Items

Advanced search

A global perspective on aerosol from low-volatility organic compounds

Global production of organic aerosol from primary emissions of semivolatile (SVOCs) and intermediate (IVOCs) volatility organic compounds is estimated using the global chemical transport model, GEOS-Chem. SVOC oxidation is predicted to be a larger global source of net aerosol production than oxidation of traditional parent hydrocarbons (terpenes, isoprene, and aromatics). Using a prescribed rate constant and reduction in volatility for atmospheric oxidation, the yield of aerosol from SVOCs is predicted to be about 75% on a global, annually-averaged basis. For IVOCs, the use of a naphthalene-like surrogate with different high-NOx and low-NOx parameterizations produces a global aerosol yield of about 30%, or roughly 5 Tg/yr of aerosol. Estimates of the total global organic aerosol source presented here range between 60 and 100 Tg/yr. This range reflects uncertainty in the parameters for SVOC volatility, SVOC oxidation, SVOC emissions, and IVOC emissions, as well as wet deposition. The highest estimates result if SVOC emissions are significantly underestimated (by more than a factor of 2) or if wet deposition of the gas-phase semivolatile species is less effective than previous estimates. A significant increase in SVOC emissions, a reduction of the volatility of the SVOC emissions, or an increase in the enthalpy of vaporization of the organic aerosol all lead to an appreciable reduction of prediction/measurement discrepancy. In addition, if current primary organic aerosol (POA) inventories capture only about one-half of the SVOC emission and the Henrys Law coefficient for oxidized semivolatiles is on the order of 103 M/atm, a global estimate of OA production is not inconsistent with the top-down estimate of 140 Tg/yr by (Goldstein and Galbally, 2007). Additional information is needed to constrain the emissions and treatment of SVOCs and IVOCs, which have traditionally not been included in models.
Ozone reservoir layers in a coastal environment – a case study in southern Taiwan

The air layer between the nocturnal boundary layer and the top of the daily mixing layer in an ozone-polluted area is known to serve as an ozone reservoir since the ozone that is produced in the mixing layer on the preceding day is effectively preserved throughout the night in the air layer. Ozone reservoir layers existing at night can enhance the accumulation of surface ozone on the following day. However, our knowledge of the characteristics of ozone reservoir layers and their effects on the daily ozone accumulations is limited. In this work, ozone reservoir layers were experimentally investigated at a coastal, near-mountain site in southern Taiwan, 30 km away from the coastline. Tethered ozone soundings were performed to obtain vertical profiles of ozone and meteorological variables during a four-day ozone episode in November 2006. Observation-based methods are adopted to evaluate the effects of the ozone reservoir layers on the surface ozone accumulation during the four-day ozone episode. Ozone reservoir layers were found to develop every evening with a depth of 1200–1400 m. Ozone concentrations within the reservoir layers reached over 140 parts per billion (ppb). From each evening to midnight, the size of the ozone reservoir layer and the ozone concentration inside dramatically changed. As a result, a concentrated, elevated ozone reservoir layer formed with a depth of 400 m at 800–1200 m every midnight. For the rest of each night, the elevated ozone reservoir layer gradually descended until it reached 500–900 m in the next morning. The observed ozone reservoir layer is formed by the invasion of a cool, marine air mass into a relatively warm, ozone-rich mixing layer in the evening. The descending is related to nocturnal coastal subsidence as well. The ozone concentration at the study site was maximal at 15:00–17:00 LT daily because of the addition of the daily produced ozone on the preceding day. The rate of increase of surface ozone concentration due to the downward mixing of the ozone in the ozone reservoir layers can be as high as 12–24 ppb/h in the late morning. The contribution of the ozone carried over from the preceding day can be 60–85 ppb, which contributes over 50% to the daily ozone pollution as compared with ozone produced on the study day.
Measurements and comparison of primary biological aerosol above and below a tropical forest canopy using a dual channel fluorescence spectrometer

