Isotopic tracing of leachate percolation from municipal solid waste dump sites to groundwater in diverse climatic zones of India.

Groundwater resources in tropical regions are largely dependent on recharge by rainwater infiltration through soil layers with variable time. However, the rainwater infiltration through soil is a serious concern in urban tropics where it interacts with landfills at the dumpsites, potentially contaminating adjoining groundwater. In this study, the stable isotopic compositions of oxygen and hydrogen (δ18O and δ2H, respectively) in groundwater and leachates, adjoining municipal dumpsites in urban tropics (Bangalore, Kolkata and Durgapur located in diverse rainfall zonation of India), were analyzed to investigate their recharge sources and trace the possible mixing of leachate contaminants under three diverse climatology. The measured values of δ18O and δ2H suggested that the groundwater in these sites reflects higher recharge by rainwater. However, the d-excess values indicated secondary effects suggesting the groundwater has experienced significant modifications. The end member analysis using δ18O-d-excess relation pinpointed an additional leachate contribution from adjoining dumpsites. The critical fraction of leachate infiltration to groundwater quantified using two component mixing model ranged between (i) 1 and 33% in Bangalore, (ii) 5 and 13% in Kolkata and (iii) 18 and 76% in Durgapur, with its variability dependent on seasonality and aquifer connectivity. This information is crucial for groundwater management to secure water quality and to quantify potential hydrological contaminants particularly in drier seasons and drier regions, when and where the demand for groundwater is high, respectively.

New constraints of terrestrial and oceanic global gross primary productions from the triple oxygen isotopic composition of atmospheric CO2 and O2.

Representations of the changing global carbon cycle under climatic and environmental perturbations require highly detailed accounting of all atmosphere and biosphere exchange. These fluxes remain unsatisfactory, as a consequence of only having data with limited spatiotemporal coverage and precision, which restrict accurate assessments. Through the nature of intimate coupling of global carbon and oxygen cycles via O2 and CO2 and their unique triple oxygen isotope compositions in the biosphere and atmosphere, greater insight is available. We report analysis of their isotopic compositions with the widest geographical and temporal coverage (123 new measurements for CO2) and constrain, on an annual basis, the global CO2 recycling time (1.5 ± 0.2 year) and gross primary productivities of terrestrial (~ 170-200 PgC/year) and oceanic (~ 90-120 PgC/year) biospheres. Observed inter-annual variations in CO2 triple oxygen isotopic compositions were observed at a magnitude close to the largest contrast set by the terrestrial and oceanic biospheres. The seasonal cycles between the east and west Pacific Ocean were found to be drastically different. This intra-annual variability implies that the entire atmospheric CO2 turnover time is not much longer than the tropospheric mixing time (less than ~ 5 months), verifying the derived recycling time. The new measurements, analyses, and incorporation of other global data sets allow development of an independent approach, providing a strong constraint to biogeochemical models.

Seasonal Variations of Solar-Induced Fluorescence, Precipitation, and Carbon Dioxide Over the Amazon.

Previous studies suggested that the Amazon, the largest rainforest on Earth, changes from a CO2 sink to a CO2 source during the dry/fire season. However, the biospheric contributions to atmospheric CO2 are not well understood during the two main seasons, the dry/fire season and the wet season. In this article, we utilize Orbiting Carbon Observatory 2 (OCO-2) Solar-Induced Fluorescence (SIF) to explore photosynthetic activity during the different seasons. The spatiotemporal variability of OCO-2 SIF, OCO-2 CO2, precipitation, and burned area are investigated over the Amazon from September 2014 to December 2019. Averaging over the entire Amazon region, we found a positive temporal correlation (0.94) between OCO-2 SIF and Global Precipitation Climatology Project precipitation and a negative temporal correlation (-0.64) between OCO-2 SIF and OCO-2 CO2, consistent with the fact that precipitation enhances photosynthesis, which results in higher values for SIF and rate of removal of CO2 from the atmosphere above the Amazon region. We also observed seasonality in the spatial variability of these variables within the Amazon region. During the dry/fire (August-October) season, low SIF values, low precipitation, high vapor pressure deficit (VPD), large burned areas, and high atmospheric CO2 are mainly found over the southern Amazon region. In contrast, during the wet season (January-March), high SIF values, high precipitation, low VPD, smaller burned areas, and low CO2 are found over both the central and southern Amazon regions. The seasonal difference in SIF suggests that photosynthetic activity is reduced during the dry/fire season relative to the wet season as a result of low precipitation and high VPD, especially over the southern Amazon region, which will contribute to more CO2 in the atmosphere during the dry/fire season.

