on the N2O distribution width at MLO. A comparison with the use of O3 is given. N2O is discussed to be a robust and linear (season and latitude independent) tracer of STE mixing proportions. We propose that CARIBIC data coupled with CO2 isotopic data published for the stratosphere and data of NOAA stations can be used as a frame of reference for δ18O(CO2) and Δ17O(CO2) STE fluxes. The Δ17O(CO2) flux is of particular interest as it is thought to constrain estimates of biosphere productivity, atmospheric oxygen cycle and global gross CO2 fluxes. CARBIC data can also help tracing STE flux by deep stratospheric intrusions and a data analysis is given for the Walliguan (WLG) observatory on the Tibetan Plateau.

ALMA observations of the variable12CO/13CO ratio around the asymptotic giant branch star R Sculptoris

[abridged] The 12CO/13CO ratio is often used as a measure of the 12C/13C ratio in the circumstellar environment, carrying important information about the stellar nucleosynthesis. External processes can change the 12CO and 13CO abundances, and spatially resolved studies of the 12CO/13CO ratio are needed to quantify the effect of these processes on the globally determined values. Additionally, such studies provide important information on the conditions in the circumstellar environment. The detached-shell source R Scl, displaying CO emission from recent mass loss, in a binary-induced spiral structure as well as in a clumpy shell produced during a thermal pulse, provides a unique laboratory for studying the differences in CO isotope abundances throughout its recent evolution. We observed both the 12CO(J=3-2) and the 13CO(J=3-2) line using ALMA. We find significant variations in the 12CO/13CO intensity ratios and consequently in the abundance ratios. The average CO isotope abundance ratio is at least a factor three lower in the shell (~19) than that in the present-day (<300 years) mass loss (>60). Additionally, variations in the ratio of more than an order of magnitude are found in the shell itself. We attribute these variations to the competition between selective dissociation and isotope fractionation in the shell, of which large parts cannot be warmer than ~35 K. However, we also find that the 12CO/13CO ratio in the present-day mass loss is significantly higher than the 12C/13C ratio determined in the stellar photosphere from molecular tracers (~19). The origin of this discrepancy is still unclear, but we speculate that it is due to an embedded source of UV-radiation that is primarily photo-dissociating 13CO. This radiation source could be the hitherto hidden companion. Alternatively, the UV-radiation could originate from an active chromosphere of R Scl itself....