Atmosphere-Ocean Ozone Exchange – A Global Modeling Study of Biogeochemical, Atmospheric and Water-Side Turbulence Dependencies

The significance of the removal of tropospheric ozone by the oceans, covering ~2/3 of the Earth's surface, has only been addressed in a few studies involving water tank, aircraft, and tower flux measurements. On the basis of results from these few observations of the ozone dry deposition velocity (VdO3), atmospheric chemistry models generally apply an empirical, constant ocean uptake rate of 0.05 cm s-1. This value is substantially smaller than the atmospheric turbulent transport velocity for ozone. On the other hand, the uptake is higher than expected from the solubility of ozone in clean water alone, suggesting that there is an enhancement in oceanic ozone uptake, e.g., through a chemical destruction mechanism. We present an evaluation of a global-scale analysis with a new mechanistic representation of atmosphere-ocean ozone exchange. The applied atmosphere chemistry-climate model includes not only atmospheric but also waterside turbulence and the role of waterside chemical loss processes as a function of oceanic biogeochemistry. The simulations suggest a larger role of biogeochemistry in tropical and subtropical ozone oceanic uptake with a relative small temporal variability, whereas in midlatitude and high-latitude regions, highly variable ozone uptake rates are expected because of the stronger influence of waterside turbulence. Despite a relatively large range in the explicitly calculated ocean uptake rate, there is a surprisingly small sensitivity of simulated Marine Boundary Layer ozone concentrations compared to the sensitivity for the commonly applied constant ocean uptake approach. This small sensitivity points at compensating effects through inclusion of the process-based ocean uptake mechanisms to consider variability in oceanic O3 deposition consistent with that in atmospheric and oceanic physical, chemical, and biological processe

Sesquiterpene emissions from vegetation: a review

International audienceThis literature review summarizes the environmental controls governing biogenic sesquiterpene (SQT) emissions and presents a compendium of numerous SQT-emitting plant species as well as the quantities and ratios of SQT species they have been observed to emit. The results of many enclosure-based studies indicate that temporal SQT emission variations appear to be dominated mainly by ambient temperatures although other factors contribute (e.g., seasonal variations). This implies that SQT emissions have increased significance at certain times of the year, especially in late spring to mid-summer. The strong temperature dependency of SQT emissions also creates the distinct possibility of increasing SQT emissions in a warmer climate. Disturbances to vegetation (from herbivores and possibly violent weather events) are clearly also important in controlling short-term SQT emissions bursts, though the relative contribution of disturbance-induced emissions is not known. Based on the biogenic SQT emissions studies reviewed here, SQT emission rates among numerous species have been observed to cover a wide range of values, and exhibit substantial variability between individuals and across species, as well as at different environmental and phenological states. These emission rates span several orders of magnitude (10s?1000s of ng gDW-1 h?1). Many of the higher rates were reported by early SQT studies, which may have included artificially-elevated SQT emission rates due to higher-than-ambient enclosure temperatures and disturbances to enclosed vegetation prior to and during sample collection. When predicting landscape-level SQT fluxes, modelers must consider the numerous sources of variability driving observed SQT emissions. Characterizations of landscape and global SQT fluxes are highly uncertain given differences and uncertainties in experimental protocols and measurements, the high variability in observed emission rates from different species, the selection of species that have been studied so far, and ambiguities regarding controls over emissions. This underscores the need for standardized experimental protocols, better characterization of disturbance-induced emissions, screening of dominant plant species, and the collection of multiple replicates from several individuals within a given species or genus as well as a better understanding of seasonal dependencies of SQT emissions in order to improve the representation of SQT emission rates

The role of ozone atmosphere-snow gas exchange on polar, boundary-layer tropospheric ozone ? a review and sensitivity analysis

International audienceRecent research on snowpack processes and atmosphere-snow gas exchange has demonstrated that chemical and physical interactions between the snowpack and the overlaying atmosphere have a substantial impact on the composition of the lower troposphere. These observations also imply that ozone deposition to the snowpack possibly depends on parameters including the quantity and composition of deposited trace gases, solar irradiance, snow temperature and the substrate below the snowpack. Current literature spans a remarkably wide range of ozone deposition velocities (vdO3); several studies even reported positive ozone fluxes out of the snow. Overall, published values range from ~?

