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Lagrangian mixing in an axisymmetric hurricane model

This paper discusses the extension of established Lagrangian mixing measures to make them applicable to data extracted from a 2-D axisymmetric hurricane simulation. Because of the non-steady and unbounded characteristics of the simulation, the previous measures are extended to a moving frame approach to create time-dependent mixing rates that are dependent upon the initial time of particle integration, and are computed for nonlocal regions. The global measures of mixing derived from finite-time Lyapunov exponents, relative dispersion, and a measured mixing rate are applied to distinct regions representing different characteristic feautures within the model. It is shown that these time-dependent mixing rates exhibit correlations with maximal tangential winds during a quasi-steady state, establishing a connection between mixing and hurricane intensity.
Dust aerosol effect on semi-arid climate over Northwest China detected from A-Train satellite measurements

The impact of dust aerosols on the semi-arid climate of Northwest China is analyzed by comparing aerosol and cloud properties derived over the China semi-arid region (hereafter, CSR) and the United States semi-arid region (hereafter, USR) using several years of surface and A-Train satellite observations during active dust event seasons. These regions have similar climatic conditions, but aerosol concentrations are greater over the CSR. Because the CSR is close to two major dust source regions (Taklamakan and Gobi deserts), the aerosols over the CSR not only contain local anthropogenic aerosols (agricultural dust, black carbon and other anthropogenic aerosols), but also include natural dust transported from the source regions. The aerosol optical depth, averaged over a 3-month period, derived from MODIS for the CSR is 0.27, which is 47% higher than that over the USR (0.19). Although transported natural dust only accounts for 53% of this difference, it is a major contributor to the average absorbing aerosol index, which is 27% higher in the CSR (1.07) than in the USR (0.84). During dust event periods, liquid water cloud particle size, optical depth and liquid water path are smaller by 9%, 30% and 33% compared to dust-free conditions, respectively.
Relationships between mineral dust and cloud properties in the West African Sahel

Aerosol cloud interactions are known to be of great importance to many parts of the climate system. Five years of observations from three different satellites (Aqua, ENVISAT and Meteosat Second Generation) are used to statistically analyse the relationship of mineral dust aerosol, separated from other aerosol species, with monsoon season cloud state in the West African Sahel domain. Additionally, observations of the Tropical Rainfall Measuring Mission are used for discrimination of dry and wet seasons. The aerosol-cloud-interactions are analysed separately by season and air mass in order to minimise spurious correlations with meteorological conditions. The detailed analysis uncovers different counteracting relationships of the mineral dust aerosol with the cloud state, which is also evident from an analysis of the spatial distribution patterns of cloud properties changes with dust activity. The aerosol-cloud relationships found from the analysis of this multiple year dataset are mainly consistent with the hypothesis of a suppression of convective activity, but also indications of lifetime enhancement and thus increased cloud cover and convective intensity are found in some subsets.
An investigation of the sub-grid variability of trace gases and aerosols for global climate modeling

One fundamental property and limitation of grid based models is their inability to identify spatial details smaller than the grid cell size. While decades of work have gone into developing sub-grid treatments for clouds and land surface processes in climate models, the quantitative understanding of sub-grid processes and variability for aerosols and their precursors is much poorer. In this study, WRF-Chem is used to simulate the trace gases and aerosols over central Mexico during the 2006 MILAGRO field campaign, with multiple spatial resolutions and emission/terrain scenarios. Our analysis focuses on quantifying the sub-grid variability (SGV) of trace gases and aerosols within a typical global climate model grid cell, i.e. 75×75 km2. Our results suggest that a simulation with 3-km horizontal grid spacing adequately reproduces the overall transport and mixing of trace gases and aerosols downwind of Mexico City, while 75-km horizontal grid spacing is insufficient to represent local emission and terrain-induced flows along the mountain ridge, subsequently affecting the transport and mixing of plumes from nearby sources. Therefore, the coarse model grid cell average may not correctly represent aerosol properties measured over polluted areas. Probability density functions (PDFs) for trace gases and aerosols show that secondary trace gases and aerosols, such as O3, sulfate, ammonium, and nitrate, are more likely to have a relatively uniform probability distribution (i.e. smaller SGV) over a narrow range of concentration values. Mostly inert and long-lived trace gases and aerosols, such as CO and BC, are more likely to have broad and skewed distributions (i.e. larger SGV) over polluted regions. Over remote areas, all trace gases and aerosols are more uniformly distributed compared to polluted areas. Both CO and O3 SGV vertical profiles are nearly constant within the PBL during daytime, indicating that trace gases are very efficiently transported and mixed vertically by turbulence. But, simulated horizontal variability indicates that trace gases and aerosols are not well mixed horizontally in the PBL. During nighttime the SGV for trace gases is maximum at the surface, and quickly decreases with height. Unlike the trace gases, the SGV of BC and secondary aerosols reaches a maximum at the PBL top during the day. The SGV decreases with distance away from the polluted urban area, has a more rapid decrease for long-lived trace gases and aerosols than for secondary ones, and is greater during daytime than nighttime. The SGV of trace gases and aerosols is generally larger than for meteorological quantities. Emissions can account for up to 50% of the SGV over urban areas such as Mexico City during daytime for less-reactive trace gases and aerosols, such as CO and BC. The impact of emission spatial variability on SGV decays with altitude in the PBL and is insignificant in the free troposphere. The emission variability affects SGV more significantly during daytime (rather than nighttime) and over urban (rather than rural or remote) areas. The terrain, through its impact on meteorological fields such as wind and the PBL structure, affects dispersion and transport of trace gases and aerosols and their SGV.
Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes – if any – a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm−3 s−1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of radical sources and radical chain reactions in photochemical models. Since the photochemical processing of pollutants in the MCMA is radical limited, our analysis identifies the drivers for ozone and SOA formation. We conclude that reductions in VOC emissions provide an efficient opportunity to reduce peak concentrations of these secondary pollutants, because (1) about 70% of radical production is linked to VOC precursors; (2) lowering the VOC/NOx ratio has the further benefit of reducing the radical re-cycling efficiency from radical chain reactions (chemical amplification of radical sources); (3) a positive feedback is identified: lowering the rate of radical production from organic precursors also reduces that from inorganic precursors, like ozone, as pollution export from the MCMA caps the amount of ozone that accumulates at a lower rate inside the MCMA. Continued VOC reductions will in the future result in decreasing peak concentrations of ozone and SOA in the MCMA.
Oxidative capacity of the Mexico City atmosphere – Part 2: A ROx radical cycling perspective