Isotopic assessment of soil N2O emission from a sub-tropical agricultural soil under varying N-inputs.

Nitrogen fertilizers result in high crop productivity but also enhance the emission of N2O, an environmentally harmful greenhouse gas. Only approximately a half of the applied nitrogen is utilized by crops and the rest is either vaporized, leached, or lost as NO, N2O and N2 via soil microbial activity. Thus, improving the nitrogen use efficiency of cropping systems has become a global concern. Factors such as types and rates of fertilizer application, soil texture, moisture level, pH, and microbial activity/diversity play important roles in N2O production. Here, we report the results of N2O production from a set of chamber experiments on an acidic sandy-loam agricultural soil under varying levels of an inorganic N-fertilizer, urea. Stable isotope technique was employed to determine the effect of increasing N-fertilizer levels on N2O emissions and identify the microbial processes involved in fertilizer N-transformation that give rise to N2O. We monitored the isotopic changes in both substrate (ammonium and nitrate) and the product N2O during the entire course of the incubation experiments. Peak N2O emissions of 122 ± 98 µg N2O-N m-2 h-1, 338 ± 49 µg N2O-N m-2 h-1 and 739 ± 296 µg N2O-N m-2 h-1 were observed for urea application rate of 40, 80, and 120 µg N g-1. The duration of emissions also increased with urea levels. The concentration and isotopic compositions of the substrates and product showed time-bound variation. Combining the observations of isotopic effects in δ15N, δ18O, and 15N site preference, we inferred co-occurrence of several microbial N2O production pathways with nitrification and/or fungal denitrification as the dominant processes responsible for N2O emissions. Besides this, dominant signatures of bacterial denitrification were observed in a second N2O emission pulse in intermediate urea-N levels. Signature of N2O consumption by reduction could be traced during declining emissions in treatment with high urea level.

Role of Vehicular Catalytic Converter Temperature in Emission of Pollutants: An Assessment Based on Isotopic Analysis of CO2 and N2O.

Vehicular catalytic converters are used to regulate, reduce, and convert toxic and environmentally unfriendly compounds in exhaust gases into relatively inert and less harmful chemical species. The efficiency, however, is largely affected by the operating temperature of the converter which is set by the hot exhaust gas released from the combustion chamber. A major gas released during combustion is CO2, and its multiply substituted isotopocule, namely, 13C16O18O, provides a window of opportunity to probe directly the effective temperature of the converter in operation. Here, we report multiple isotopic measurements in exhaust CO2 (δ13C, δ17O, δ18O, and Δ47) of diesel (trucks and buses) and gasoline (sedans, trucks, and two-wheel motorcycles)-powered vehicles. For investigating the efficiency of a converter in reducing toxic compounds, we studied NOx processes through isotopic analysis of the exhaust N2O. We found that the degree of N2O reduction to N2 in gasoline-powered vehicles is high when the temperature is above 200 °C (inferred by Δ47). In contrast, diesel-powered vehicles produce N2O in abundance, probably a consequence of selective catalytic reduction of NOx, and the reduction efficiency depends on the converter temperature. In other words, the catalytic converters act as sinks and sources of N2O to the atmosphere in gasoline- and diesel-operated vehicles, respectively. We also report a new set of field data by measuring the isotopic compositions of CO2 and N2O in the Hsuehshan tunnel, a ∼13 km long highway tunnel in Taiwan. Elevated N2O concentrations inside the tunnel indicate that the emission of N2O by heavy-duty diesel vehicles is much higher compared to the reduction by gasoline-operated passenger cars, making the vehicular exhausts a net source of N2O to the atmosphere. The combined study of clumped isotopes and N2O concentration in exhaust gases suggests that it is useful to probe the operational temperature of catalytic converters and monitor the pollution level in operation, thus providing an opportunity for manufacturers to optimize the catalytic efficiency to reduce the level of toxic pollutants to the environment.

Utilization of Δ17O for nitrate dynamics in a subtropical freshwater reservoir.

