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Use of a global model to understand speciated atmospheric mercury observations at five high-elevation sites

Atmospheric mercury (Hg) measurements using the Tekran® analytical system from five high-elevation sites (1400–3200 m elevation), one in Asia and four in the western US, were compiled over multiple seasons and years, and these data were compared with the GEOS-Chem global model. Mercury data consisted of gaseous elemental Hg (GEM) and "reactive Hg" (RM), which is a combination of the gaseous oxidized (GOM) and particulate bound (< 2.5 μm) (PBM) fractions as measured by the Tekran® system. We used a subset of the observations by defining a "free tropospheric" (FT) data set by screening using measured water vapor mixing ratios. The oxidation scheme used by the GEOS-Chem model was varied between the standard run with Br oxidation and an alternative run with OH–O3 oxidation. We used this model–measurement comparison to help interpret the spatio-temporal trends in, and relationships among, the Hg species and ancillary parameters, to understand better the sources and fate of atmospheric RM. The most salient feature of the data across sites, seen more in summer relative to spring, was that RM was negatively correlated with GEM and water vapor mixing ratios (WV) and positively correlated with ozone (O3), both in the standard model and the observations, indicating that RM was formed in dry upper altitude air from the photo-oxidation of GEM. During a free tropospheric transport high RM event observed sequentially at three sites from Oregon to Nevada, the slope of the RM / GEM relationship at the westernmost site was −1020 ± 209 pg ng−1, indicating near-quantitative GEM-to-RM photochemical conversion. An improved correlation between the observations and the model was seen when the model was run with the OH–O3 oxidation scheme instead of the Br oxidation scheme. This simulation produced higher concentrations of RM and lower concentrations of GEM, especially at the desert sites in northwestern Nevada. This suggests that future work should investigate the effect of Br- and O3-initiated gas-phase oxidation occurring simultaneously in the atmosphere, as well as aqueous and heterogeneous reactions to understand whether there are multiple global oxidants for GEM and hence multiple forms of RM in the atmosphere. If the chemical forms of RM were known, then the collection efficiency of the analytical method could be evaluated better.
Influence of biomass burning plumes on HONO chemistry in eastern China

Nitrous acid (HONO) plays a key role in atmospheric chemistry by influencing the budget of hydroxyl radical (OH). In this study, a two-month measurement of HONO and related quantities were analyzed during a biomass burning season in 2012 at a suburban site in the western Yangtze River delta, eastern China. An overall high HONO concentration with the mean value of 0.76 ppbv (0.01 ppbv to 5.95 ppbv) was observed. During biomass burning (BB) periods, both HONO concentration and HONO/NO2 ratio were enhanced significantly (more than a factor of 2, p < 0.01) compared with non-biomass burning (non-BB) periods. A correlation analysis showed that the HONO in BB plumes was more correlated with nitrogen dioxide (NO2) than that with potassium (a tracer of BB). Estimation by the method of potassium tracing suggests a maximum contribution of 17 ± 12% from BB emission to the observed HONO concentrations, and the other over 80% of the observed nighttime HONO concentrations during BB periods were secondarily produced by the heterogeneous conversion of NO2. The NO2-to-HONO conversion rate (CHONO) in BB plumes was almost twice as that in non-BB plumes (0.0062 hr−1 vs. 0.0032 hr−1). Given that the residence time of the BB air masses was lower than that of non-BB air masses, these results suggest BB aerosols have higher NO2 conversion potentials to form HONO than non-BB aerosols. A further analysis based on comparing the surface area at similar particle mass levels and HONO/NO2 ratios at similar surface area levels suggested larger specific surface areas and higher NO2 conversion efficiencies of BB aerosols. A mixed plume of BB and anthropogenic fossil fuel (FF) emissions was observed on 10 June with even higher HONO concentrations and HONO/NO2 ratios. The strong HONO production potential (high HONO/NO2 to PM2.5 ratio) was accompanied with a high sulfate concentration in this plume, suggesting a promotion of mixed aerosols to the HONO formation. In summary, our study suggests an important role of BB in atmospheric chemistry by affecting the HONO budget. This can be especially important in eastern China, where agricultural burning plumes are inevitably mixed with urban and industrial pollution.
On the use of radon for quantifying the effects of atmospheric stability on urban emissions

