Leaf-scale quantification of the effect of photosynthetic gas exchange on δ ¹⁷O of atmospheric CO ₂

Understanding the processes that affect the triple oxygen isotope composition of atmospheric CO2during gas exchange can help constrain the interaction and fluxes between the atmosphere and the biosphere. We conducted leaf cuvette experiments under controlled conditions using three plant species. The experiments were conducted at two different light intensities and using CO2with different δ17O. We directly quantify the effect of photosynthesis on δ17O of atmospheric CO2for the first time. Our results demonstrate the established theory for δ18O is applicable to δ17O.CO2/at leaf level, and we confirm that the following two key factors determine the effect of photosynthetic gas exchange on the δ17O of atmospheric CO2. The relative difference between δ17O of the CO2entering the leaf and the CO2in equilibrium with leaf water and the back-diffusion flux of CO2from the leaf to the atmosphere, which can be quantified by the cm=ca ratio, where ca is the CO2mole fraction in the surrounding air and cm is the one at the site of oxygen isotope exchange between CO2and H2O. At low cm=ca ratios the discrimination is governed mainly by diffusion into the leaf, and at high cm=ca ratios it is governed by back-diffusion of CO2that has equilibrated with the leaf water. Plants with a higher cm=ca ratio modify the 117O of atmospheric CO2more strongly than plants with a lower cm=ca ratio. Based on the leaf cuvette experiments, the global value for discrimination against δ17O of atmospheric CO2during photosynthetic gas exchange is estimated to be-0:57±0:14% using cm=ca values of 0.3 and 0.7 for C4and C3plants, respectively. The main uncertainties in this global estimate arise from variation in cm=ca ratios among plants and growth conditions.</p

Chemical characterization of organic particulate matter from on-road traffic in Sao Paulo, Brazil

This study reports emission of organic particulate matter by light-duty vehicles (LDVs) and heavy-duty vehicles (HDVs) in the city of São Paulo, Brazil, where vehicles run on three different fuel types: gasoline with 25 % ethanol (called gasohol, E25), hydrated ethanol (E100), and diesel (with 5 % biodiesel). The experiments were performed at two tunnels: Jânio Quadros (TJQ), where 99 % of the vehicles are LDVs, and RodoAnel Mário Covas (TRA), where up to 30 % of the fleet are HDVs. Fine particulate matter (PM2.5) samples were collected on quartz filters in May and July 2011 at TJQ and TRA, respectively. The samples were analyzed by thermal-desorption proton-transfer-reaction mass spectrometry (TD-PTR-MS) and by thermal–optical transmittance (TOT). Emission factors (EFs) for organic aerosol (OA) and organic carbon (OC) were calculated for the HDV and the LDV fleet. We found that HDVs emitted more PM2.5 than LDVs, with OC EFs of 108 and 523 mg kg−1 burned fuel for LDVs and HDVs, respectively. More than 700 ions were identified by TD-PTR-MS and the EF profiles obtained from HDVs and LDVs exhibited distinct features. Unique organic tracers for gasoline, biodiesel, and tire wear have been tentatively identified. nitrogen-containing compounds contributed around 20 % to the EF values for both types of vehicles, possibly associated with incomplete fuel burning or fast secondary production. Additionally, 70 and 65 % of the emitted mass (i.e. the OA) originates from oxygenated compounds from LDVs and HDVs, respectively. This may be a consequence of the high oxygen content of the fuel. On the other hand, additional oxygenation may occur during fuel combustion. The high fractions of nitrogen- and oxygen-containing compounds show that chemical processing close to the engine / tailpipe region is an important factor influencing primary OA emission. The thermal-desorption analysis showed that HDVs emitted compounds with higher volatility, and with mainly oxygenated and longer chain hydrocarbons than LDVs

Development and evaluation of a suite of isotope reference gases for methane in air

Measurements from multiple laboratories have to be related to unifying and traceable reference material in order to be comparable. However, such fundamental reference materials are not available for isotope ratios in atmospheric methane, which led to misinterpretations of combined data sets in the past. We developed a method to produce a suite of synthetic CH4-in-air standard gases that can be used to unify methane isotope ratio measurements of laboratories in the atmospheric monitoring community. Therefore, we calibrated a suite of pure methane gases of different methanogenic origin against international referencing materials that define the VSMOW (Vienna Standard Mean Ocean Water) and VPDB (Vienna Pee Dee Belemnite) isotope scales. The isotope ratios of our pure methane gases range between -320 and +40% for delta H-2-CH4 and between -70 and -40% for delta C-13-CH4, enveloping the isotope ratios of tropospheric methane (about -85 and -47% for delta H-2-CH4 and delta C-13-CH4 respectively). Estimated uncertainties, including the full traceability chain, are</p

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy:method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, µmole mole−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition

Gravitational Radiation from Gamma-Ray Burst Progenitors

We study gravitational radiation from various proposed gamma-ray burst (GRB) progenitor models, in particular compact mergers and massive stellar collapses. These models have in common a high angular rotation rate, and the final stage involves a rotating black hole and accretion disk system. We consider the in-spiral, merger and ringing phases, and for massive collapses we consider the possible effects of asymmetric collapse and break-up, as well bar-mode instabilities in the disks. We calculate the strain and frequency of the gravitational waves expected from various progenitors, at distances based on occurrence rate estimates. Based on simplifying assumptions, we give estimates of the probability of detection of gravitational waves by the advanced LIGO system from the different GRB scenarios.Comment: 26 pages, 5 figures, accepted for publication in Ap

Methane Feedbacks to the Global Climate System in a Warmer World

Methane (CH4) is produced in many natural systems that are vulnerable to change under a warming climate, yet current CH4 budgets, as well as future shifts in CH4 emissions, have high uncertainties. Climate change has the potential to increase CH4 emissions from critical systems such as wetlands, marine and freshwater systems, permafrost, and methane hydrates, through shifts in temperature, hydrology, vegetation, landscape disturbance, and sea level rise. Increased CH4 emissions from these systems would in turn induce further climate change, resulting in a positive climate feedback. Here we synthesize biological, geochemical, and physically focused CH4 climate feedback literature, bringing together the key findings of these disciplines. We discuss environment-specific feedback processes, including the microbial, physical, and geochemical interlinkages and the timescales on which they operate, and present the current state of knowledge of CH4 climate feedbacks in the immediate and distant future. The important linkages between microbial activity and climate warming are discussed with the aim to better constrain the sensitivity of the CH4 cycle to future climate predictions. We determine that wetlands will form the majority of the CH4 climate feedback up to 2100. Beyond this timescale, CH4 emissions from marine and freshwater systems and permafrost environments could become more important. Significant CH4 emissions to the atmosphere from the dissociation of methane hydrates are not expected in the near future. Our key findings highlight the importance of quantifying whether CH4 consumption can counterbalance CH4 production under future climate scenarios