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

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<sup>−1</sup>, 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<sup>−1</sup>, 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:NO<sub>x</sub> 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<sup>−1</sup>. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a<sup>−1</sup>) and anthropogenic emissions (2 Tg a<sup>−1</sup>). 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 NO<sub>x</sub>: 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<sup>−1</sup> and 7.8 Tg a<sup>−1</sup>, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel

The Role of the Ocean in the Global Atmospheric Budget of Acetone

[1] Acetone is one of the most abundant carbonyl compounds in the atmosphere and it plays an important role in atmospheric chemistry. The role of the ocean in the global atmospheric acetone budget is highly uncertain, with past studies reaching opposite conclusions as to whether the ocean is a source or sink. Here we use a global 3-D chemical transport model (GEOS-Chem) simulation of atmospheric acetone to evaluate the role of air-sea exchange in the global budget. Inclusion of updated (slower) photolysis loss in the model means that a large net ocean source is not needed to explain observed acetone in marine air. We find that a simulation with a fixed seawater acetone concentration of 15 nM based on observations can reproduce the observed global patterns of atmospheric concentrations and air-sea fluxes. The Northern Hemisphere oceans are a net sink for acetone while the tropical oceans are a net source. On a global scale the ocean is in near-equilibrium with the atmosphere. Prescribing an ocean concentration of acetone as a boundary condition in the model assumes that ocean concentrations are controlled by internal production and loss, rather than by air-sea exchange. An implication is that the ocean plays a major role in controlling atmospheric acetone. This hypothesis needs to be tested by better quantification of oceanic acetone sources and sinks.Engineering and Applied Science

Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations

We describe measurements of total peroxy nitrates (ΣPNs), NO₂, O₃ and several aldehydes at Granite Bay, California, during the Chemistry and Transport of the Sacramento Urban Plume-2001 (CATSUP 2001) campaign, from 19 July–16 September 2001. We observed a strong photochemically driven variation of ΣPNs during the day with the median of 1.2 ppb at noon. Acetaldehyde, pentanal, hexanal and methacrolein had median abundances in the daytime of 1.2 ppb, 0.093 ppb, 0.14 ppb, and 0.27 ppb, respectively. We compare steady state and time dependent calculations of the dependence of ΣPNs on aldehydes, OH, NO and NO₂ showing that the steady state calculations are accurate to ±30% between 10:00 and 18:00 h. We use the steady state calculation to investigate the composition of ΣPNs and the concentration of OH at Granite Bay. We find that PN molecules that have never been observed before make up an unreasonably large fraction of the ΣPNs unless we assume that there exists a PAN source that is much larger than the acetaldehyde source. We calculate that OH at the site varied between 2 and 7×10⁶ molecule cm^−3 at noon during the 8 weeks of the experiment

Impact of the assimilation of ozone from the Tropospheric Emission Spectrometer on surface ozone across North America

We examine the impact of assimilating ozone observations from the Tropospheric Emission Spectrometer (TES) on North American surface ozone abundances in the GEOS-Chem model in August 2006. The assimilation reduces the negative bias in the modeled free tropospheric ozone, which enhances the ozone flux into the boundary layer. Surface ozone abundances increased by as much as 9 ppb in western North America and by less than 2 ppb in the southeast, resulting in a total background source of ozone of 20-40 ppb. The enhanced ozone in the model reduced the model bias with respect to surface ozone observations in the western USA, but exacerbated it in the east. This increase in the bias in the boundary layer in the east, despite the agreement between the assimilation and ozonesonde measurements in the free troposphere, suggests errors in the ozone sources or sinks or in boundary layer mixing in the model. © 2009

The weekend effect within and downwind of Sacramento ─ Part 1: Observations of ozone, nitrogen oxides, and VOC reactivity