A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study oxidative capacity (our ability to predict OH radicals) and ROx (ROx=OH+HO2+RO2+RO) radical cycling in a polluted (i.e., very high NOx=NO+NO2) atmosphere. Model simulations were performed using the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds (VOC)), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx (=OH+HO2) concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. We conclude that the most likely scenario to reconcile model predictions with observations is the existence of a currently unidentified additional source for RO2 radicals, in combination with an additional sink for HO2 radicals that does not form OH. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length. We present a first attempt to calculate chain length rigorously i.e., we define two parameters that account for atmospheric complexity, and are based on (1) radical initiation, n(OH), and (2) radical termination, ω. We find very high values of n(OH) in the early morning are incompatible with our current understanding of ROx termination routes. We also observe missing reactivity in the rate of ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. We argue that this uncertainty is partly accounted for in lumped chemical codes that are optimized to predict ozone concentrations; however, these codes do not reflect the true uncertainty in oxidative capacity that is relevant to other aspects of air quality management, such as the formation of secondary organic aerosol (SOA). Our analysis highlights that apart from uncertainties in emissions, and meteorology, there is an additional major uncertainty in chemical mechanisms that affects our ability to predict ozone and SOA formation with confidence.
Identification of potential regional sources of atmospheric total gaseous mercury in Windsor, Ontario, Canada using hybrid receptor modeling

Windsor (Ontario, Canada) experiences trans-boundary air pollution as it is located on the border immediately downwind of industrialized regions of the United States of America. A study was conducted in 2007 to identify the potential regional sources of total gaseous mercury (TGM) and investigate the effects of regional sources and other factors on seasonal variability of TGM concentrations in Windsor. TGM concentration was measured at the University of Windsor campus using a Tekran® 2537A Hg vapour analyzer. An annual mean of 2.02±1.63 ng/m3 was observed in 2007. The average TGM concentration was high in the summer (2.48±2.68 ng/m3) and winter (2.17±2.01 ng/m3), compared to spring (1.88±0.78 ng/m3) and fall (1.76±0.58 ng/m3). Hybrid receptor modeling potential source contribution function (PSCF) was used by incorporating 72-h backward trajectories and measurements of TGM in Windsor. The results of PSCF were analyzed in conjunction with the Hg emissions inventory of North America (by state/province) to identify regions affecting Windsor. In addition to annual modeling, seasonal PSCF modeling was also conducted. The potential source region was identified between 24–61° N and 51–143° W. Annual PSCF modeling identified major sources southwest of Windsor, stretching from Ohio to Texas. The emissions inventory also supported the findings, as Hg emissions were high in those regions. Results of seasonal PSCF modeling were analyzed to find the combined effects of regional sources, meteorological conditions, and surface re-emissions, on seasonal variability of Hg concentrations. It was found that the summer and winter highs of atmospheric Hg can be attributed to areas where large numbers of coal fired power plants are located in the USA. Weak atmospheric dispersion due to low winds and high re-emission from surfaces due to higher temperatures also contributed to high concentrations in the summer. In the winter, the atmospheric removal of Hg was slow, but strong winds led to more dispersion, resulting in lower concentrations than the summer. Future studies could use smaller grid sizes and refined emission inventories, for more accurate analysis of source-receptor relationship of atmospheric Hg.
Laboratory study on new particle formation from the reaction OH + SO2: influence of experimental conditions, H2O vapour, NH3 and the amine tert-butylamine on the overall process

