scholarly journals The impact of monoaromatic hydrocarbons on OH reactivity in the coastal UK boundary layer and free troposphere

2014 ◽  
Vol 14 (13) ◽  
pp. 6677-6693 ◽  
Author(s):  
R. T. Lidster ◽  
J. F. Hamilton ◽  
J. D. Lee ◽  
A. C. Lewis ◽  
J. R. Hopkins ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Gas Chromatography ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Ethyl Benzene ◽  
Free Troposphere ◽  
Flight Mass Spectrometry ◽  
Benzene Toluene ◽  
The Uk ◽  
The Impact

Abstract. Reaction with the hydroxyl radical (OH) is the dominant removal mechanism for virtually all volatile organic compounds (VOCs) in the atmosphere; however, it can be difficult to reconcile measured OH reactivity with known sinks. Unresolved higher molecular weight VOCs contribute to OH sinks, of which monoaromatics are potentially an important sub-class. A method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) has been developed that extends the degree with which larger VOCs can be individually speciated from whole air samples (WAS). The technique showed excellent sensitivity, resolution and good agreement with an established gas chromatography–flame ionisation (GC-FID) method, for compounds amenable to analysis on both instruments. Measurements have been made of VOCs within the UK east coast marine boundary layer and free troposphere, using samples collected from five aircraft flights in winter 2011. Ten monoaromatic compounds with an array of different alkyl ring substituents have been quantified, in addition to the simple aromatics, benzene, toluene, ethyl benzene and Σm- and p-xylene. These additional compounds were then included in constrained box model simulations of atmospheric chemistry occurring at two UK rural and suburban field sites in order to assess the potential impact of these larger monoaromatics species on OH reactivity; they have been calculated to contribute an additional 2–6% to the overall modelled OH loss rate, providing a maximum additional OH sink of ~0.9 s−1.

scholarly journals The impact of monoaromatic hydrocarbons on OH reactivity in the North Sea boundary layer and free troposphere

2013 ◽  
Vol 13 (12) ◽  
pp. 32423-32457 ◽  
Author(s):  
R. T. Lidster ◽  
J. F. Hamilton ◽  
J. D. Lee ◽  
A. C. Lewis ◽  
J. R. Hopkins ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Ethyl Benzene ◽  
Free Troposphere ◽  
The North ◽  
Flight Mass Spectrometry ◽  
The North Sea ◽  
The Uk ◽  
The Impact

Abstract. Reaction with the hydroxyl radical (OH) is the dominant removal mechanism for virtually all volatile organic compounds (VOCs) in the atmosphere, however it can be difficult to reconcile measured OH reactivity with known sinks. Unresolved higher molecular weight VOCs contribute to OH sinks, of which monoaromatics are potentially an important sub-class. A method based on comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS) has been developed that extends the degree with which larger VOCs can be individually speciated from whole air samples (WAS). The technique showed excellent sensitivity, resolution and good agreement with an established GC-FID method, for compounds amenable to analysis on both instruments. Measurements have been made of VOCs within the UK east coast marine boundary layer and free troposphere, using samples collected from five aircraft flights in winter 2011. Ten monoaromatic compounds with an array of different alkyl ring substituents have been quantified, in addition to the simple aromatics, benzene, toluene, ethyl benzene and σm- and p-xylene. These additional compounds were then included into constrained box model simulations of atmospheric chemistry occurring at two UK rural and suburban field sites in order to assess the potential impact of these larger monoaromatics species on OH reactivity; they have been calculated to contribute an additional 2–6% to the overall modelled OH loss rate, providing a~maximum additional OH sink of ~0.9 s−1.

scholarly journals Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations

2010 ◽  
Vol 10 (7) ◽  
pp. 3405-3425 ◽  
Author(s):  
D. B. Millet ◽  
A. Guenther ◽  
D. A. Siegel ◽  
N. B. Nelson ◽  
H. B. Singh ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Quantitative Model ◽  
Turnover Time ◽  
Chemical Mechanism ◽  
Free Troposphere ◽  
Terrestrial Plants ◽  
D Model ◽  
Present Understanding

Abstract. We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a−1, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a−1, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a−1. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a−1) and anthropogenic emissions (2 Tg a−1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a−1 and 7.8 Tg a−1, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel.

scholarly journals Surface fluxes of bromoform and dibromomethane over the tropical western Pacific inferred from airborne in situ measurements

2017 ◽  
Author(s):  
Liang Feng ◽  
Paul I. Palmer ◽  
Robyn Butler ◽  
Stephen J. Andrews ◽  
Elliot L. Atlas ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Current Knowledge ◽  
A Priori ◽  
Surface Fluxes ◽  
Western Pacific ◽  
Study Region ◽  
The Western Pacific ◽  
Aircraft Data