Feitsui Reservoir, a freshwater body in Taiwan with minimal anthropogenic stress, meets the water demand for the population of more than five million living in Taipei city. In view of the biogeochemical processes controlling the long-term trophic status of this socio-economically and ecologically important aquatic system, probing the nitrogen cycle and its dynamics is essential. Here, we monitored the concentration and stable isotopic compositions (δ15N, δ18O, and Δ17O) of nitrate in the Feitsui Reservoir and in the atmospheric wet deposition at intervals of 1-2 weeks for a year, along with measurements of environmental data such as chlorophyll a, dissolved oxygen, and community respiration. Emphasis was laid on Δ17O (= δ17O - 0.52 × Î´18O) because of the mass-conservative behavior of Δ17O during partial assimilation and denitrification. The present approach offered an effective method to quantify the gross nitrification and removal/uptake rates of nitrate in the reservoir. The atmospheric nitrate exhibited elevated Δ17O values ranging from 12.6‰ to 30.1‰ (23.3 ± 5.0‰), compared to the lower Δ17O values of ~0 to 4.6‰ (1.1 ± 0.7‰) recorded in the reservoir nitrate. Utilizing Δ17O for dissolved nitrates, we observed a seasonal trend of higher nitrification and removal rates during the summer than in the winter. Our estimates showed annually-averaged nitrification rate of 55 ± 11 mmol m-2 d-1 and removal/uptake rate of 57 ± 11 mmol m-2 d-1 (or a nitrate turnover time of ~2.5 months), representing the active nature of nitrogen cycling in this preserved subtropical reservoir.

Variable thermoregulation of Late Cretaceous dinosaurs inferred by clumped isotope analysis of fossilized eggshell carbonates.

The thermal physiology of non-avian dinosaurs, especially the endothermic/ectothermic nature of their metabolism, inferred indirectly using body mass, biophysical modelling, bone histology and growth rate, has long been a matter of debate. Clumped isotope thermometry, based on the thermodynamically driven preference of 13C-18O bond in carbonate minerals of fossilized eggshells, yields temperature of egg formation in the oviduct and can delineate the nature of thermoregulation of some extinct dinosaur taxa. In the present study, the clumped isotope thermometry was applied to the eggshells of a few species of modern birds and reptiles to show that it is possible to obtain the body temperatures of these species in most of the cases. We then used this method to the fossil eggshells of Late Cretaceous sauropods and theropods recovered from western and central India. The estimated body temperatures varied between 29 °C and 46 °C, with an overall average of 37 °C, significantly higher than the environmental temperature (about 25 °C) of this region during the Late Cretaceous. The results also show that the theropod species with low body masses (~800 kg) had high body temperature (~38 °C), while some gigantic (~20000 kg) sauropods had low body temperatures that were comparable to or slightly higher than the environmental temperature. Our analyses suggest that these Late Cretaceous giant species were endowed with a capacity of variable thermoregulation to control their body temperature.

Ab initio quantum chemical studies of isotopic fractionation during acid digestion reaction of dolomite for clumped isotope application.

RATIONALE: In 'clumped isotope paleothermometry' carbonates are reacted with anhydrous phosphoric acid to extract CO2 that carries the isotopic signature of the reacting carbonates, and the amount of clumping in the product CO2 is measured. Previous theoretical models for determining clumped isotopic fractionation in product CO2 during acid digestion of carbonates are independent of the cations present in the carbonate lattice. Hence further study is required to understand the cationic effect. METHODS: We studied the acid reaction mechanism based on the protonation of carbonates, calculated the acid fractionation factor for dolomite using the partition functions and vibrational frequencies obtained for the transition state structure, and determined the effect of cations on the acid fractionation factor. Experimentally, carbonates are reacted using the modified sealed vessel method and analyzed in the dual inlet of a ThermoFinnigan MAT 253 isotope ratio mass spectrometer. RESULTS: The oretically obtained acid fractionation factor can be expressed as Δ47 acid fractionation in dolomite = -0.28563 + 0.49508 * (105 /T2 ) - 0.08231 * (105 /T2 )2 for a temperature range between 278.15 and 383.15 K. The theoretical slope of the dolomite-acid digestion curve is lower than that of the calcite-acid digestion curve obtained using the identical reaction mechanism. Our theoretical slope is consistent with the result from the common acid bath experiments but higher than the slope obtained in our experimental study using the modified sealed vessel method and in a previous theoretical study using the H2 CO3 model. CONCLUSIONS: The transition state structure, obtained in our study, includes the cations present in the carbonate minerals and provides distinct acid fractionation factors for calcite and dolomite. The observed gentler slope of the theoretically calculated dolomite-acid digestion curve than of the calcite curve is expected considering the stronger Mg-O bond. Our experimental approach invokes post-digestion isotopic exchange and agrees with the previous theoretical estimates where post-digestion isotopic fractionation was considered.

