We report Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) measurements of the composition of ambient 10–33 nm diameter particles formed from nucleation on 16 March 2006 in Tecamac, ...Mexico during the Megacity Initiative: Local and Global Research Observations (MILAGRO) field study. On this day, nucleated particles contained far more organics than sulfates: average ion molar ratios with measurement uncertainties for nitrate, organics and sulfur species were 6 ± 2%, 84 ± 5%, and 10 ± 1%, respectively. The measured organic species include nitrogen‐containing organic compounds, organic acids, and hydroxy organic acids. Independent calculations show that sulfuric acid condensation could have accounted for only 10 ± 2% of the growth that was observed on this day, which is consistent with the TDCIMS measurements of composition. It follows that organic compounds play a dominant role the high growth rates that were observed.
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The impact of aerosols on regional air quality and climate necessitates improved understanding of their emission and microphysical properties. The size distributions of black carbon (BC) and light ...scattering particles (LSP) were measured with a single particle soot photometer on board the NASA DC‐8 aircraft during the ARCTAS mission 2008. Air sampling was made in the air plumes of both urban and forest fire emissions over California during the CARB (California Air Resources Board) phase of the mission. A total of eleven plumes were identified using SO2 and CH3CN tracers for fossil fuel (FF) combustion and biomass burning (BB), respectively. The enhancements of BC and LSP in BB plumes were significantly higher compared to those in FF plumes. The average mass concentration of BC in BB plumes was more than twice that in FF plumes. Except for the BC/CO ratio, distinct emission ratios of BC/CO2, BC/CH3CN, CH3CN/CO, and CO/CO2 were observed in the plumes from the two sources. Similarly, the microphysical properties of BC and LSP also showed distinct behaviors. The BC count median diameter (CMD) of 115 ± 5 nm in FF plumes was smaller compared to 141 ± 9 nm in the BB plumes. BC aerosols were thickly coated in BB plumes, the average shell/core ratios were 1.47 and 1.24 in BB and FF plumes, respectively. In the total mass of submicron aerosols, organic aerosols constituted about 67% in the FF plumes and 84% in BB plumes. The contribution of sulfate was also significant in the FF plumes.
Key Points
Distributions of black carbon over California during NASA ARCTAS‐CARB mission
Emission ratios of aerosols from anthropogenic and biomass burning sources
Study of microphysical properties of aerosols emitted from different sources
Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. ...Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid (H2SO4), dimethylamine (DMA) and trimethylamine (TMA), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2H2SO42 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of H2SO4, temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).
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 mid-day 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.
Active molecular iodine photochemistry in the Arctic Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W. ...
Proceedings of the National Academy of Sciences - PNAS,
09/2017, Volume:
114, Issue:
38
Journal Article
Peer reviewed
Open access
During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric ...composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I₂) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I₂ and snowpack iodide (I⁻) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I₂ was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I⁻ measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I⁻/Na⁺, consistent with iodine activation and recycling. Modeling shows that observed I₂ levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I₂ is likely a dominant source of iodine atoms in the Arctic.
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An instrument to detect gaseous amines and ammonia is described, and representative data from an urban site and a laboratory setting are presented. The instrument, an Ambient pressure Proton transfer ...Mass Spectrometer (AmPMS), consists of a chemical ionization and drift region at atmospheric pressure coupled to a standard quadrupole mass spectrometer. Calibrations show that AmPMS sensitivity is good for amines, and AmPMS backgrounds were suitably determined by diverting sampled air through a catalytic converter. In urban air at a site in Atlanta, amines were detected at subpptv levels for methyl and dimethyl amine which were generally at a low abundance of <1 and ∼3 pptv, respectively. Trimethyl amine (or isomers) was on average about 4 pptv in the morning and increased to 15 pptv in the afternoon, while triethyl amine (or isomers or amides) increased to 25 pptv on average in the late afternoon. The background levels for the 4 and 5 carbon amines and ammonia were high, and data are very limited for these species. Improvements in detecting amines and ammonia from a smog chamber were evident due to improvements in AmPMS background determination; notably dimethyl amine and its OH oxidation products were followed along with impurity ammonia and other species. Future work will focus on accurate calibration standards and on improving the sample gas inlet.
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We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing ...on the budgets of ROx (OH + HO2 + RO2 ) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h-1 , among the highest found in urban atmospheres. The largest primary ROx source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h-1 and 1.7 ppbv h-1 , respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h-1 , much larger than that of O1 D+H2 O (0.4 ppbv h-1 ). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h-1 ), followed by formation of RO2 NO2 (1.0 ppbv h-1 ) and RONO2 (0.7 ppbv h-1 ). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h-1 and 6.2 ppbv h-1 , respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2 ) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.