Abstract. We infer surface fluxes of bromoform (CHBr3) and dibromoform (CH2Br2) from aircraft observations over the western Pacific using a tagged version of the GEOS-Chem global 3-D atmospheric chemistry model and a Maximum A Posteriori inverse model. The distribution of a priori ocean emissions of these gases are reasonably consistent with observed atmospheric mole fractions of CHBr3 (r = 0.62) and CH2Br2 (r = 0.38). These a priori emissions result in a positive model bias in CHBr3 peaking in the marine boundary layer, but capture observed values of CH2Br2 with no significant bias by virtue of its longer atmospheric lifetime. Using GEOS-Chem, we find that observed variations in atmospheric CHBr3 are determined equally by sources over the western Pacific and those outside the study region, but observed variations in CH2Br2 are determined mainly by sources outside the western Pacific. Numerical closed-loop experiments show that the spatial and temporal distribution of boundary layer aircraft data have the potential to substantially improve current knowledge of these fluxes, with improvements related to data density. Using the aircraft data, we estimate aggregated regional fluxes of 3.6 ± 0.3 × 108 g/month and 0.7 ± 0.1 × 108 g/month for CHBr3 and CH2Br2 over 130°–155° E and 0°–12° N, respectively, which represent reductions of 20–40 % and substantial spatial deviations from the a priori inventory. We find no evidence to support a robust linear relationship between CHBr3 and CH2Br2 oceanic emissions, as used by previous studies.

scholarly journals Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

2011 ◽  
Vol 11 (3) ◽  
pp. 7045-7093 ◽  
Author(s):  
Z. Hosaynali Beygi ◽  
H. Fischer ◽  
H. D. Harder ◽  
M. Martinez ◽  
R. Sander ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Steady State ◽  
Atlantic Ocean ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Air Pollutant ◽  
Photochemical Oxidant ◽  
Important Region ◽  
Atmospheric Observations ◽  
Oxidation Efficiency

Abstract. Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NOx conditions (5–25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°–60° S over the Atlantic Ocean.

scholarly journals New Particle Formation and impact on CCN concentrations in the boundary layer and free troposphere at the high altitude station of Chacaltaya (5240 m a.s.l.), Bolivia

2016 ◽  
Author(s):  
C. Rose ◽  
K. Sellegri ◽  
I. Moreno ◽  
F. Velarde ◽  
M. Ramonet ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Particle Number ◽  
Particle Growth ◽  
Particle Formation ◽  
Number Concentration ◽  
Particle Number Concentration ◽  
Free Troposphere ◽  
New Particle Formation ◽  
Radiative Processes ◽  
The Impact

Abstract. Global models predict that new particle formation (NPF) is, in some environments, responsible for a substantial fraction of the total atmospheric particle number concentration and subsequently contribute significantly to cloud condensation nuclei (CCN) concentrations. NPF events were frequently observed at the highest atmospheric observatory in the world, Chacaltaya (5240 m a.s.l.), Bolivia. The present study focuses on the impact of NPF on CCN population. Neutral cluster and Air Ion Spectrometer and mobility particle size spectrometer measurements were simultaneously used to follow the growth of particles from cluster sizes down to ~ 2 nm up to CCN threshold sizes set to 50, 80 and 100 nm. Using measurements performed between January 1 and December 31 2012, we found that 61% of the 94 analysed events showed a clear particle growth and significant enhancement of the CCN-relevant particle number concentration. We evaluated the contribution of NPF events relative to the transport of pre-existing particles to the site. The averaged production of 50 nm particles during those events was 5072 cm−3, and 1481 cm−3 for 100 nm particles, with a larger contribution of NPF compared to transport, especially during the wet season. The data set was further segregated into boundary layer (BL) and free troposphere (FT) conditions at the site. The NPF frequency of occurrence was higher in the BL (48 %) compared to the FT (39 %). Particle condensational growth was more frequently observed for events initiated in the FT, but on average faster for those initiated in the BL, when the amount of condensable species was most probably larger. As a result, the potential to form new CCN was higher for events initiated in the BL (67 % against 56 % in the FT). In contrast, higher CCN number concentration increases were found when the NPF process initially occurred in the FT, under less polluted conditions. This work highlights the competition between particle growth and the removal of freshly nucleated particles by coagulation processes. The results support model predictions which suggest that NPF is an effective source of CCN in some environments, and thus may influence regional climate through cloud related radiative processes.

scholarly journals Observationally constrained analysis of sea salt aerosol in the marine atmosphere

2019 ◽  
Author(s):  
Huisheng Bian ◽  
Karl Froyd ◽  
Daniel M. Murphy ◽  
Jack Dibb ◽  
Mian Chin ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Marine Boundary Layer ◽  
Model Simulation ◽  
In Situ Measurements ◽  
Sea Salt ◽  
Boreal Summer ◽  
Integrated Analysis ◽  
Marine Atmosphere