Aerosol particle size distributions were measured below and above a tropical rainforest canopy in Borneo, Malaysia, in June/July 2008 using the WIBS-3: a single particle dual channel fluorescence spectrometer. Material in the size range 0.8–20 μm was characterized according to optical equivalent diameter (DP), morphology and fluorescence at 310–400 nm and 400–600 nm following excitation at 280 nm and 370 nm respectively. Particles fluorescent after both excitations are likely to be fluorescent primary biological aerosol particles (FBAP). Measured FBAP number concentration (NFBAP) at both sites exhibited clear diurnal cycles. The largest variability was observed in the understorey, where NFBAP reached a minimum of 50–100 L−1 in late morning. In mid afternoon it exhibited strong transient fluctuations as large as 4000 L−1 that were followed by sustained concentrations of 1000–2500 L−1 that reduced steadily between midnight and sunrise. Above the canopy FBAP number ranged from 50–100 L−1 during the daytime to 200–400 L−1 at night but did not exhibit the transient enhancements seen in the understorey. The strong FBAP fluctuations were attributed to the release of fungal spores below the canopy and appeared to be linked to elevated relative humidity. The mean FBAP number fraction in the size range 0.8 μm<DP<20 μm was 55% in the understorey and 28% above canopy. A size mode at 2 μm<DP<4 μm appears at both sites and is primarily FBAP, which dominated the coarse (DP≥2.5 μm) number concentration at both sites, accounting for 75% in the understorey and 57% above the canopy. In contrast, the concentration of non-fluorescent particles (NNON) at both sites was typically 200–500 L−1, the majority of which occupied a size mode at 0.8<DP<1.5 μm. Enhanced understorey NNON was observed daily in mid-afternoon and also at midday on three occasions: the former coincided with the FBAP enhancements and measured approximately 10% of their magnitude; the latter occurred independently of the NFBAP diurnal cycle and comprised particles smaller than 2 μm. Particle diameter of 3–5 μm is consistent with smaller fungal spores, though absolute identification of biological species is not possible with the UV-LIF technique. Based on the measured FBAP and non-fluorescent particle abundances and their observed recovery times following rain showers, FBAP originated beneath the canopy while the non-fluorescent material was transported from further away. It is concluded that these separate sources contributed the majority of the aerosol measured by the WIBS-3 at both sites.
Patterns of mercury dispersion from local and regional emission sources, rural Central Wisconsin, USA

Simultaneous real-time changes in mercury (Hg) speciation- reactive gaseous Hg (RGM), elemental Hg (Hg°), and fine particulate Hg (Hg-PM2.5), were determined from June to November, 2007, in ambient air at three locations in rural Central Wisconsin. Known Hg emission sources within the airshed of the monitoring sites include: 1) a 1114 megawatt (MW) coal-fired electric utility generating station; 2) a Hg-bed chlor-alkali plant; and 3) a smaller (465 MW) coal-burning electric utility. Monitoring sites, showing sporadic elevation of Hg°, Hg-PM2.5, and RGM were positioned at distances of 25, 50 and 100 km northward of the larger electric utility. Median concentrations of Hg°, Hg-PM2.5, and RGM were 1.3–1.4 ng m−3, 2.6–5.0 pg m−3, and 0.6–0.8 pg m−3, respectively. A series of RGM events were recorded at each site. The largest, on 23 September, occurred under prevailing southerly winds, with a maximum RGM value (56.8 pg m-3) measured at the 100 km site, and corresponding elevated SO2 (10.4 ppbv; measured at 50 km site). The finding that RGM, Hg°, and Hg-PM2.5 are not always highest at the 25 km site, closest to the large generating station, contradicts the idea that RGM decreases with distance from a large point source. This may be explained if: 1) the 100 km site was influenced by emissions from the chlor-alkali facility or by RGM from regional urban sources; 2) the emission stack height of the larger power plant promoted plume transport at an elevation where the Hg is carried over the closest site; or 3) RGM was being generated in the plume through oxidation of Hg°. Operational changes at each emitter since 2007 should reduce their Hg output, potentially allowing quantification of the environmental benefit in future studies.
Direct radiative effect of aerosols emitted by transport: from road, shipping and aviation

Aerosols and their precursors are emitted abundantly by transport activities. Transportation constitutes one of the fastest growing activities and its growth is predicted to increase significantly in the future. Previous studies have estimated the aerosol direct radiative forcing from one transport sub-sector, but only one study to our knowledge estimated the range of radiative forcing from the main aerosol components (sulphate, black carbon (BC) and organic carbon) for the whole transportation sector. In this study, we compare results from two different chemical transport models and three radiation codes under different hypothesis of mixing: internal and external mixing using emission inventories for the year 2000. The main results from this study consist of a positive direct radiative forcing for aerosols emitted by road traffic of +20±11 mW m−2 for an externally mixed aerosol, and of +32±13 mW m−2 when BC is internally mixed. These direct radiative forcings are much higher than the previously published estimate of +3±11 mW m−2. For transport activities from shipping, the net direct aerosol radiative forcing is negative. This forcing is dominated by the contribution of the sulphate. For both an external and an internal mixture, the radiative forcing from shipping is estimated at −26±4 mW m−2. These estimates are in very good agreement with the range of a previously published one (from −46 to −13 mW m−2) but with a much narrower range. By contrast, the direct aerosol forcing from aviation is estimated to be small, and in the range −0.9 to +0.3 mW m−2.
Marine boundary layer over the subtropical southeast Pacific during VOCALS-REx – Part 1: Mean structure and diurnal cycle

