The chemistry and dry deposition of atmospheric nitrogen at a rural site in the northeastern United States

Measurements of N gas (HNO\sb3, NH\sb3) and aerosol (NO\sb3\sp-, NH\sb4\sp+) species were made between 1991-1995 to examine the nature of atmospheric N chemistry and to estimate the importance of N dry deposition to the Harvard Forest (Petersham, MA). This U.S. site was influenced by aged rural air masses advected from the northwest (NW) and fresh industrial emissions from the southwest (SW). Mean midday HNO\sb3 and aerosol N mixing ratios were four times higher in SW surface winds. Diel cycles provided evidence of the entrainment of HNO\sb3 and aerosol NO\sb3\sp- from aloft as the nocturnal inversion broke down. HNO\sb3 made up about 20% of NO\sb{\rm Y} at midday, while the sum of measured NO\sb{\rm Y} species accounted for 60-80% of NO\sb{\rm Y} suggesting that PAN and other organic nitrates were significant at this predominantly oak site. The deposition velocity (V\sb{\rm d} of HNO\sb3 was estimated using the modified-Bowen ratio (MBR) and an inferential method. Hourly averaged V\sb{\rm d} for HNO\sb3 ranged from $\approx$1 cm s\sp{-1} at night to $\approx$6 cm s\sp{-1} at midday. HNO\sb3 deposition was typically 3-4 times higher than the measured NO\sb{\rm Y} flux. Measurement bias, storage effects, and the flux of other NO\sb{\rm Y} species probably contributed to this discrepancy. NH\sb3 levels were suppressed by atmospheric SO\sb4\sp{2-} to mixing ratios of 200-300 pptv, below the NH\sb3 compensation point of the canopy. The SO\sb4\sp{2-} regulation of NH\sb{\rm X} (NH\sb3 + NH\sb4\sp+) partitioning changed exponentially as a function of air temperature. The bulk aerosol was as a mixture of submicron ammonium (bi)sulfate aerosols with smaller amounts of soil particles. Aerosols from the SW were rarely neutralized, especially when SO\sb4\sp{2-} concentrations were greater than $\approx$100 nmol m\sp{-3}, suggesting an upper limit for NH\sb{\rm X} emissions from this region. Aerosol NO\sb3\sp- was 4-8 times lower than NH\sb4\sp+, and associated with supermicron Ca\sp{2+}. The higher V\sb{\rm d} of coarse mode NO\sb3\sp- resulted in similar dry deposition fluxes of 1 kg N ha\sp{-1} yr\sp{-1} for both N aerosol species. These aerosol deposition fluxes were considerably smaller than measured N (NO\sb3\sp{-} + NH\sb4\sp+) wet deposition ($\approx$8 kg N ha\sp{-1} yr\sp{-1}) and estimates of HNO\sb3 inputs (1-7 kg N ha\sp{-1} yr\sp{-1}) to this forest ecosystem

Source attribution of ozone in Southeast Texas before and after the Deepwater Horizon accident using satellite, sonde, surface monitor, and air mass trajectory data

Since the summer of 2004, over 300 ozonesondes have been launched from Rice University (29.7 N, 95.4 W) or the University of Houston (29.7 N, 95.3 W), each \u3c 5 km from downtown Houston. The Texas Commission on Environmental Quality maintains a large database of hourly surface ozone observations in Southeast Texas. In this study, we identify the contributions to surface ozone pollution levels from natural and anthropogenic sources, both local and remote in nature. This source identification is performed two ways: 1) through an analysis of sonde data, including ozone concentrations, wind speed and direction, and relative humidity data, and 2) through an analysis that combines trajectory calculations with surface monitor data. We also examine regional changes in Ozone Monitoring Instrument (OMI) measurements of formaldehyde and ozone from 2004 – 2010. In particular, we compare the 2010 sonde, surface monitor, and satellite data after the Deepwater Horizon accident with data from previous years to determine the impact, if any, of the large source of hydrocarbons in the Gulf of Mexico on air quality in Southeast Texas

Seasonal distributions of fine aerosol sulfate in the North American Arctic basin during TOPSE

We used the mist chamber/ion chromatography technique to quantify fine aerosol SO4=(\u3c2.7 μm) in the Arctic during the Tropospheric Ozone Production about the Spring Equinox Experiment (TOPSE) with about 2.5 min time resolution. Our effective sample area ranged from 50° to 86°N and 53° to 100°W. The seasonal evolution of fine aerosol sulfate in the Arctic troposphere during TOPSE was consistent with the phenomenon of Arctic haze. Arctic haze has been attributed to pollution from sources in the Arctic and pollution transported meridionally along stable isentropes into the Arctic in geographically broad but vertically narrow bands. These layers became more prevalent at higher altitudes as the season progressed toward summer, and the relevant isentropes are not held so close to the surface. Mean fine particle SO4= mixing ratios during TOPSE in February below 1000 m were elevated (112 pptv) and highly variable (between 28 and 290 pptv) but were significantly lower at higher altitudes (about 40 pptv). As the season progressed, elevated mixing ratios and higher variability were observed at higher altitudes, up to 7 km. In May, mixing ratios at the lowest altitudes declined but still remained higher than in February at all altitudes. The high variability in our measurements likely reflects the vertical heterogeneity of the wintertime Arctic atmosphere as the airborne sampling platform passed in and out of these layers. It is presumed that mixing ratios and variability will continue to decline at all altitudes into the summer as wet deposition processes become important in removing aerosol SO4= from the troposphere