Radon is increasingly being used as a tool for quantifying stability influences on urban pollutant concentrations. Bulk radon gradients are ideal for this purpose, since the vertical differencing substantially removes contributions from processes on timescales greater than diurnal and (assuming a constant radon source) gradients are directly related to the intensity of nocturnal mixing. More commonly, however, radon measurements are available only at a single height. In this study we argue that single-height radon observations should not be used quantitatively as an indicator of atmospheric stability without prior conditioning of the time series to remove contributions from larger-scale "non-local" processes. We outline a simple technique to obtain an approximation of the diurnal radon gradient signal from a single-height measurement time series, and use it to derive a four category classification scheme for atmospheric stability on a "whole night" basis. A selection of climatological and pollution observations in the Sydney region are then subdivided according to the radon-based scheme on an annual and seasonal basis. We compare the radon-based scheme against a commonly used Pasquill–Gifford (P–G) type stability classification and reveal that the most stable category in the P–G scheme is less selective of the strongly stable nights than the radon-based scheme; this lead to significant underestimation of pollutant concentrations on the most stable nights by the P–G scheme. Lastly, we applied the radon-based classification scheme to mixing height estimates calculated from the diurnal radon accumulation time series, which provided insight to the range of nocturnal mixing depths expected at the site for each of the stability classes.
Recent satellite-based trends of tropospheric nitrogen dioxide over large urban agglomerations worldwide

Trends in tropospheric nitrogen dioxide (NO2) columns over 66 large urban agglomerations worldwide have been computed using data from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument onboard the Envisat platform for the period August 2002 to March 2012. A seasonal model including a linear trend was fitted to the satellite-based time series over each site. The results indicate distinct spatial patterns in trends. While agglomerations in Europe, North America, and some locations in East Asia/Oceania show decreasing tropospheric NO2 levels on the order of −5% yr−1, rapidly increasing levels of tropospheric NO2 are found for agglomerations in large parts of Asia, Africa, and South America. The site with the most rapidly increasing absolute levels of tropospheric NO2 was found to be Tianjin in China with a trend of 3.04 (±0.47) × 1015 molecules cm−2yr−1, whereas the site with the most rapidly increasing relative trend was Kabul in Afghanistan with 14.3 (±2.2) % yr−1. In total, 34 sites exhibited increasing trends of tropospheric NO2 throughout the study period, 24 of which were found to be statistically significant. A total of 32 sites showed decreasing levels of tropospheric NO2 during the study period, of which 20 sites did so at statistically significant magnitudes. Overall, going beyond the relatively small set of megacities investigated previously, this study provides the first consistent analysis of recent changes in tropospheric NO2 levels over most large urban agglomerations worldwide, and indicates that changes in urban NO2 levels are subject to substantial regional differences as well as influenced by economic and demographic factors.
Can positive matrix factorization help to understand patterns of organic trace gases at the continental Global Atmosphere Watch site Hohenpeissenberg?

From the rural Global Atmosphere Watch (GAW) site Hohenpeissenberg in the pre-alpine area of southern Germany, a data set of 24 C2–C8 non-methane hydrocarbons over a period of 7 years was analyzed. Receptor modeling was performed by positive matrix factorization (PMF) and the resulting factors were interpreted with respect to source profiles and photochemical aging. Differing from other studies, no direct source attribution was intended because, due to chemistry along transport, mass conservation from source to receptor is not given. However, at remote sites such as Hohenpeissenberg, the observed patterns of non-methane hydrocarbons can be derived from combinations of factors determined by PMF. A six-factor solution showed high stability and the most plausible results. In addition to a biogenic and a background factor of very stable compounds, four additional anthropogenic factors were resolved that could be divided into two short- and two long-lived patterns from evaporative sources/natural gas leakage and incomplete combustion processes. The volume or mass contribution at the site over the entire period was, in decreasing order, from the following factor categories: background, gas leakage and long-lived evaporative, residential heating and long-lived combustion, short-lived evaporative, short-lived combustion, and biogenic. The importance with respect to reactivity contribution was generally in reverse order, with the biogenic and the short-lived combustion factors contributing most. The seasonality of the factors was analyzed and compared to results of a simple box model using constant emissions and the photochemical decay calculated from the measured annual cycles of OH radicals and ozone. Two of the factors, short-lived combustion and gas leakage/long-lived evaporative, showed winter/summer ratios of about 9 and 7, respectively, as expected from constant source estimations. Contrarily, the short-lived evaporative emissions were about 3 times higher in summer than in winter, while residential heating/long-lived combustion emissions were about 2 times higher in winter than in summer.
On the relationship between open cellular convective cloud patterns and the spatial distribution of precipitation