Atmospheric subsidence over the subtropical southeast Pacific (SEP) leads to a low-level anticyclonic circulation, a cool sea surface and a cloud-topped marine boundary layer (MBL). Observations in this region from a major field campaign during October and November 2008, the VOCALS Regional Experiment, provide ample data to characterize the lower atmospheric features over the SEP. The observations are also useful to test the ability of an area-limited, high-resolution atmospheric model to simulate the SEP conditions. Observations and model-results (where appropriate) improve the characterization of the mean state (Part 1) and variability (Part 2) of the lower troposphere including circulation, MBL characteristics and the upsidence wave. Along 20° S the MBL is generally deeper offshore (1600 m at 85° W) but there is also considerable variability. MBL depth and variability decrease towards the coast and maximum inversion strength is detected between 74–76° W. Weather Research and Forecasting (WRF) simulations underestimate MBL height the most near the coast but improve offshore. Southeasterly trades prevail within the MBL although the wind speed decreases toward the coast. Above the MBL along the coast of Chile, flow is northerly, has a maximum at 3 km, and extends westward to ~74° W, apparently due to the mechanical blocking exerted by the Andes upon the westerly flow aloft. Mean MBL features along northern Chile (18–25° S) are remarkably similar (e.g., MBL depth just below 1 km) in spite of different SST. Observed diurnal cycles of the temperature at the coast and further offshore exhibit a number of conspicuous features that are consistent with the southwestward propagation of an upsidence wave initiated during late evening along the south Peru coast. Furthermore, the passage of the vertical motion results in either constructive or deconstructive interference with the radiatively-forced diurnal cycle of MBL depth. Interference is clearly seen in the soundings at Iquique which are driven by a strong upsidence wave contrary to the radiation-driven cycle, leading to a diurnal cycle opposite of the other sites. Because WRF simulations have a lower MBL height, the speed of the simulated gravity wave is slower than observations and accounts for most of the discrepancy between observed and simulated phase speeds.
Marine boundary layer over the subtropical southeast Pacific during VOCALS-REx – Part 2: Synoptic variability

In the second part of this work we study the day-to-day variability of the marine atmospheric boundary layer (MBL) over the subtropical southeast Pacific using primarily results from a numerical simulation that covered the whole VOCALS-REx period (October–November 2008). In situ and satellite-derived observations of the MBL height in the offshore region indicate rapid, significant variations (from 500 m to 1700 m a.s.l. over a few days) during October. These MBL changes are connected with the passage of midlatitude troughs that altered the large-scale environment over the VOCALS-REx region. In contrast, the synoptic forcing and MBL changes were less prominent during November. Modelled and observed MBL depth at Point Omega (20° S, 85° W) compare quite well during October (but the simulation is on average 200 m lower) while in November the simulation does not perform as well. In the prognostic local MBL height equation the height change, the horizontal MBL height advection, and the large scale vertical velocity at MBL top are calculated explicitly from the simulation. The entrainment velocity is calculated as the residual of the other terms in the equation. While the vertical velocity and residual terms are opposing and generally have the largest magnitude on average, it is the variability in the advection that explains most of the large changes in the MBL depth. Examination of several cases during VOCALS-REx suggests that the advective term is in turn largely controlled by changes in wind direction, driven by midlatitude activity, acting on a MBL that generally slopes down toward the coast. In one phase, the subtropical anticyclone is reinforced and extends toward the Chilean coast, leading to easterly wind that advects low MBL heights from the coast as far as Point Omega. The opposite phase occurs after the passage of an extratropical cyclone over southern Chile, leading to southwesterly wind that advects a deeper MBL towards subtropical latitudes.
Characteristics of size distributions at urban and rural locations in New York

