Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns

A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some alkanes are underestimated in the emissions inventory, while some olefins and aromatics are overestimated

Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003

International audienceThe Mexico City Metropolitan Area (MCMA) study in April 2003 had measurements of most atmospheric constituents including OH and HO2. It provided a unique opportunity to examine atmospheric oxidation in a megacity that has more pollution than typical US and European cities. OH typically reached 0.35 pptv (~7×106 cm?3), comparable to amounts observed in US cities, but HO2 reached 40 pptv in the early afternoon, more than observed in most US cities. A steady-state photochemical model simulated the measured OH and HO2 for day and night to within combined measurement and modeling uncertainties for 2/3 of the results. For OH, measured = 0.65 (modeled) + 0.026 pptv, with R2=0.80. For HO2, observed = 0.70 (modeled) + 3.4 pptv, with R2=0.64. Measurements tended to be higher during night and rush hour; the model was higher by ~30% during midday. With a large median measured OH reactivity of more than 120 s?1 during morning rush hour, median ozone production from observed HO2 reached 50 ppb hr?1; RO2 was calculated to have a similar ozone production rate. For both the HO2/OH ratio and the ozone production, the measured values have the essentially same dependence on NO as the modeled values. This similarity is unlike other urban studies in which the NO-dependence of the measured HO2/OH ratio was much less than the modeled ratio and the ozone production rate that was calculated from measured HO2 unexpectedly appeared to increase as a function of NO with no obvious peak

Comparison of aromatic hydrocarbon measurements made by PTR-MS, DOAS and GC-FID during the MCMA 2003 Field Experiment

A comparison of aromatic hydrocarbon measurements is reported for the CENICA supersite in the district of Iztapalapa during the Mexico City Metropolitan Area field experiment in April 2003 (MCMA 2003). Data from three different measurement methods were compared: a Proton Transfer Reaction Mass Spectrometer (PTR-MS), long path measurements using a UV Differential Optical Absorption Spectrometer (DOAS), and Gas Chromatography-Flame Ionization analysis (GC-FID) of canister samples. The principle focus was on the comparison between PTR-MS and DOAS data. Lab tests established that the PTR-MS and DOAS calibrations were consistent for a suite of aromatic compounds including benzene, toluene, p-xylene, ethylbenzene, 1,2,4-trimethylbenzene, phenol and styrene. The point sampling measurements by the PTR-MS and GC-FID showed good correlations (r=0.6), and were in reasonable agreement for toluene, C2-alkylbenzenes and C3-alkylbenzenes. The PTR-MS benzene data were consistently high, indicating interference from ethylbenzene fragmentation for the 145 Td drift field intensity used in the experiment. Correlations between the open-path data measured at 16-m height over a 860-m path length (retroreflector in 430 m distance), and the point measurements collected at 37-m sampling height were best for benzene (r=0.61), and reasonably good for toluene, C2-alkylbenzenes, naphthalene, styrene, cresols and phenol (r>0.5). There was good agreement between DOAS and PTR-MS measurements of benzene after correction for the PTR-MS ethylbenzene interference. Mixing ratios measured by DOAS were on average a factor of 1.7 times greater than the PTR-MS data for toluene, C2-alkylbenzenes, naphthalene and styrene. The level of agreement for the toluene data displayed a modest dependence on wind direction, establishing that spatial gradients – horizontal, vertical, or both – in toluene mixing ratios were significant, and up to a factor of 2 despite the fact that all measurements were conducted above roof level. Our analysis highlights a potential problem in defining a VOC sampling strategy that is meaningful for the comparison with photochemical transport models: meaningful measurements require a spatial fetch that is comparable to the grid cell size of models, which is typically a few 10 km2. Long-path DOAS measurements inherently average over a larger spatial scale than point measurements. The spatial representativeness can be further increased if observations are conducted outside the surface roughness sublayer, which might require measurements at altitudes as high as 10 s of metres above roof level.Alexander von Humboldt-Stiftung (Feodor Lynen fellowship)Henry & Camille Dreyfus Foundation (Postdoctral Fellowship in Environmental Chemistry

Eddy covariance flux measurements of pollutant gases in urban Mexico City

Eddy covariance (EC) flux measurements of the atmosphere/surface exchange of gases over an urban area are a direct way to improve and evaluate emissions inventories, and, in turn, to better understand urban atmospheric chemistry and the role that cities play in regional and global chemical cycles. As part of the MCMA-2003 study, we demonstrated the feasibility of using eddy covariance techniques to measure fluxes of selected volatile organic compounds (VOCs) and CO2 [CO subscript 2] from a residential district of Mexico City (Velasco et al., 2005a, b). During the MILAGRO/MCMA-2006 field campaign, a second flux measurement study was conducted in a different district of Mexico City to corroborate the 2003 flux measurements, to expand the number of species measured, and to obtain additional data for evaluation of the local emissions inventory. Fluxes of CO2 [CO subscript 2] and olefins were measured by the conventional EC technique using an open path CO2 [CO subscript 2] sensor and a Fast Isoprene Sensor calibrated with a propylene standard. In addition, fluxes of toluene, benzene, methanol and C2-benzenes [C subscript 2 - benzenes] were measured using a virtual disjunct EC method with a Proton Transfer Reaction Mass Spectrometer. The flux measurements were analyzed in terms of diurnal patterns and vehicular activity and were compared with the most recent gridded emissions inventory. In both studies, the results showed that the urban surface of Mexico City is a net source of CO2 [CO subscript 2] and VOCs with significant contributions from vehicular traffic. Evaporative emissions from commercial and other anthropogenic activities were significant sources of toluene and methanol. The data show that the emissions inventory is in reasonable agreement with measured olefin and CO2 [CO subscript 2] fluxes, while C2-benzenes [C subscript 2 - benzenes] and toluene emissions from evaporative sources are overestimated in the inventory. It appears that methanol emissions from mobile sources occur, but are not present in the mobile emissions inventory.National Science Foundation (U.S.) (Grant ATM-0528227)United States. Dept. of Energy (Award DE-FG02-05ER63980)Mexico. Comisión Ambiental MetropolitanaMolina Center for Energy and the Environmen