A reassessment of Antarctic plateau reactive nitrogen based on ANTCI 2003 airborne and ground based measurements

The first airborne measurements of nitric oxide (NO) on the Antarctic plateau have demonstrated that the previously reported elevated levels of this species extend well beyond the immediate vicinity of South Pole. Although the current database is still relatively weak and critical laboratory experiments are still needed, the findings here suggest that the chemical uniqueness of the plateau may be substantially greater than first reported. For example, South Pole ground-based findings have provided new evidence showing that the dominant process driving the release of nitrogen from the snowpack during the spring/summer season (post-depositional loss) is photochemical in nature with evaporative processes playing a lesser role. There is also new evidence suggesting that nitrogen, in the form of nitrate, may undergo multiple recycling within a given photochemical season. Speculation here is that this may be a unique property of the plateau and much related to its having persistent cold temperatures even during summer. These conditions promote the efficient adsorption of molecules like HNO3 (and very likely HO2NO2) onto snow-pack surface ice where we have hypothesized enhanced photochemical processing can occur, leading to the efficient release of NOx to the atmosphere. In addition, to these process-oriented tentative conclusions, the findings from the airborne studies, in conjunction with modeling exercises suggest a new paradigm for the plateau atmosphere. The near-surface atmosphere over this massive region can be viewed as serving as much more than a temporary reservoir or holding tank for imported chemical species. It defines an immense atmospheric chemical reactor which is capable of modifying the chemical characteristics of select atmospheric constituents. This reactor has most likely been in place over geological time, and may have led to the chemical modulation of some trace species now found in ice cores. Reactive nitrogen has played a critical role in both establishing and in maintaining this reactor. © 2007 Elsevier Ltd. All rights reserved

Impacts of anthropogenic and boreal fire emissions in the central North Atlantic lower free troposphere: summertime observations at the PICO-NARE observatory.

ICARTT 2004 Data Workshop. Durham, New Hampshire, August 9-12, 2005.We present measurements of CO, O3, aerosol Black Carbon (BC) made over the central North Atlantic lower Free Troposphere (FT) during the summers of 2001-2004 along with measurements of nitrogen oxides (NOx and NOy) made during the summer of 2004 (ICARTT period) and non-methane hydrocarbons (NMHCs) made during the winter 2004-spring 2005

Large-scale impacts of anthropogenic and boreal fire emissions apparent in multi-year free tropospheric observations in the Azores.

Gordon conference - Atmospheric Chemistry. Big Sky, Montana, September 4-9 2005.Pico Mountain in the Azores Islands provides an ideal location for studies of the central N. Atlantic lower free troposphere. The PICO-NARE station has operated there since summer 2001. Here, we present key findings from summertime measurements, during 2001-2004. Main Findings: Anthropogenic and boreal wildfire emissions dominate variations in CO and have major impacts on O3, nitrogen oxides, non-methane hydrocarbons (NMHCs) and black carbon

Changes to the chemical state of the Northern Hemisphere atmosphere during the second half of the twentieth century

The NOx (NO and NO2) and HOx (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOx and HOx are highly variable in space and time, and so the measurements of these species are of limited value for examining long-term, large-scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the production efficiency of which is dependent on the atmospheric [NO] ∕ [HO2] ratio. We derive long-term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 3–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOx, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increased from around 1970 to the late 1990s. This is consistent with large changes to the [NO] ∕ [HO2] ratio in the Northern Hemisphere atmosphere during this period. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic

Formaldehyde (HCHO) in air, snow and interstitial air at Concordia (East Antarctic plateau) in summer

During the 2011/12 and 2012/13 austral summers, HCHO was investigated for the first time in ambient air, snow, and interstitial air at the Concordia site, located near Dome C on the East Antarctic Plateau, by deploying an Aerolaser AL-4021 analyzer. Snow emission fluxes were estimated from vertical gradients of mixing ratios observed at 1 cm and 1 m above the snow surface as well as in interstitial air a few centimeters below the surface and in air just above the snowpack. Typical flux values range between 1 and 2 × 1012 molecules m−2 s−1 at night and 3 and 5 × 1012 molecules m−2 s−1 at noon. Shading experiments suggest that the photochemical HCHO production in the snowpack at Concordia remains negligible compared to temperature-driven air–snow exchanges. At 1 m above the snow surface, the observed mean mixing ratio of 130 pptv and its diurnal cycle characterized by a slight decrease around noon are quite well reproduced by 1-D simulations that include snow emissions and gas-phase methane oxidation chemistry. Simulations indicate that the gas-phase production from CH4 oxidation largely contributes (66%) to the observed HCHO mixing ratios. In addition, HCHO snow emissions account for ~ 30% at night and ~ 10% at noon to the observed HCHO levels