Precipitation is thought to be a necessary but insufficient condition for the transformation of stratocumulus-topped closed cellular convection to open cellular cumuliform convection. Here we test the hypothesis that the spatial distribution of precipitation is a key element of the closed-to-open cell transition. A series of idealized 3-D simulations are conducted to evaluate the dependency of the transformation on the areal coverage of rain, and to explore the role of interactions between multiple rainy areas in the formation of the open cells. When rain is restricted to a small area, even substantial rain (order few mm day−1) does not result in a transition. With increasing areal coverage of the rain, the transition becomes possible provided that the rain rate is sufficiently large. When multiple small rain regions interact with each other, the transition occurs and spreads over a wider area, provided that the distance between the rain regions is short. When the distance between the rain areas is large, the transition eventually occurs, albeit slowly. For much longer distances between rain regions the system is anticipated to remain in a closed-cell state. These results suggest a connection to the recently hypothesized remote control of open-cell formation. Finally it is shown that this transition occurs along a consistent path in the phase space of the mean vs. coefficient of variation of the liquid water path, droplet number and optical depth. This could be used as a diagnostic tool for global analyses of the statistics of closed- and open-cell occurrence and transitions between them.
Impact of updated traffic emissions on HONO mixing ratios simulated for urban site in Houston, Texas

Recent measurements in Houston show that HONO traffic emissions are 1.7% of NOx emissions, which is about twice the previously estimated value of 0.8% based on tunnel measurements in 2001. The 0.8% value is widely used to estimate mobile emissions of HONO for air quality modeling applications. This study applies the newly estimated HONO / NOx ratio in the WRF–SMOKE–CMAQ modeling system and estimates the impact of higher HONO traffic emissions on its mixing ratios. Since applied emission inventory resulted in overestimates of NOx mixing ratios and because HONO emissions and chemical formation depend on the magnitude of NOx, thus, before proceeding with HONO emission modifications emissions of NOx were adjusted to reflect current emission trends. The modeled mixing ratios of NOx were evaluated against measured data from a number of sites in the Houston area. Overall, the NOx mean value dropped from 11.11 ppbv in the base case to 7.59 ppbv in the NOx-adjusted case becoming much closer to the observed mean of 7.76 ppbv. The index of agreement (IOA) is improved in the reduced NOx case (0.71 vs. 0.75) and the absolute mean error (AME) is lowered from 6.76 to 4.94. The modeled mixing ratios of HONO were evaluated against the actual observed values attained at the Moody Tower in Houston. The model could not reproduce the morning HONO peaks when the low HONO / NOx ratio of 0.008 was used to estimate HONO emissions. Doubling HONO emissions from mobile sources resulted in higher mixing ratios, and the mean value increased from 0.30 to 0.41 ppbv becoming closer to the observed mean concentrations of 0.69 but still low; AME was slightly reduced from 0.46 to 0.43. IOA for simulation that used the 2001 emission values is 0.63 while for simulation with higher HONO emission it increased to 0.70. Increased HONO emissions from mobile sources resulted in a 14% increase in OH during morning time at the location of the Moody Tower and 3% when averaged over an urban area. The increase calculated for daytime was 7 and 1% for the Moody Tower and the urban area, respectively. The impact on ozone was found to be marginal. This study results shed light on the underestimated HONO and OH in the morning from global/regional chemical transport models with the typical emission of 0.8% HONO emission out of the total NOx emissions.
Evaluation of CALIOP 532 nm aerosol optical depth over opaque water clouds