Oil sands comprise 30% of the world's oil reserves and the crude oil reserves in Canada's oil sands deposits are second only to Saudi Arabia. The extraction and processing of oil sands is much more ...challenging than for light sweet crude oils because of the high viscosity of the bitumen contained within the oil sands and because the bitumen is mixed with sand and contains chemical impurities such as sulphur. Despite these challenges, the importance of oil sands is increasing in the energy market. To our best knowledge this is the first peer-reviewed study to characterize volatile organic compounds (VOCs) emitted from Alberta's oil sands mining sites. We present high-precision gas chromatography measurements of 76 speciated C2 -C10 VOCs (alkanes, alkenes, alkynes, cycloalkanes, aromatics, monoterpenes, oxygenated hydrocarbons, halocarbons and sulphur compounds) in 17 boundary layer air samples collected over surface mining operations in northeast Alberta on 10 July 2008, using the NASA DC-8 airborne laboratory as a research platform. In addition to the VOCs, we present simultaneous measurements of CO2 , CH4 , CO, NO, NO2 , NOy , O3 and SO2 , which were measured in situ aboard the DC-8. Carbon dioxide, CH4 , CO, NO, NO2 , NOy , SO2 and 53 VOCs (e.g., non-methane hydrocarbons, halocarbons, sulphur species) showed clear statistical enhancements (1.1-397×) over the oil sands compared to local background values and, with the exception of CO, were greater over the oil sands than at any other time during the flight. Twenty halocarbons (e.g., CFCs, HFCs, halons, brominated species) either were not enhanced or were minimally enhanced (<10%) over the oil sands. Ozone levels remained low because of titration by NO, and three VOCs (propyne, furan, MTBE) remained below their 3 pptv detection limit throughout the flight. Based on their correlations with one another, the compounds emitted by the oil sands industry fell into two groups: (1) evaporative emissions from the oil sands and its products and/or from the diluent used to lower the viscosity of the extracted bitumen (i.e., C4 -C9 alkanes, C5 -C6 cycloalkanes, C6 -C8 aromatics), together with CO; and (2) emissions associated with the mining effort, such as upgraders (i.e., CO2 , CO, CH4 , NO, NO2 , NOy , SO2 , C2 -C4 alkanes, C2 -C4 alkenes, C9 aromatics, short-lived solvents such as C2 Cl4 and C2 HCl3 , and longer-lived species such as HCFC-22 and HCFC-142b). Prominent in the second group, SO2 and NO were remarkably enhanced over the oil sands, with maximum mixing ratios of 38.7 ppbv and 5.0 ppbv, or 383× and 319× the local background, respectively. These SO2 levels are comparable to maximum values measured in heavily polluted megacities such as Mexico City and are attributed to coke combustion. By contrast, relatively poor correlations between CH4 , ethane and propane suggest low levels of natural gas leakage despite its heavy use at the surface mining sites. Instead the elevated CH4 levels are attributed to methanogenic tailings pond emissions. In addition to the emission of many trace gases, the natural drawdown of OCS by vegetation was absent above the surface mining operations, presumably because of the widespread land disturbance. Unexpectedly, the mixing ratios of α-pinene and β-pinene were much greater over the oil sands (up to 217 pptv and 610 pptv, respectively) than over vegetation in the background boundary layer (20±7 pptv and 84±24 pptv, respectively), and the pinenes correlated well with several industrial tracers that were elevated in the oil sands plumes. Because so few independent measurements from the oil sands mining industry exist, this study provides an important initial characterization of trace gas emissions from oil sands surface mining operations.
A simple dimensionless parameter, L, is shown to determine whether or not new particle formation can occur in the atmosphere on a given day. The criterion accounts for the probability that clusters, ...formed by nucleation, will coagulate with preexisting particles before they grow to a detectable size. Data acquired in an intensive atmospheric measurement campaign in Atlanta, Georgia, during August 2002 (ANARChE) were used to test the validity of this criterion. Measurements included aerosol size distributions down to 3 nm, properties and composition of freshly nucleated particles, and concentrations of gases including ammonia and sulfuric acid. Nucleation and subsequent growth of particles at this site were often dominated by sulfuric acid. New particle formation was observed when L was less than ∼1 but not when L was greater than ∼1. Furthermore, new particle formation was only observed when sulfuric acid concentrations exceeded 5 × 106 cm−3. The data suggest that there was a positive association between concentrations of particles produced by nucleation and ammonia, but this was not shown definitively. Ammonia mixing ratios during this study were mostly in the 1 to 10 ppbv range.
Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NOx(NO ...plus NO2) concentration, which is determined by plant NOxemission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NOxand volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NOxemission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NOxreductions from these sources.
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