Items

Advanced search

Mercury dynamics and mass balance in a subtropical forest, southwestern China

The mid-subtropical forest area in southwest China was affected by anthropogenic mercury (Hg) emissions over the past 3 decades. We quantified mercury dynamics on the forest field and measured fluxes and pools of Hg in litterfall, throughfall, stream water and forest soil in an evergreen broadleaved forest field in southwestern China. Total Hg (THg) input by the throughfall and litterfall was assessed at 32.2 and 42.9 µg m−2 yr−1, respectively, which was remarkably higher than those observed from other forest fields in the background of North America and Europe. Hg fluxes across the soil–air interface (18.6 mg m−2 yr−1) and runoff and/or stream flow (7.2 µg m−2 yr−1) were regarded as the dominant ways for THg export from the forest field. The forest field hosts an enormous amount of atmospheric Hg, and its reserves is estimated to be 25 341 µg m2. The ratio of output to input Hg fluxes (0.34) is higher compared with other study sites. The higher output / input ratio may represent an important ecological risk for the downstream aquatic ecosystems, even if the forest field could be an effective sink of Hg.
Photochemical age of air pollutants, ozone, and secondary organic aerosol in transboundary air observed on Fukue Island, Nagasaki, Japan

To better understand the secondary air pollution in transboundary air over westernmost Japan, ground-based field measurements of the chemical composition of fine particulate matter ( ≤  1 µm), mixing ratios of trace gas species (CO, O3, NOx, NOy, i-pentane, toluene, and ethyne), and meteorological elements were conducted with a suite of instrumentation. The CO mixing ratio dependence on wind direction showed that there was no significant influence from primary emission sources near the monitoring site, indicating long- and/or mid-range transport of the measured chemical species. Despite the considerably different atmospheric lifetimes of NOy and CO, these mixing ratios were correlated (r2 = 0.67). The photochemical age of the pollutants, t[OH] (the reaction time × the mean concentration of OH radical during the atmospheric transport), was calculated from both the NOx ∕ NOy concentration ratio (NOx ∕ NOy clock) and the toluene ∕ ethyne concentration ratio (hydrocarbon clock). It was found that the toluene / ethyne concentration ratio was significantly influenced by dilution with background air containing 0.16 ppbv of ethyne, causing significant bias in the estimation of t[OH]. In contrast, the influence of the reaction of NOx with O3, a potentially biasing reaction channel on [NOx] / [NOy], was small. The t[OH] values obtained with the NOx ∕ NOy clock ranged from 2.9  ×  105 to 1.3  ×  108 h molecule cm−3 and were compared with the fractional contribution of the m∕z 44 signal to the total signal in the organic aerosol mass spectra (f44, a quantitative oxidation indicator of carboxylic acids) and O3 mixing ratio. The comparison of t[OH] with f44 showed evidence for a systematic increase of f44 as t[OH] increased, an indication of secondary organic aerosol (SOA) formation. To a first approximation, the f44 increase rate was (1.05 ± 0.03)  ×  10−9  ×  [OH] h−1, which is comparable to the background-corrected increase rate observed during the New England Air Quality Study in summer 2002. The similarity may imply the production of similar SOA component, possibly humic-like substances. Meanwhile, the comparison of t[OH] with O3 mixing ratio showed that there was a strong proportional relationship between O3 mixing ratio and t[OH]. A first approximation gave the increasing rate and background mixing ratio of ozone as (3.48 ± 0.06)  ×  10−7  ×  [OH] ppbv h−1 and 30.7 ppbv, respectively. The information given here can be used for prediction of secondary pollution magnitude in the outflow from the Asian continent.
Hotspot of glyoxal over the Pearl River delta seen from the OMI satellite instrument: implications for emissions of aromatic hydrocarbons