With its height-resolved measurements and near global coverage, the CALIOP lidar onboard the CALIPSO satellite offers a new capability for aerosol retrievals in cloudy skies. Validation of these retrievals is difficult, however, as independent, collocated and co-temporal data sets are generally not available. In this paper, we evaluate CALIOP aerosol products above opaque water clouds by applying multiple retrieval techniques to CALIOP Level 1 profile data and comparing the results. This approach allows us to both characterize the accuracy of the CALIOP above-cloud aerosol optical depth (AOD) and develop an error budget that quantifies the relative contributions of different error sources. We focus on two spatial domains: the African dust transport pathway over the tropical North Atlantic and the African smoke transport pathway over the southeastern Atlantic. Six years of CALIOP observations (2007–2012) from the northern hemisphere summer and early fall are analyzed. The analysis is limited to cases where aerosol layers are located above opaque water clouds so that a constrained retrieval technique can be used to directly retrieve 532 nm aerosol optical depth and lidar ratio. For the moderately dense Sahara dust layers detected in the CALIOP data used in this study, the mean/median values of the lidar ratios derived from a constrained opaque water cloud (OWC) technique are 45.1/44.4 ± 8.8 sr, which are somewhat larger than the value of 40 ± 20 sr used in the CALIOP Level 2 (L2) data products. Comparisons of CALIOP L2 AOD with the OWC-retrieved AOD reveal that for nighttime conditions the L2 AOD in the dust region is underestimated on average by ~26% (0.183 vs. 0.247). Examination of the error sources indicates that errors in the L2 dust AOD are primarily due to using a lidar ratio that is somewhat too small. The mean/median lidar ratio retrieved for smoke is 70.8/70.4 ± 16.2 sr, which is consistent with the modeled value of 70 ± 28 sr used in the CALIOP L2 retrieval. Smoke AOD is found to be underestimated, on average, by ~39% (0.191 vs. 0.311). The primary cause of AOD differences in the smoke transport region is the tendency of the CALIOP layer detection scheme to prematurely assign layer base altitudes and thus underestimate the geometric thickness of smoke layers.
MAX-DOAS tropospheric nitrogen dioxide column measurements compared with the Lotos-Euros air quality model

A 14-month data set of MAX-DOAS (Multi-Axis Differential Optical Absorption Spectroscopy) tropospheric NO2 column observations in De Bilt, the Netherlands, has been compared with the regional air quality model Lotos-Euros. The model was run on a 7×7 km2 grid, the same resolution as the emission inventory used. A study was performed to assess the effect of clouds on the retrieval accuracy of the MAX-DOAS observations. Good agreement was found between modeled and measured tropospheric NO2 columns, with an average difference of less than 1% of the average tropospheric column (14.5 · 1015 molec cm−2). The comparisons show little cloud cover dependence after cloud corrections for which ceilometer data were used. Hourly differences between observations and model show a Gaussian behavior with a standard deviation (σ) of 5.5 · 1015 molec cm−2. For daily averages of tropospheric NO2 columns, a correlation of 0.72 was found for all observations, and 0.79 for cloud free conditions. The measured and modeled tropospheric NO2 columns have an almost identical distribution over the wind direction. A significant difference between model and measurements was found for the average weekly cycle, which shows a much stronger decrease during the weekend for the observations; for the diurnal cycle, the observed range is about twice as large as the modeled range. The results of the comparison demonstrate that averaged over a long time period, the tropospheric NO2 column observations are representative for a large spatial area despite the fact that they were obtained in an urban region. This makes the MAX-DOAS technique especially suitable for validation of satellite observations and air quality models in urban regions.
Insights into characteristics, sources, and evolution of submicron aerosols during harvest seasons in the Yangtze River delta region, China

Atmospheric submicron particulate matter (PM1) is one of the most significant pollution components in China. Despite its current popularity in the studies of aerosol chemistry, the characteristics, sources and evolution of atmospheric PM1 species are still poorly understood in China, particularly for the two harvest seasons, namely, the summer wheat harvest and autumn rice harvest. An Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was deployed for online monitoring of PM1 components during summer and autumn harvest seasons in urban Nanjing, in the Yangtze River delta (YRD) region of China. PM1 components were shown to be dominated by organic aerosol (OA, 39 and 41%) and nitrate (23 and 20%) during the harvest seasons (the summer and autumn harvest). Positive matrix factorization (PMF) analysis of the ACSM OA mass spectra resolved four OA factors: hydrocarbon-like mixed with cooking-related OA (HOA + COA), fresh biomass-burning OA (BBOA), oxidized biomass-burning-influenced OA (OOA-BB), and highly oxidized OA (OOA); in particular the oxidized BBOA contributes ~80% of the total BBOA loadings. Both fresh and oxidized BBOA exhibited apparent diurnal cycles with peak concentration at night, when the high ambient relative humidity and low temperature facilitated the partitioning of semi-volatile organic species into the particle phase. The fresh BBOA concentrations for the harvests are estimated as BBOA = 15.1 × (m/z 60–0.26% × OA), where m/z (mass-to-charge ratio) 60 is a marker for levoglucosan-like species. The (BBOA + OOA-BB)/ΔCO, (ΔCO is the CO minus background CO), decreases as a function of f44 (fraction of m/z 44 in OA signal), which might indicate that BBOA was oxidized to less volatile OOA, e.g., more aged and low volatility OOA (LV-OOA) during the aging process. Analysis of air mass back trajectories indicates that the high BB pollutant concentrations are linked to the air masses from the western (summer harvest) and southern (autumn harvest) areas.