A new perspective of probing the level of pollution in the megacity Delhi affected by crop residue burning using the triple oxygen isotope technique in atmospheric CO2.

Air quality in the megacity Delhi is affected not only by local emissions but also by pollutants from crop residue burning in the surrounding areas of the city, particularly the rice straw burning in the post monsoon season. As a major burning product, gaseous CO2, which is rather inert in the polluted atmosphere, provides an alternative solution to characterize the impact of biomass burning from a new perspective that other common tracers such as particulate matters are limited because of their physical and chemical reactiveness. Here, we report conventional ([CO2], δ13C, and δ18O) and unconventional (Δ17O) isotope data for CO2 collected at Connaught Place (CP), a core area in the megacity Delhi, and two surrounding remote regions during a field campaign in October 18-20, 2017. We also measured the isotopic ratios near a rice straw burning site in Taiwan to constrain their end member isotopic compositions. Rice straw burning produces CO2 with δ13C, δ18O, and Δ17O values of -29.02 ± 0.65, 19.63 ± 1.16, and 0.05 ± 0.02‰, respectively. The first two isotopic tracers are less distinguishable from those emitted by fossil fuel combustion but the last one is significantly different. We then utilize these end member isotopic ratios, with emphasis on Δ17O for the reason given above, for partitioning sources that affect the CO2 level in Delhi. Anthropogenic fraction of CO2 at CP ranges from 4 to 40%. Further analysis done by employing a three-component (background, rice straw burning, and fuel combustion) mixing model with constraints from the Δ17O values yields that rice straw burning contributes as much as ∼70% of the total anthropogenic CO2, which is more than double of the fossil fuel contribution (∼30%), during the study days.

Sulfur isotope analysis for representative regional background atmospheric aerosols collected at Mt. Lulin, Taiwan.

Air pollution resulted from fossil fuel burning has been an environmental issue in developing countries in Asia. Sulfur-bearing compounds, in particular, are species that are regulated and monitored routinely. To assess how the species affect at local and global scales, regional background level has to be defined. Here, we report analysis of sulfur isotopes in atmospheric sulfate, the oxidation end product of sulfur species, in particulate phase collected at the Lulin observatory located at 2862 m above mean sea level in 2010. The averaged sulfate concentration for 44 selected samples is 2.7 ± 2.3 (1-σ standard deviation) µg m-3, and the averaged δ34S is 2.2 ± 1.6‰, with respect to the international standard Vienna Canyon Diablo Troilite. Regardless of the origins of air masses, no noticeable difference between the low-altitude Pacific and high-altitude free troposphere sulfate aerosols is observed. Also, no identifiable seasonal cycle in seen. Correlation analysis with respect to coal burning tracers such as lead and oil industry tracers such as vanadium shows sulfate concentration is in better correlation with vanadium (R2 = 0.86, p-value < 0.001) than with lead (R2 = 0.45, p-value < 0.001) but no statistically significant correlation is found in δ34S with any of physical quantities measured. We suggest the sulfate collected at Lulin can best represent the regional background level in the Western Pacific, a quantity that is needed in order to quantitatively assess the budget of sulfur in local to country scales.

Global 3-D Simulations of the Triple Oxygen Isotope Signature Δ17O in Atmospheric CO2.