Negation and lexical morphology across languages: Insights from a trilingual translation corpus

This paper proposes an exploratory cross-linguistic bird's eye-view of negative lexical morphology by examining English, French and Italian negative derivational affixes. More specifically, it aims to uncover the French and Italian equivalents of the English affixes de, dis, in, non, un and less. These include morphological equivalents (i.e. negative prefixes in French and Italian) as well as non-morphological equivalents (i.e. single words devoid of negative affixation, multi-word units or paraphrases). The study relies on a nine-million-word trilingual translation corpus made up of texts from the Europarl corpus and shows that the systematic analysis of translation data makes it possible to identify the major morphological dissimilarities between the three languages investigated. The frequent use of non-morphological translations in French and Italian reflects fundamental differences between the source language (English) and the two target lan-guages (French and Italian), hence pointing to possible translation difficulties. Morphological translations, on the other hand, bring to light cross-linguistic similarities in the use of negative affixe

Modeling chemistry in and above snow at Summit, Greenland – Part 1: Model description and results

Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the 1-D atmospheric boundary layer model MISTRA. The new 1-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid-like layer (LLL) on the grain surface. The coupled model, referred to as MISTRA-SNOW, was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June–13 June, 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow can sustain atmospheric NO and BrO mixing ratios measured at Summit, Greenland during this period

Stratospheric influence on the northern North American free troposphere during TOPSE: 7Be as a stratospheric tracer

We use 7Be, with HNO3 and O3, to identify air masses sampled from the NCAR C-130 during TOPSE that retained clear evidence of stratospheric influence. A total of 43 such air masses, spread fairly evenly across the February to May sampling period, and 40°N–86°N latitude range, were encountered. South of 55°N, nearly all clear stratospheric influence was restricted to altitudes above 6 km. At higher latitudes stratospherically influenced air masses were encountered as low as 2 km. Approximately 12% of all TOPSE sampling time at altitudes above 2 km was spent in stratospherically impacted air, above 6 km this increased to more than half of the time. Because it is not certain how much of this stratospherically influenced air irreversibly injected mass (and chemical compounds) into the troposphere, we estimate the stratospheric fraction of O3 in high latitude TOPSE samples based on a linear relationship to7Be and compare it to in situ O3. This analysis indicates that the stratospheric source can account for a dominant fraction (\u3e85%) of in situ O3 throughout TOPSE, but that the stratospheric contribution was nearly constant through the 4 month campaign. In February and March the 7Be based estimates of stratospheric O3 account for 10–15% more O3 than was measured, but by April and May there is up to about 10% more O3 than expected from the stratospheric source. This trend suggests that a seasonal transition from O3 depletion to photochemical production in the high latitude North American troposphere is the major cause of the springtime increase in O3

Modeling chemistry in and above snow at Summit, Greenland – Part 2: Impact of snowpack chemistry on the oxidation capacity of the boundary layer

The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the midday OH concentrations. Bromine chemistry increases the OH concentration by 10–18 % (10 % at noon LT), while snow sourced NOx increases OH concentrations by 20–50 % (27 % at noon LT). We show for the first time, using a coupled one dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss

Essential Role of P-Selectin in the Initiation of the Inflammatory Response Induced by Hemorrhage and Reinfusion

Resuscitation from hemorrhage induces profound pathophysiologic alterations and activates inflammatory cascades able to initiate neutrophil accumulation in a variety of tissues. This process is accompanied by acute organ damage (e.g., lungs and liver). We have previously demonstrated that significant leukocyte–endothelium interactions occur very early in other forms of ischemia/reperfusion (i.e., splanchnic ischemia/reperfusion and traumatic shock) which are largely mediated by increased expression of the adhesion molecule, P-selectin, on the vascular endothelium. Here we postulated that increased endothelial expression of P-selectin in the microvasculature would play an essential role in initiating the inflammatory signaling of hemorrhagic shock. Using intravital microscopy, we found that hemorrhagic shock significantly increased the number of rolling and adherent leukocytes in the mouse splanchnic microcirculation. In contrast, mice genetically deficient in P-selectin, or wild-type mice given either an anti–P-selectin monoclonal antibody or a recombinant soluble P-selectin glycoprotein ligand (PSGL)-1 immunoglobulin, exhibited markedly attenuated leukocyte–endothelium interaction after hemorrhagic shock. Thus, activation of P-selectin protein on the microvascular endothelium is essential for the initial upregulation of the inflammatory response occurring in hemorrhagic shock. Moreover, endogenous levels of PSGL-1 mRNA were significantly increased in the lung, liver, and small intestine of wild-type mice subjected to hemorrhagic shock. Since PSGL-1 promotes adhesive interactions largely through P-selectin expressed on the vascular endothelium, this result further supports the crucial role played by P-selectin in the recruitment of leukocytes during hemorrhagic shock

Hydroxyl concentration estimates in the sunlit snowpack at Summit, Greenland

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10-12 July), with peak values of more than 3.2×106 molecules cm-3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 molecules cm-3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 molecules cm-3 in the early afternoon on 15 April and 1.5×106 molecules cm-3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer. © 2007 Elsevier Ltd. All rights reserved