The Pearl River delta (PRD) is a densely populated hub of industrial activity located in southern China. OMI (Ozone Monitoring Instrument) satellite observations reveal a large hotspot of glyoxal (CHOCHO) over the PRD that is almost twice as large as any other in Asia. Formaldehyde (HCHO) and NO2 observed by OMI are also high in the PRD but no more than in other urban/industrial areas of China. The CHOCHO hotspot over the PRD can be explained by industrial paint and solvent emissions of aromatic volatile organic compounds (VOCs), with toluene being a dominant contributor. By contrast, HCHO in the PRD originates mostly from VOCs emitted by combustion (principally vehicles). By applying a plume transport model to wind-segregated OMI data, we show that the CHOCHO and HCHO enhancements over the PRD observed by OMI are consistent with current VOC emission inventories. Prior work using CHOCHO retrievals from the SCIAMACHY satellite instrument suggested that emission inventories for aromatic VOCs in the PRD were too low by a factor of 10–20; we attribute this result in part to bias in the SCIAMACHY data and in part to underestimated CHOCHO yields from oxidation of aromatics. Our work points to the importance of better understanding CHOCHO yields from the oxidation of aromatics in order to interpret space-based CHOCHO observations in polluted environments.
Exploring atmospheric blocking with GPS radio occultation observations

Atmospheric blocking has been closely investigated in recent years due to its impact on weather and climate, such as heat waves, droughts, and flooding. We use, for the first time, satellite-based observations from Global Positioning System (GPS) radio occultation (RO) and explore their ability to resolve blocking in order to potentially open up new avenues complementing models and reanalyses. RO delivers globally available and vertically highly resolved profiles of atmospheric variables such as temperature and geopotential height (GPH). Applying a standard blocking detection algorithm, we find that RO data robustly capture blocking as demonstrated for two well-known blocking events over Russia in summer 2010 and over Greenland in late winter 2013. During blocking episodes, vertically resolved GPH gradients show a distinct anomalous behavior compared to climatological conditions up to 300 hPa and sometimes even further up into the tropopause. The accompanying increase in GPH of up to 300 m in the upper troposphere yields a pronounced tropopause height increase. Corresponding temperatures rise up to 10 K in the middle and lower troposphere. These results demonstrate the feasibility and potential of RO to detect and resolve blocking and in particular to explore the vertical structure of the atmosphere during blocking episodes. This new observation-based view is available globally at the same quality so that blocking in the Southern Hemisphere can also be studied with the same reliability as in the Northern Hemisphere.
Particle water and pH in the eastern Mediterranean: source variability and implications for nutrient availability

Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope  =  0.92, R2  =  0.8, n  =  5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10–15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m−3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 µg m−3; thus, organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening, and nighttime hours.The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air mass origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.
Studying the vertical aerosol extinction coefficient by comparing in situ airborne data and elastic backscatter lidar

Vertical profiles of aerosol particle optical properties were explored in a case study near the San Pietro Capofiume (SPC) ground station during the PEGASOS Po Valley campaign in the summer of 2012. A Zeppelin NT airship was employed to investigate the effect of the dynamics of the planetary boundary layer at altitudes between ∼  50 and 800 m above ground. Determined properties included the aerosol particle size distribution, the hygroscopic growth factor, the effective index of refraction and the light absorption coefficient. The first three parameters were used to retrieve the light scattering coefficient. Simultaneously, direct measurements of both the scattering and absorption coefficient were carried out at the SPC ground station. Additionally, a single wavelength polarization diversity elastic lidar system provided estimates of aerosol extinction coefficients using the Klett method to accomplish the inversion of the signal, for a vertically resolved comparison between in situ and remote-sensing results. Note, however, that the comparison was for the most part done in the altitude range where the overlap function is incomplete and accordingly uncertainties are larger. First, the airborne results at low altitudes were validated with the ground measurements. Agreement within approximately ±25 and ±20 % was found for the dry scattering and absorption coefficient, respectively. The single scattering albedo, ranged between 0.83 and 0.95, indicating the importance of the absorbing particles in the Po Valley region. A clear layering of the atmosphere was observed during the beginning of the flight (until ∼  10:00 LT – local time) before the mixing layer (ML) was fully developed. Highest extinction coefficients were found at low altitudes, in the new ML, while values in the residual layer, which could be probed at the beginning of the flight at elevated altitudes, were lower. At the end of the flight (after ∼  12:00 LT) the ML was fully developed, resulting in constant extinction coefficients at all altitudes measured on the Zeppelin NT. Lidar estimates captured these dynamic features well and good agreement was found for the extinction coefficients compared to the in situ results, using fixed lidar ratios (LR) between 30 and 70 sr for the altitudes probed with the Zeppelin. These LR are consistent with values for continental aerosol particles that can be expected in this region.
Spatiotemporal variations in atmospheric aerosols in East Asia: Identifying local pollutants and transported Asian aerosols in Osaka, Japan using DRAGON