The triple oxygen isotope signature Δ17O in atmospheric CO2, also known as its "17O excess," has been proposed as a tracer for gross primary production (the gross uptake of CO2 by vegetation through photosynthesis). We present the first global 3-D model simulations for Δ17O in atmospheric CO2 together with a detailed model description and sensitivity analyses. In our 3-D model framework we include the stratospheric source of Δ17O in CO2 and the surface sinks from vegetation, soils, ocean, biomass burning, and fossil fuel combustion. The effect of oxidation of atmospheric CO on Δ17O in CO2 is also included in our model. We estimate that the global mean Δ17O (defined as Δ 17 O = ln ( δ 17 O + 1 ) - λ RL · ln ( δ 18 O + 1 ) with λ RL = 0.5229) of CO2 in the lowest 500 m of the atmosphere is 39.6 per meg, which is ∼20 per meg lower than estimates from existing box models. We compare our model results with a measured stratospheric Δ17O in CO2 profile from Sodankylä (Finland), which shows good agreement. In addition, we compare our model results with tropospheric measurements of Δ17O in CO2 from Göttingen (Germany) and Taipei (Taiwan), which shows some agreement but we also find substantial discrepancies that are subsequently discussed. Finally, we show model results for Zotino (Russia), Mauna Loa (United States), Manaus (Brazil), and South Pole, which we propose as possible locations for future measurements of Δ17O in tropospheric CO2 that can help to further increase our understanding of the global budget of Δ17O in atmospheric CO2.

A global database of water vapor isotopes measured with high temporal resolution infrared laser spectroscopy.

The isotopic composition of water vapour provides integrated perspectives on the hydrological histories of air masses and has been widely used for tracing physical processes in hydrological and climatic studies. Over the last two decades, the infrared laser spectroscopy technique has been used to measure the isotopic composition of water vapour near the Earth's surface. Here, we have assembled a global database of high temporal resolution stable water vapour isotope ratios (δ18O and δD) observed using this measurement technique. As of March 2018, the database includes data collected at 35 sites in 15 Köppen climate zones from the years 2004 to 2017. The key variables in each dataset are hourly values of δ18O and δD in atmospheric water vapour. To support interpretation of the isotopologue data, synchronized time series of standard meteorological variables from in situ observations and ERA5 reanalyses are also provided. This database is intended to serve as a centralized platform allowing researchers to share their vapour isotope datasets, thus facilitating investigations that transcend disciplinary and geographic boundaries.

Distribution of CO2 in Western Pacific, Studied Using Isotope Data Made in Taiwan, OCO-2 Satellite Retrievals, and CarbonTracker Products.

To assess sources and processes that affect the variability of CO2 at local to regional scales, we have analyzed the mixing ratio [CO2] and stable isotopic compositions (δ13C and δ18O) of atmospheric CO2 for three years (2014-2016) in urban and sub-urban areas in Taipei, Taiwan. The data are compared with those from some background sites, viz., Lulin, Mauna Loa, and Minamitorishima, to evaluate how local emissions affect CO2 level regionally. [CO2] over the urban and sub-urban stations are significantly higher than that observed at the three aforementioned remote sites mainly due to local emissions, which partly mask the seasonal cycle caused by photosynthesis and respiration. Likewise, significantly low δ13C and δ18O values observed at two Taipei stations also point to anthropogenic emissions. The seasonal cycles in [CO2] and in the isotopic compositions are retrieved using the ensemble empirical mode decomposition method. Regional impact is assessed using CO2 products from the Orbiting Carbon Observatory-2 satellite, the NOAA/EARL CarbonTracker project, and meteorological data from European Centre for Medium range Weather Forecast-Interim. We found that besides local emissions, Taiwan is largely affected by external CO2 in winter and spring originated from north, west and southwest landmasses. In winter air masses with elevated CO2 concentrations, originated in eastern China influence Taipei. In spring season, about 2 ppmv enhancement in CO2 observed at the top of Lulin, a high mountain station (2.8 km), could be linked to CO2 produced by biomass burning in the southeast Asian countries and transported to the region by easterly winds.

Oxygen isotope anomaly in tropospheric CO2 and implications for CO2 residence time in the atmosphere and gross primary productivity.

The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, Δ17O (=ln(1 + δ17O) - 0.516 × ln(1 + δ18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we analyze Δ17O data from four places (Taipei, Taiwan; South China Sea; La Jolla, United States; Jerusalem, Israel) in the northern hemisphere (with a total of 455 measurements) and find a rather narrow range (0.326 ± 0.005‰). A conservative estimate places a lower limit of 345 ± 70 PgC year-1 on the cycling flux between the terrestrial biosphere and atmosphere and infers a residence time of CO2 of 1.9 ± 0.3 years (upper limit) in the atmosphere. A Monte Carlo simulation that takes various plant uptake scenarios into account yields a terrestrial gross primary productivity of 120 ± 30 PgC year-1 and soil invasion of 110 ± 30 PgC year-1, providing a quantitative assessment utilizing the oxygen isotope anomaly for quantifying CO2 cycling.