Day-of-week patterns in human activities can be used to examine the ways in which differences in primary emissions result in changes in the rates of photochemical reactions, and the production of secondary pollutants. Data from twelve California Air Resources Board monitoring sites in Sacramento, CA, and the downwind Mountain Counties air basin are analyzed to reveal day of week patterns in ozone and its precursors in the summers of 1998–2002. Measurements of non-methane hydrocarbons are available for the summers of 2001–2003 at three of these sites and NO_x at six of these sites for the full time period. This routine monitoring data is complemented by data sets of ozone and nitrogen oxide concentrations obtained in the summers of 2001 and 2003 at three sites in the region and comprehensive measurements of VOC reactivity at two sites in 2001. Daytime concentrations of nitrogen oxides (NO_x≡NO+NO₂) are approximately 35% lower on weekends at all the sites, whereas the VOC reactivity changes by less than 10%. All six sites in the Sacramento Valley have higher 8-h maximum average ozone on the weekend and are more likely to exceed the national standard of 85 ppb on the weekend. In contrast, all the sites in the Mountain Counties are less likely to exceed the federal ozone standard on the weekend. Analysis of the day-of-week trends in odd oxygen show that the weekend effect of ozone within Sacramento is strongly influenced by NO sources close to the monitoring sites. This suggests that ozone measurements from monitoring sites close to highways, including two rural locations, may not be representative of the regional abundance, and lead to underestimates of long term exposure for humans and ecosystems

Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations

International audienceWe describe measurements of total peroxy nitrates (?PNs), NO2, O3 and several aldehydes at Granite Bay, California, during the Chemistry and Transport of the Sacramento Urban Plume-2001 (CATSUP 2001) campaign, from 19 July?16 September 2001. We observed a strong photochemically driven variation of ?PNs during the day with the median of 1.2 ppb at noon. Acetaldehyde, pentanal, hexanal and methacrolein had median abundances in the daytime of 1.2 ppb, 0.093 ppb, 0.14 ppb, and 0.27 ppb, respectively. We compare steady state and time dependent calculations of the dependence of ?PNs on aldehydes, OH, NO and NO2 showing that the steady state calculations are accurate to ±30% between 10:00 and 18:00 h. We use the steady state calculation to investigate the composition of ?PNs and the concentration of OH at Granite Bay. We find that PN molecules that have never been observed before make up an unreasonably large fraction of the ?PNs unless we assume that there exists a PAN source that is much larger than the acetaldehyde source. We calculate that OH at the site varied between 2 and 7×106 molecule cm?3 at noon during the 8 weeks of the experiment

Long-range antiferromagnetic order in the S=1 chain compound LiVGe2O6

The phase transition in the compound LiVGe2O6 has been proposed as a unique example of a spin-Peierls transition in an S=1 antiferromagnetic chain. We report neutron and x-ray diffraction measurements of LiVGe2O6 above and below the phase transition at T=24 K. No evidence is seen for any structural distortion associated with the transition. The neutron results indicate that the low temperature state is antiferromagnetic, driven by ferromagnetic interchain couplings.Comment: 4 pages, 4 ps figures, REVTEX, submitted to PR

A low-dimensional spin S = 1/2 system at the quantum critical limit: Na2V2O7

We report the results of measurements of the dc-susceptibility and the 23Na-NMR response of Na2V2O7, a recently synthesized, non metallic low dimensional spin system. Our results indicate that upon reducing the temperature to below 100 K, the V^{4+} moments are gradually quenched, leaving only one moment out of 9 active. The NMR data reveal a phase transition at very low temperatures. With decreasing applied field H, the critical temperature shifts towards T = 0 K, suggesting that Na2V2O7 may be regarded as an insulator reaching a quantum critical point at H = 0.Comment: 4 pages, 5 figure

Observations of total alkyl nitrates within the Sacramento Urban Plume

International audienceDuring the summer of 2001, NO2, total peroxy nitrates (?PNs), total alkyl nitrates (?ANs), HNO3, volatile organic compounds (VOC), CO2, O3, and meteorological variables were measured at Granite Bay, CA. The diurnal variation in ?PNs, ?ANs and HNO3 were all strongly correlated with sunlight, indicating both that they are photochemically produced and that they have a lifetime of a few hours at this site. The mixing ratios of ?ANs ranged as high as 2 ppbv. Mixing ratios at night averaged 0.4 ppbv. Odd-oxygen (Ox=O3+NO2) and ?ANs were strongly correlated reflecting both the common chemical source terms and the similar lifetimes of both species. Several approaches to interpreting the simultaneous variations of Ox and ?ANs are described, and used to derive a best estimate of the ?AN yield from the VOC mixture at this site of 4.2% and an estimate of the range that is consistent with the observations of 3.9?5.8%. A yield of 4.2% implies termination of the HOx catalytic cycle by ?AN formation once every 24 cycles. Analysis of the HNO3 observations in combination with the ?AN and O3 measurements suggests that NOx terminations limit the HOx chain length to between 4.7 and 6.3