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.

Measurement of 18 O18 O and 17 O18 O in atmospheric O2 using the 253 Ultra mass spectrometer and applications to stratospheric and tropospheric air samples.

RATIONALE: The doubly substituted isotopologues (e.g., 18 O18 O, 17 O18 O) in atmospheric O2 are potential tracers for ozone photochemistry and atmospheric temperatures. Their low abundances and isobaric interference are the major analytical challenges. The 253 Ultra high-resolution stable isotope ratio mass spectrometer is suitable for resolving isobaric interferences. METHODS: O2 from air is purified using gas chromatography on a packed column filled with molecular sieve 5 Å and cooled to -78°C. The δ17 O, δ18 O, Δ17 O, Δ35 and Δ36 values are measured on the extracted O2 with the 253 Ultra at medium mass resolution (M/ΔM ~10000) using Faraday detectors for the singly substituted isotopologues and ion counters for the doubly substituted isotopologues. RESULTS: Interferences from isobars, mainly 35 Cl for 17 O18 O and H35 Cl and 36 Ar for 18 O18 O, are sufficiently resolved to enable high-precision determination of Δ35 and Δ36 . The Δ35 and Δ36 values of O2 after photochemical isotope equilibration at -63°C and heating to 850°C agree with the theoretical prediction. The stratospheric Δ35 and Δ36 values are close to isotopic equilibrium at the ambient temperatures. However, the values for tropospheric O2 differ from those expected at equilibrium. CONCLUSIONS: The 253 Ultra allows interference-free clumped isotope measurements of O2 at medium mass resolution. The Δ35 and Δ36 signatures in atmospheric O2 are mainly governed by O3 photochemistry, temperature and atmospheric transport. Tropospheric O2 is isotopically well mixed and retains a significant stratospheric signature.

Determination of the triple oxygen and carbon isotopic composition of CO2 from atomic ion fragments formed in the ion source of the 253 Ultra high-resolution isotope ratio mass spectrometer.

RATIONALE: Determination of δ17 O values directly from CO2 with traditional gas source isotope ratio mass spectrometry is not possible due to isobaric interference of 13 C16 O16 O on 12 C17 O16 O. The methods developed so far use either chemical conversion or isotope equilibration to determine the δ17 O value of CO2 . In addition, δ13 C measurements require correction for the interference from 12 C17 O16 O on 13 C16 O16 O since it is not possible to resolve the two isotopologues. METHODS: We present a technique to determine the δ17 O, δ18 O and δ13 C values of CO2 from the fragment ions that are formed upon electron ionization in the ion source of the Thermo Scientific 253 Ultra high-resolution isotope ratio mass spectrometer (hereafter 253 Ultra). The new technique is compared with the CO2 -O2 exchange method and the 17 O-correction algorithm for δ17 O and δ13 C values, respectively. RESULTS: The scale contractions for δ13 C and δ18 O values are slightly larger for fragment ion measurements than for molecular ion measurements. The δ17 O and Δ17 O values of CO2 can be measured on the 17 O+ fragment with an internal error that is a factor 1-2 above the counting statistics limit. The ultimate precision depends on the signal intensity and on the total time that the 17 O+ beam is monitored; a precision of 14 ppm (parts per million) (standard error of the mean) was achieved in 20 hours at the University of Göttingen. The Δ17 O measurements with the O-fragment method agree with the CO2 -O2 exchange method over a range of Δ17 O values of -0.3 to +0.7‰. CONCLUSIONS: Isotope measurements on atom fragment ions of CO2 can be used as an alternative method to determine the carbon and oxygen isotopic composition of CO2 without chemical processing or corrections for mass interferences.

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.

Gravitational sampling electrospray ionization mass spectrometry for real-time reaction monitoring.

RATIONALE: The elucidation of chemical reaction mechanisms has attracted tremendous interest in recent years. Here, gravitational sampling electrospray ionization mass spectrometry (GS-ESI-MS) is used to explore a simple method for the real-time monitoring of chemical and biochemical reactions. METHODS: A sample solution in a stainless steel sample well is directly delivered through a fused-silica capillary due to the forces of gravity, capillary action, and electroosmotic flow (EOF). Analyte ions are continuously generated via electrospray ionization from the capillary tip when a high voltage is applied on the sample well. RESULTS: Liquid solutions (<5 µL) of small organic compounds (e.g., crystal violet) and large biomolecules (e.g., reserpine, angiotensin II, and insulin) were directly analyzed via GS-ESI-MS. In addition, the technique was successfully applied to continuously monitor chemical [e.g. chelation of ethylenediaminetetraacetic acid (EDTA) with copper(II), and addition-elimination of aminophenol and acetic anhydride] and biochemical (e.g., unfolding of cytochrome c) reactions in real time, where chelation complexes, reaction intermediates, and protein conformation changes were observed. CONCLUSIONS: GS-ESI-MS is a very simple modification of the ESI technique that does not require sample delivery pumps or nebulizer gases. It is particularly suitable for the analysis of liquid samples and the real-time monitoring of inorganic/organic chemical or biochemical reactions.

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.

Southern hemisphere forced millennial scale Indian summer monsoon variability during the late Pleistocene.

Peninsular India hosts the initial rain-down of the Indian Summer Monsoon (ISM) after which winds travel further east inwards into Asia. Stalagmite oxygen isotope composition from this region, such as those from Belum Cave, preserve the vital signals of the past ISM variability. These archives experience a single wet season with a single dominant moisture source annually. Here we present high-resolution δ18O, δ13C and trace element (Mg/Ca, Sr/Ca, Ba/Ca, Mn/Ca) time series from a Belum Cave stalagmite spanning glacial MIS-6 (from ~ 183 to ~ 175 kyr) and interglacial substages MIS-5c-5a (~ 104 kyr to ~ 82 kyr). With most paleomonsoon reconstructions reporting coherent evolution of northern hemisphere summer insolation and ISM variability on orbital timescale, we focus on understanding the mechanisms behind millennial scale variability. Finding that the two are decoupled over millennial timescales, we address the role of the Southern Hemisphere processes in modulating monsoon strength as a part of the Hadley circulation. We identify several strong and weak episodes of ISM intensity during 104-82 kyr. Some of the weak episodes correspond to warming in the southern hemisphere associated with weak cross-equatorial winds. We show that during the MIS-5 substages, ISM strength gradually declined with millennial scale variability linked to Southern Hemisphere temperature changes which in turn modulate the strength of the Mascarene High.

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.

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.

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.

Stable carbon isotopes in dissolved inorganic carbon: extraction and implications for quantifying the contributions from silicate and carbonate weathering in the Krishna River system during peak discharge.

We present a comparative study of two offline methods, a newly developed method and an existing one, for the measurement of the stable carbon isotopic composition (δ(13)C) of dissolved inorganic carbon (DIC; δ(13)CDIC) in natural waters. The measured δ(13)CDIC values of different water samples, prepared from laboratory Na2CO3, ground and oceanic waters, and a laboratory carbonate isotope standard, are found to be accurate and reproducible to within 0.5 ‰\ (1σ). The extraction of CO2 from water samples by these methods does not require pre-treatment or sample poisoning and can be applied to a variety of natural waters to address carbon cycling in the hydrosphere. In addition, we present a simple method (based on a two-end-member mixing model) to estimate the silicate-weathering contribution to DIC in a river system by using the concentration of DIC and its δ(13)C. This approach is tested with data from the Krishna River system as a case study, thereby quantifying the contribution of silicate and carbonate weathering to DIC, particularly during peak discharge.