Identification of Anthropogenic CO2 Using Triple Oxygen and Clumped Isotopes.

Quantification of contributions from various sources of CO2 is important for understanding the atmospheric CO2 budget. Considering the number and diversity of sources and sinks, the widely used proxies such as concentration and conventional isotopic compositions (δ13C and δ18O) are not always sufficient to fully constrain the CO2 budget. Additional constraints may help in understanding the mechanisms of CO2 production and consumption. The anomaly in triple oxygen isotopes or 17O excess (denoted by Δ17O) and molecules containing two rare isotopes, called clumped isotopes, are two recently developed tracers with potentials to independently constrain some important processes that regulate CO2 in the atmosphere. The clumped isotope for CO2, denoted by Δ47, is the excess of 13C16O18O over a random distribution of isotopes in a CO2 molecule. We measured the concentrations of δ13C, δ18O, Δ17O, and Δ47 in air CO2 samples collected from the Hsuehshan tunnel (length: 12.9 km), and applied linear and polynomial regressions to obtain the fossil fuel end-members for all these isotope proxies. The other end-members, the values of all these proxies for background air CO2, are either assumed or taken as the values obtained over the tunnel and ocean. The fossil fuel (anthropogenic) CO2 end-member values for δ13C, δ18O, Δ17O, and Δ47 are estimated using the two component mixing approach: the derived values are -26.76 ± 0.25‰, 24.57 ± 0.33‰, -0.219 ± 0.021‰, and 0.267 ± 0.036‰, respectively. These four major CO2 isotope tracers along with the concentration were used to estimate the anthropogenic contribution in the atmospheric CO2 in urban and suburban locations. We demonstrate that Δ17O and Δ47 have the potential to independently estimate anthropogenic contribution, and the advantages of these two over the conventional isotope proxies are discussed.

Development of a multicopter-carried whole air sampling apparatus and its applications in environmental studies.

To advance the capabilities of probing chemical composition aloft, we designed a lightweight remote-controlled whole air sampling component (WASC) and integrated it into a multicopter drone with agile maneuverability to perform aerial whole air sampling. A field mission hovering over an exhaust shaft of a roadway tunnel to collect air samples was performed to demonstrate the applicability of the multicopter-carried WASC apparatus. Ten aerial air samples surrounding the shaft vent were collected by the multicopter-carried WASC. Additional five samples were collected manually inside the shaft for comparison. These samples were then analyzed in the laboratory for the chemical composition of 109 volatile organic compounds (VOCs), CH4, CO, CO2, or CO2 isotopologues. Most of the VOCs in the upwind samples (the least affected by shaft exhaust) were low in concentrations (5.9 ppbv for total 109 VOCs), posting a strong contrast to those in the shaft exhaust (235.8 ppbv for total 109 VOCs). By comparing the aerial samples with the in-shaft samples for chemical compositions, the influence of the shaft exhaust on the surrounding natural air was estimated. Through the aerial measurements, three major advantages of the multicopter-carried WASC were demonstrated: 1. The highly maneuverable multicopter-carried WASC can be readily deployed for three-dimensional environmental studies at a local scale (0-1.5 km); 2. Aerial sampling with superior sample integrity and preservation conditions can now be performed with ease; and 3. Data with spatial resolution for a large array of gaseous species with high precision can be easily obtained.

An improved method of high-precision determination of Δ(17)O of CO2 by catalyzed exchange with O2 using hot platinum.

