Martin Graus

Bio: Martin Graus is an academic researcher from University of Innsbruck. The author has contributed to research in topics: Isoprene & Eddy covariance. The author has an hindex of 41, co-authored 111 publications receiving 4730 citations. Previous affiliations of Martin Graus include Earth System Research Laboratory & Colorado State University.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin

Abstract: Data from the oil- and gas-producing basin of northeastern Utah and a box model are used to assess the photochemical reactions of nitrogen oxides and volatile organic compounds that lead to excessive atmospheric ozone pollution in winter. The US experience with air quality degradation from shale gas extraction presents a measurement and modelling framework relevant to similar developments in other regions projected for the near future. High ozone mixing ratios have been observed in oil and gas producing basins in the United States during winter, but the underlying chemistry involved is not fully understood. This study presents a quantitative assessment of the underlying chemistry responsible for the winter ozone pollution events based on data from an oil and gas basin in Utah and a chemical 'box model' simulation. The results show that very high volatile organic carbon concentrations optimize the ozone production efficiency of nitrogen oxides with carbonyl photolysis as a dominant oxidant source. The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality1 to the influence of increased methane leakage on climate2, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides3,4 (NOx = NO + NO2) and volatile organic compounds5,6,7 (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects8. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter9,10,11,12,13. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

On-line breath analysis with PTR-TOF.

Abstract: We report on on-line breath gas analysis with a new type of analytical instrument, which represents the next generation of proton-transfer-reaction mass spectrometers. This time-of-flight mass spectrometer in combination with the soft proton-transfer-reaction ionization (PTR-TOF) offers numerous advantages for the sensitive detection of volatile organic compounds and overcomes several limitations. First, a time-of-flight instrument allows for a measurement of a complete mass spectrum within a fraction of a second. Second, a high mass resolving power enables the separation of isobaric molecules and the identification of their chemical composition. We present the first on-line breath measurements with a PTR-TOF and demonstrate the advantages for on-line breath analysis. In combination with buffered end-tidal (BET) sampling, we obtain a complete mass spectrum up to 320 Th within one exhalation with a signal-to-noise ratio sufficient to measure down to pptv levels. We exploit the high mass resolving power to identify the main components in the breath composition of several healthy volunteers.

A large and ubiquitous source of atmospheric formic acid

Abstract: . Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

Contribution of Different Carbon Sources to Isoprene Biosynthesis in Poplar Leaves

Abstract: This study was performed to test if alternative carbon sources besides recently photosynthetically fixed CO2 are used for isoprene formation in the leaves of young poplar (Populus x canescens) trees. In a 13CO2 atmosphere under steady state conditions, only about 75% of isoprene became 13C labeled within minutes. A considerable part of the unlabeled carbon may be derived from xylem transported carbohydrates, as may be shown by feeding leaves with [U-13C]Glc. As a consequence of this treatment approximately 8% to 10% of the carbon emitted as isoprene was 13C labeled. In order to identify further carbon sources, poplar leaves were depleted of leaf internal carbon pools and the carbon pools were refilled with 13C labeled carbon by exposure to 13CO2. Results from this treatment showed that about 30% of isoprene carbon became 13C labeled, clearly suggesting that, in addition to xylem transported carbon and CO2, leaf internal carbon pools, e.g. starch, are used for isoprene formation. This use was even increased when net assimilation was reduced, for example by abscisic acid application. The data provide clear evidence of a dynamic exchange of carbon between different cellular precursors for isoprene biosynthesis, and an increasing importance of these alternative carbon pools under conditions of limited photosynthesis. Feeding [1,2-13C]Glc and [3-13C]Glc to leaves via the xylem suggested that alternative carbon sources are probably derived from cytosolic pyruvate/phosphoenolpyruvate equivalents and incorporated into isoprene according to the predicted cleavage of the 3-C position of pyruvate during the initial step of the plastidic deoxyxylulose-5-phosphate pathway.

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation

Abstract: Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100–1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H_(2)SO_(4)–H_(2)O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Secondary Organic Aerosol Formation from Anthropogenic Air Pollution: Rapid and Higher than Expected

Abstract: [1] The atmospheric chemistry of volatile organic compounds (VOCs) in urban areas results in the formation of ‘photochemical smog’, including secondary organic aerosol (SOA). State-of-the-art SOA models parameterize the results of simulation chamber experiments that bracket the conditions found in the polluted urban atmosphere. Here we show that in the real urban atmosphere reactive anthropogenic VOCs (AVOCs) produce much larger amounts of SOA than these models predict, even shortly after sunrise. Contrary to current belief, a significant fraction of the excess SOA is formed from first-generation AVOC oxidation products. Global models deem AVOCs a very minor contributor to SOA compared to biogenic VOCs (BVOCs). If our results are extrapolated to other urban areas, AVOCs could be responsible for additional 3–25 Tg yr−1 SOA production globally, and cause up to −0.1 W m−2 additional top-of-the-atmosphere radiative cooling.

Formation of Urban Fine Particulate Matter

Abstract: Urban air pollution represents one of the greatest environmental challenges facing mankind in the 21st century. Noticeably, many developing countries, such as China and India, have experienced severe air pollution because of their fast-developing economy and urbanization. Globally, the urbanization trend is projected to continue: 70% of the world population will reside in urban centers by 2050, and there will exist 41 megacities (with more than 10 million inhabitants) by 2030. Air pollutants consist of a complex combination of gases and particulate matter (PM). In particular, fine PM (particles with the aerodynamic diameter smaller than 2.5 μm or PM_(2.5)) profoundly impacts human health, visibility, the ecosystem, the weather, and the climate, and these PM effects are largely dependent on the aerosol properties, including the number concentration, size, and chemical composition. PM is emitted directly into the atmosphere (primary) or formed in the atmosphere through gas-to-particle conversion (secondary) (Figure 1). Also, primary and secondary PM undergoes chemical and physical transformations and is subjected to transport, cloud processing, and removal from the atmosphere.

Tropospheric ozone and its precursors from the urban to the global scale from air quality to short-lived climate forcer

Abstract: Ozone holds a certain fascination in atmospheric science. It is ubiquitous in the atmosphere, central to tropospheric oxidation chemistry, yet harmful to human and ecosystem health as well as being an important greenhouse gas. It is not emitted into the atmosphere but is a by-product of the very oxidation chemistry it largely initiates. Much effort is focussed on the reduction of surface levels of ozone owing to its health impacts but recent efforts to achieve reductions in exposure at a country scale have proved difficult to achieve due to increases in background ozone at the zonal hemispheric scale. There is also a growing realisation that the role of ozone as a short-lived climate pollutant could be important in integrated air quality climate-change mitigation. This review examines current understanding of the processes regulating tropospheric ozone at global to local scales from both measurements and models. It takes the view that knowledge across the scales is important for dealing with air quality and climate change in a synergistic manner.