Quantification of biogenic volatile organic compounds with a flame ionization detector using the effective carbon number concept

Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere by plants and include isoprene, monoterpenes, sesquiterpenes, and their oxygenated derivatives. These BVOCs are among the principal factors influencing the oxidative capacity of the atmosphere in forested regions. BVOC emission rates are often measured by collecting samples onto adsorptive cartridges in the field and then transporting these samples to the laboratory for chromatographic analysis. One of the most commonly used detectors in chromatographic analysis is the flame ionization detector (FID). For quantitative analysis with an FID, relative response factors may be estimated using the effective carbon number (ECN) concept. The purpose of this study was to determine the ECN for a variety of terpenoid compounds to enable improved quantification of BVOC measurements. A dynamic dilution system was developed to make quantitative gas standards of VOCs with mixing ratios from 20–55 ppb. For each experiment using this system, one terpene standard was co-injected with an internal reference, n-octane, and analyzed via an automated cryofocusing system interfaced to a gas chromatograph flame ionization detector and mass spectrometer (GC/MS/FID). The ECNs of 16 compounds (14 BVOCs) were evaluated with this approach, with each test compound analyzed at least three times. The difference between the actual carbon number and measured ECN ranged from −24% to −2%. The difference between theoretical ECN and measured ECN ranged from −22% to 9%. Measured ECN values were within 10% of theoretical ECN values for most terpenoid compounds

Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 and 2003 field campaigns

International audienceA wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3

Gyroscopic motion of superfluid trapped atomic condensates

The gyroscopic motion of a trapped Bose gas containing a vortex is studied. We model the system as a classical top, as a superposition of coherent hydrodynamic states, by solution of the Bogoliubov equations, and by integration of the time-dependent Gross-Pitaevskii equation. The frequency spectrum of Bogoliubov excitations, including quantum frequency shifts, is calculated and the quantal precession frequency is found to be consistent with experimental results, though a small discrepancy exists. The superfluid precession is found to be well described by the classical and hydrodynamic models. However the frequency shifts and helical oscillations associated with vortex bending and twisting require a quantal treatment. In gyroscopic precession, the vortex excitation modes $m=\pm 1$ are the dominant features giving a vortex kink or bend, while the $m=+2$ is found to be the dominant Kelvin wave associated with vortex twisting.Comment: 18 pages, 7 figures, 1 tabl

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry

Regularizing Portfolio Optimization

The optimization of large portfolios displays an inherent instability to estimation error. This poses a fundamental problem, because solutions that are not stable under sample fluctuations may look optimal for a given sample, but are, in effect, very far from optimal with respect to the average risk. In this paper, we approach the problem from the point of view of statistical learning theory. The occurrence of the instability is intimately related to over-fitting which can be avoided using known regularization methods. We show how regularized portfolio optimization with the expected shortfall as a risk measure is related to support vector regression. The budget constraint dictates a modification. We present the resulting optimization problem and discuss the solution. The L2 norm of the weight vector is used as a regularizer, which corresponds to a diversification "pressure". This means that diversification, besides counteracting downward fluctuations in some assets by upward fluctuations in others, is also crucial because it improves the stability of the solution. The approach we provide here allows for the simultaneous treatment of optimization and diversification in one framework that enables the investor to trade-off between the two, depending on the size of the available data set

Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) [([O subscript x] ≡ [O subscript 3] + [NO subscript 2])] and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox [O subscript x] measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg [mu g] m−3/ppm [m superscript -3 / ppm] (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg [mu g] m−3/ppm [m superscript -3 / ppm] in Mexico City, where typical values were near 120 μg [mu g] m−3/ppm [m superscript -3 / ppm]. On several days in Mexico City, the [OOA]/[Ox] [[OOA] / O subscript x]] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox [O subscript x] production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] [[OOA] / O subscript x]] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not successful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) [P (SOA) / P (O subscript x)] can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.National Science Foundation (U.S.) (Grant ATM-528227)National Science Foundation (U.S.) (Grant ATM-0528170)National Science Foundation (U.S.) (Grant ATM-0513116)National Science Foundation (U.S.) (Grant ATM-0449815)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FGO2-05ER63982)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DEFGO2- 05ER63980)United States. Dept. of Energy. Office of Biological and Environmental Research. Atmospheric Science Program (Grant DE-FG02-08ER64627)United States. National Oceanic and Atmospheric Administration (Grant NA08OAR4310656