RATIONALE: CO2 and O2 can exchange their oxygen isotopes rapidly in the presence of hot (~670 °C) platinum and this has led to a method for determining the δ(17)O value of a CO2 sample. We have improved the method to achieve a precision of 0.008 ‰ (1-σ standard deviation) in the determination of δ(17)O values. Such high precision is essential to identify the stratospheric component in tropospheric CO2 and use it for global carbon flux studies. The crucial issue in the accurate determination of the δ(17)O value is estimation of a correction factor, which depends on the amount ratio CO2/O2. An attempt was also made to investigate the mechanism of exchange with their controlling parameters. METHODS: The oxygen isotopes of a CO2 sample gas are exchanged with those of an appropriate amount of tank O2 in the presence of hot platinum. The pre-exchange CO2 and O2 gas samples as well as the post-exchange O2 sample are analyzed by isotope ratio mass spectrometry. A mixing model was developed involving the δ(18)O value of the CO2 and δ(17)O and δ(18)O values of pre- and post-exchange O2 to obtain the δ(17)O value of the CO2 sample. A correction to the measured value was determined to obtain the actual value with high accuracy and precision. RESULTS: To obtain a precision better than 0.01 ‰ requires the amount ratio CO2/O2 to be controlled to better than ~15 %. We also find that the oxygen isotopes are nearly homogeneously distributed between the O2 and the CO2 molecules. In addition, determination of the (16) O(13)C(18)O/(16)O(12)C(16)O isotopologue ratio in the CO2 shows that the abundance of (16)O(13)C(18)O is close to that expected for random partitioning of the isotopes among the CO2 isotopologues. CONCLUSIONS: The isotopic scrambling between O2 and CO2 that occurs on hot platinum allows one to accurately determine the δ(17)O values of CO2 through isotopic analysis of O2.

Oxygen anomaly in near surface carbon dioxide reveals deep stratospheric intrusion.

Stratosphere-troposphere exchange could be enhanced by tropopause folding, linked to variability in the subtropical jet stream. Relevant to tropospheric biogeochemistry is irreversible transport from the stratosphere, associated with deep intrusions. Here, oxygen anomalies in near surface air CO2 are used to study the irreversible transport from the stratosphere, where the triple oxygen isotopes of CO2 are distinct from those originating from the Earth's surface. We show that the oxygen anomaly in CO2 is observable at sea level and the magnitude of the signal increases during the course of our sampling period (September 2013-February 2014), concordant with the strengthening of the subtropical jet system and the East Asia winter monsoon. The trend of the anomaly is found to be 0.1‰/month (R(2) = 0.6) during the jet development period in October. Implications for utilizing the oxygen anomaly in CO2 for CO2 biogeochemical cycle study and stratospheric intrusion flux at the surface are discussed.

A new feature in the internal heavy isotope distribution in ozone.

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ((18)O/(16)O and (17)O/(16)O ratio) which does not follow normal mass fractionation rule: δ(17)O ∼ 0.52(*)δ(18)O, expressed as an anomaly Δ(17)O = δ(17)O - 0.52(*)δ(18)O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ(18)O (s) or δ(18)O (as) (and similarly for δ(17)O) as well as position dependent isotope anomaly Δ(17)O (s) and Δ(17)O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ(17)O (s) is zero. Consequently, Δ(17)O (as) = 1.5 (*) Δ(17)O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

Interlaboratory assessment of nitrous oxide isotopomer analysis by isotope ratio mass spectrometry and laser spectroscopy: current status and perspectives.

RATIONALE: In recent years, research and applications of the N2O site-specific nitrogen isotope composition have advanced, reflecting awareness of the contribution of N2O to the anthropogenic greenhouse effect, and leading to significant progress in instrument development. Further dissemination of N2O isotopomer analysis, however, is hampered by a lack of internationally agreed gaseous N2O reference materials and an uncertain compatibility of different laboratories and analytical techniques. METHODS: In a first comparison approach, eleven laboratories were each provided with N2O at tropospheric mole fractions (target gas T) and two reference gases (REF1 and REF2). The laboratories analysed all gases, applying their specific analytical routines. Compatibility of laboratories was assessed based on N2O isotopocule data for T, REF1 and REF2. Results for T were then standardised using REF1 and REF2 to evaluate the potential of N2O reference materials for improving compatibility between laboratories. RESULTS: Compatibility between laboratories depended on the analytical technique: isotope ratio mass spectrometry (IRMS) results showed better compatibility for δ(15)N values, while the performance of laser spectroscopy was superior with respect to N2O site preference. This comparison, however, is restricted by the small number of participating laboratories applying laser spectroscopy. Offset and two-point calibration correction of the N2O isotopomer data significantly improved the consistency of position-dependent nitrogen isotope data while the effect on δ(15)N values was only minor. CONCLUSIONS: The study reveals that for future research on N2O isotopocules, standardisation against N2O reference material is essential to improve interlaboratory compatibility. For atmospheric monitoring activities, we suggest N2O in whole air as a unifying scale anchor.