Abstract. Atmospheric sea salt plays important roles in marine cloud formation and atmospheric chemistry. We performed an integrated analysis of NASA GEOS model simulations run with the GOCART aerosol module, in situ measurements from the PALMS and SAGA instruments obtained during the NASA ATom campaign, and aerosol optical depth (AOD) measurements from AERONET Marine Aerosol Network (MAN) sun photometers and from MODIS satellite observations to better constrain sea salt in the marine atmosphere. ATom measurements and GEOS model simulation both show that sea salt concentrations over the Pacific and Atlantic oceans have a strong vertical gradient, varying up to four orders of magnitude from the marine boundary layer to free troposphere. The modeled residence times suggest that the lifetime of sea salt particles with dry diameter less than 3 μm is largely controlled by wet removal, followed next by turbulent process. During both boreal summer and winter, the GEOS simulated sea salt mass mixing ratios agree with SAGA measurements in the marine boundary layer (MBL) and with PALMS measurements above the MBL. However, comparison of AOD from GEOS with AERONET/MAN and MODIS aerosol retrievals indicated that the model underestimated AOD over the oceans where sea salt dominates. The apparent discrepancy of slightly overpredicted concentration and large underpredicted AOD could not be explained by biases in the model RH, which was found to be comparable to or larger than the in-situ measurements. This conundrum is at least partially explained by the sea salt size distribution; where the GEOS simulation has much less sea salt percentage-wise in the smaller particles than was observed by PALMS. Model sensitivity experiments indicated that the simulated sea salt is better correlated with measurements when the sea salt emission is calculated based on the friction velocity and with consideration of sea surface temperature dependence than that parameterized with the 10-m winds.

scholarly journals Characterization of a boreal convective boundary layer and its impact on atmospheric chemistry during HUMPPA-COPEC-2010

2012 ◽  
Vol 12 (19) ◽  
pp. 9335-9353 ◽  
Author(s):  
H. G. Ouwersloot ◽  
J. Vilà-Guerau de Arellano ◽  
A. C. Nölscher ◽  
M. C. Krol ◽  
L. N. Ganzeveld ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Convective Boundary Layer ◽  
Large Scale ◽  
Spatial Scales ◽  
Potential Temperature ◽  
Chemical Species ◽  
Convective Boundary ◽  
The Impact

Abstract. We studied the atmospheric boundary layer (ABL) dynamics and the impact on atmospheric chemistry during the HUMPPA-COPEC-2010 campaign. We used vertical profiles of potential temperature and specific moisture, obtained from 132 radio soundings, to determine the main boundary layer characteristics during the campaign. We propose a classification according to several main ABL prototypes. Further, we performed a case study of a single day, focusing on the convective boundary layer, to analyse the influence of the dynamics on the chemical evolution of the ABL. We used a mixed layer model, initialized and constrained by observations. In particular, we investigated the role of large scale atmospheric dynamics (subsidence and advection) on the ABL development and the evolution of chemical species concentrations. We find that, if the large scale forcings are taken into account, the ABL dynamics are represented satisfactorily. Subsequently, we studied the impact of mixing with a residual layer aloft during the morning transition on atmospheric chemistry. The time evolution of NOx and O3 concentrations, including morning peaks, can be explained and accurately simulated by incorporating the transition of the ABL dynamics from night to day. We demonstrate the importance of the ABL height evolution for the representation of atmospheric chemistry. Our findings underscore the need to couple the dynamics and chemistry at different spatial scales (from turbulence to mesoscale) in chemistry-transport models and in the interpretation of observational data.

scholarly journals The Influence of the Concentration of Cyclohexane Radicals Bonded with an Si100 Silica Gel Surface upon the Retention of Some Hydrocarbons in Gas Chromatography

2000 ◽  
Vol 18 (1) ◽  
pp. 43-53 ◽  
Author(s):  
R. Nasuto
Keyword(s):  
Gas Chromatography ◽  
Silica Gel ◽  
Stationary Phases ◽  
Ethyl Benzene ◽  
Polar Organic Compounds ◽  
Phase Concentration ◽  
Bonded Phase ◽  
Unmodified Silica ◽  
Benzene Toluene ◽  
Ethylene Chloride

Four adsorbents based on silica gel Si100 with chemically bonded cyclohexane have been prepared as stationary phases for gas chromatography. The concentrations of cyclohexane radicals thus bonded with the silica gel surface were 1.35, 3.35, 4.17 and 6.02 μmol/m2, respectively. Separation of aliphatic (C6–C12), aromatic (benzene, toluene and m-xylene) and some polar organic compounds (chloroform, ethylene chloride, chlorobenzene, p-chlorotoluene and ethyl benzene) by gas chromatography using columns packed with the prepared adsorbents was studied. It was concluded that the retention of some compounds was increased on the column packed with an adsorbent of 1.35 μmol/m2 concentration relative to that measured on the column packed with the unmodified silica gel. On columns packed with adsorbents with a higher bonded phase concentration than 1.35 μmol/m2, the retention times of all the compounds studied chromatographically decreased with an increase in the bonded phase concentration.

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