In this work, we document the spatial and temporal variations of atmospheric aerosols in East Asia, specifically focusing on the NASA/AERONET-Osaka site in March 2012 during the AERONET “DRAGON-Japan” campaign. Air pollution has become a serious issue in East Asia in recent years, with particular problems caused by fine particles having diameters of up to 2.5 μm (PM2.5). Emissions of anthropogenic aerosols are known to increase with economic growth, whereas natural dust concentrations show significant variation with season and changing wind patterns. We focus on variations in the mass concentrations of particulate matter (PM) gathered by a sampler (SPM-613D) at the NASA/AERONET-Osaka site in March 2012, and have compositionally analyzed individual PM types using a scanning electron microscope (SEM) coupled with an energy dispersive X-ray analyzer (EDX). Our data show that Asian aerosols derived from distal sources were unequivocally detected in Japan on 11th March 2012. Such pollutants can be carried by winds from continental China and subsequently merge with local emissions, thus accentuating air pollution problems.
Vortex-wide chlorine activation by a mesoscale PSC event in the Arctic winter of 2009/10

In the Arctic polar vortex of the 2009/10 winter temperatures were low enough to allow widespread formation of polar stratospheric clouds (PSCs). These clouds occurred during the initial chlorine activation phase which provided the opportunity to investigate the impact of PSCs on chlorine activation. Satellite observations of gas-phase species and PSCs are used in combination with trajectory modeling to assess this initial activation. The initial activation occurred in association with the formation of PSCs over the east coast of Greenland at the beginning of January 2010. Although this area of PSCs covered only a small portion of the vortex, it was responsible for almost the entire initial activation of chlorine vortex wide. Observations show HCl (hydrochloric acid) mixing ratios decreased rapidly in and downstream of this region. Trajectory calculations and simplified heterogeneous chemistry modeling confirmed that the initial chlorine activation continued until ClONO2 (chlorine nitrate) was completely depleted and the activated air masses were advected throughout the polar vortex. For the calculation of heterogeneous reaction rates, surface area density is estimated from backscatter observations. Modeled heterogeneous reaction rates along trajectories intersecting with the PSCs indicate that the initial phase of chlorine activation occurred in just a few hours. These calculations also indicate that chlorine activation on the binary background aerosol is significantly slower than on the PSC particles and the observed chlorine activation can only be explained by an increase in surface area density due to PSC formation. Furthermore, there is a strong correlation between the magnitude of the observed HCl depletion and PSC surface area density.
Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (<mo>•</mo>OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼  2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10−20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.
The mechanism of spray electrification: the waterfall effect

The waterfall effect describes the separation of charge by splashing at the base of a waterfall. Smaller drops that have a net negative charge are created, while larger drops and/or the bulk maintain overall charge neutrality with a net positive charge. Since it was first described by Lenard (1892) the effect has been confirmed many times, but a molecular explanation has not been available. Application of our fluctuation-correlation model of hydrophobic hydration accounts for the negative charge observed at aqueous interfaces with low permittivity materials. The negative surface charge observed in the waterfall effect is created by the preferential adsorption of hydroxide ions generated from the autolysis of water. On splashing, shear forces generate small negative drops from the surface, leaving a positive charge on the remaining large fragment. The waterfall effect is a manifestation of the general phenomenon of the negative charge at the interface between water and hydrophobic surfaces that is created by the preferential adsorption of hydroxide ions.