Paired nano- and long-tube Scanning Mobility Particle Sizer (SMPS) systems were operated for four different intensive field campaigns in New York State. Two of these campaigns were at Queens College in New York City, during the summer of 2001 and the winter of 2004. The other field campaigns were at rural sites in New York State. The data with the computed diffusion loss corrections for the sampling lines and the SMPS instruments were examined and the combined SMPS data sets for each campaign were obtained. The diffusion corrections significantly affect total number concentrations, and in New York City, affect the mode structure of the size distributions. The relationship between merged and integrated SMPS total number concentrations with the diffusion loss corrections and the CPC number concentrations yield statistically significant increases (closer to 1) in the slope and correlation coefficient compared to the uncorrected values. The measurements are compared to PM2.5 mass concentrations and ion balance indications of aerosol acidity. Analysis of particle growth rate in comparison to other observations can classify the events and illustrate that urban and rural new particle formation and growth are the result of different causes. Periods of low observed PM2.5 mass, high number concentration, and low median diameter due to small fresh particles are associated with primary emissions for the urban sites; and with particle nucleation and growth for the rural sites. The observations of high PM2.5 mass, lower number concentrations, and higher median diameter are mainly due to an enhancement of photochemical reactions leading to condensation processes in relatively aged air. There are statistically different values for the condensation sink (CS) between urban and rural areas. While there is good association (r2>0.5) between the condensation sink (CS) in the range of 8.35–283.9 nm and PM2.5 mass in the urban areas, there is no discernable association in the rural areas. The average values computed for the CS lie in the range 8.7×10−3–3.5×10−2 s−1.
A climatological perspective of deep convection penetrating the TTL during the Indian summer monsoon from the AVHRR and MODIS instruments

The impact of very deep convection on the water budget and thermal structure of the tropical tropopause layer is still not well quantified, not least because of limitations imposed by the available observation techniques. Here, we present detailed analysis of the climatology of the cloud top brightness temperatures as indicators of deep convection during the Indian summer monsoon, and the variations therein due to active and break periods. We make use of the recently newly processed data from the Advanced Very High Resolution Radiometer (AVHRR) at a nominal spatial resolution of 4 km. Using temperature thresholds from the Atmospheric Infrared Sounder (AIRS), the AVHRR brightness temperatures are converted to climatological mean (2003–2008) maps of cloud amounts at 200, 150 and 100 hPa. Further, we relate the brightness temperatures to the level of zero radiative heating, which may allow a coarse identification of convective detrainment that will subsequently ascend into the stratosphere. The AVHRR data for the period 1982–2006 are used to document the differences in deep convection between active and break conditions of the monsoon. The analysis of AVHRR data is complemented with cloud top pressure and optical depth statistics (for the period 2003–2008) from the Moderate Resolution Imaging Spectroradiometer (MODIS) onboard Aqua satellite. Generally, the two sensors provide a very similar description of deep convective clouds. Our analysis shows that most of the deep convection occurs over the Bay of Bengal and central northeast India. Very deep convection over the Tibetan plateau is comparatively weak, and may play only a secondary role in troposphere-to-stratosphere transport. The deep convection over the Indian monsoon region is most frequent in July/August, but the very highest convection (coldest tops, penetrating well into the TTL) occurs in May/June. Large variability in convection reaching the TTL is due to monsoon break/active periods. During the monsoon break period, deep convection reaching the TTL is almost entirely absent in the western part of the study area (i.e. 60 E–75 E), while the distribution over the Bay of Bengal and the Tibetan Plateau is less affected. Although the active conditions occur less frequently than the break conditions, they may have a larger bearing on the composition of the TTL within the monsoonal anticyclone, and tracer transport into the stratosphere because of deep convection occurring over anthropogenically more polluted regions.
Black carbon aerosols and the third polar ice cap

Recent thinning of glaciers over the Himalayas (sometimes referred to as the third polar region) have raised concern on future water supplies since these glaciers supply water to large river systems that support millions of people inhabiting the surrounding areas. Black carbon (BC) aerosols, released from incomplete combustion, have been increasingly implicated as causing large changes in the hydrology and radiative forcing over Asia and its deposition on snow is thought to increase snow melt. In India BC emissions from biofuel combustion is highly prevalent and compared to other regions, BC aerosol amounts are high. Here, we quantify the impact of BC aerosols on snow cover and precipitation from 1990 to 2010 over the Indian subcontinental region using two different BC emission inventories. New estimates indicate that Indian BC emissions from coal and biofuel are large and transport is expected to expand rapidly in coming years. We show that over the Himalayas, from 1990 to 2000, simulated snow/ice cover decreases by ~0.9% due to aerosols. The contribution of the enhanced Indian BC to this decline is ~36%, similar to that simulated for 2000 to 2010. Spatial patterns of modeled changes in snow cover and precipitation are similar to observations (from 1990 to 2000), and are mainly obtained with the newer BC estimates.