Nucleation experiments starting from the reaction of OH radicals with SO2 have been performed in the IfT-LFT flow tube under atmospheric conditions at 293±0.5 K for a relative humidity of 13–61%. The presence of different additives (H2, CO, 1,3,5-trimethylbenzene) for adjusting the OH radical concentration and resulting OH levels in the range (4–300) ×105 molecule cm−3 did not influence the nucleation process itself. The number of detected particles as well as the threshold H2SO4 concentration needed for nucleation was found to be strongly dependent on the counting efficiency of the used counting devices. High-sensitivity particle counters allowed the measurement of freshly nucleated particles with diameters down to about 1.5 nm. A parameterization of the experimental data was developed using power law equations for H2SO4 and H2O vapour. The exponent for H2SO4 from different measurement series was in the range of 1.7–2.1 being in good agreement with those arising from analysis of nucleation events in the atmosphere. For increasing relative humidity, an increase of the particle number was observed. The exponent for H2O vapour was found to be 3.1 representing an upper limit. Addition of 1.2×1011 molecule cm−3 or 1.2×1012 molecule cm−3 of NH3 (range of atmospheric NH3 peak concentrations) revealed that NH3 has a measureable, promoting effect on the nucleation rate under these conditions. The promoting effect was found to be more pronounced for relatively dry conditions, i.e. a rise of the particle number by 1–2 orders of magnitude at RH = 13% and only by a factor of 2–5 at RH = 47% (NH3 addition: 1.2×1012 molecule cm−3). Using the amine tert-butylamine instead of NH3, the enhancing impact of the base for nucleation and particle growth appears to be stronger. Tert-butylamine addition of about 1010 molecule cm−3 at RH = 13% enhances particle formation by about two orders of magnitude, while for NH3 only a small or negligible effect on nucleation in this range of concentration appeared. This suggests that amines can strongly influence atmospheric H2SO4-H2O nucleation and are probably promising candidates for explaining existing discrepancies between theory and observations.
Functional group composition of ambient and source organic aerosols determined by tandem mass spectrometry

The functional group composition of various organic aerosols (OA) is investigated using a recently developed analytical approach based on atmospheric pressure chemical ionisation-tandem mass spectrometry (APCI-MS/MS). The determinations of three functional groups contents are performed quantitatively by neutral loss (carboxylic and carbonyl groups, R-COOH and R-CO-R´ respectively) and precursor ion (nitro groups, R-NO2) scanning modes of a tandem mass spectrometer. Major organic aerosol sources are studied: vehicular emission and wood combustion for primary aerosol sources; and a secondary organic aerosol (SOA) produced through photooxidation of o-xylene. The results reveal significant differences in the functional group contents of these source aerosols. The laboratory generated SOA is dominated by carbonyls while carboxylics are preponderate in the wood combustion particles. On the other hand, vehicular emissions are characterised by a strong nitro content. The total amount of the three functional groups accounts for 1.7% (vehicular) to 13.5% (o-xylene photooxidation) of the organic carbon. Diagnostic functional group ratios are then used to tentatively discriminate sources of particles collected in an urban background environment located in an Alpine valley (Chamonix, France) during a strong winter pollution event. The three functional groups under study account for a total functionalisation rate of 2.2 to 3.8% of the organic carbon in this ambient aerosol, which is also dominated by carboxylic moieties. In this particular case study of a deep alpine valley during winter, we show that the nitro- and carbonyl-to-carboxylic diagnostic ratios can be a useful tool to discriminate sources. In these conditions, the total OA concentrations are highly dominated by wood combustion OA. This result is confirmed by an organic markers source apportionment approach which assess a wood burning organic carbon contribution of about 60%. Finally, examples of functional group mass spectra of all aerosols under study are presented, and additional perspectives offered by the mass spectra in terms of OA characterisation are discussed.
PTR-MS measurements of non-methane volatile organic compounds during an intensive field campaign at the summit of Mount Tai, China, in June 2006

Owing to recent industrialization, Central East China has become a significant source of air pollutants. To examine the processes controlling the chemistry and transport of tropospheric ozone, we performed on-line measurements of non-methane volatile organic compounds (NMVOCs) as part of an intensive field campaign at Mount Tai, China, in June 2006 (MTX2006), using proton transfer reaction mass spectrometry (PTR-MS). Temporal variations of NMVOCs were recorded in mass-scan mode from m/z17 to m/z 300 during 12–30 June 2006. More than thirty kinds of NMVOCs were detected up to m/z 160, including alkenes, aromatics, alcohols, aldehydes, and ketones. In combination with non-methane hydrocarbon data obtained by a gas chromatography with flame ionization detection, it was found that oxygenated VOCs were the predominant NMVOCs. Diurnal variations depending mainly on local photochemistry were observed during 24–28 June. During the night of 12 June, we observed an episode of high NMVOCs concentrations attributed to the burning of agricultural biomass. The ΔNMVOCs/ΔCO ratios derived by PTR-MS measurements for this episode (with biomass burning (BB) plume) and during 16–23 June (without BB plume) are compared to emission ratios from various types of biomass burning as reviewed by Andreae and Merlet (2001) and to ratios recently measured by PTR-MS in tropical forests (Karl et al., 2007) and at urban sites (Warneke et al., 2007).