Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L-1, respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( Nd) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients Kad (5.9-362.7 L g-1) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Optimization of a mist chamber (Cofer scrubber) for sampling water-soluble organics in air.

While the atmospheric fate and transport of biogenic and anthropogenic hydrocarbons has been extensively studied, little is known about the behavior of first-, second-, and third generation photo-oxidation products that arise from OH radical oxidation of the parent species. The results of chamber experiments establish that *OH oxidation of biogenic and anthropogenic hydrocarbons yields carbonyls, dicarbonyls, hydroxycarbonyls, and keto-acids. However, little is known about the generation and fate of these products in the ambient atmospheric environment. This is changing because of the advent of methods that rely on 0-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) derivatization of carbonyls in concert with gas chromatography/ion trap mass spectrometry. Such methods provide the means to identify and quantify water-soluble organics, which historically have been difficult to measure. A limitation of existing sampling methods, however, is the use of devices that require low flow rates (0.5-1 L min(-1)). Accordingly, long sampling times (3-4 h) are needed to obtain pptv-ppbv detection limits. The mist chamber is an attractive device because of the high flow rates (25-70 L min(-1)) compatible with its use. Herein, we evaluate a mist chamber using a flow rate of 25-30 L min(-1) to provide short (10 min) sampling times and pptv limits of detection. The results establish a relationship between the Henry's law constant (KH) and the collection efficiency and demonstrate the suitability of the method to measure analytes with KH > or = 10(3) M atm(-1). Adjusting the pH, adding quaternary ammonium salts, or decreasing the temperature of the collecting solution in the mist chamber did not significantly affect the collection efficiency. We tested the method by sampling photooxidation products of isoprene (glyoxal, methylglyoxal, hydroxyacetone, and glycolaldehyde) in the Blodgett Forest, CA. This is the first report of a study the employs the mist chamberto sample hydroxycarbonyls. The accuracy and the reproducibility of the method were evaluated by the analysis of duplicate samples and field spikes. The mean recovery of field spikes was > or =80%, and the relative standard deviation was < or =22% between duplicate measurements. The detection limits were 48, 15, 7.7, and 2.7 pptv for glycolaldehyde, hydroxyacetone, methylglyoxal, and glyoxal, respectively. This work demonstrates the power of the mist chamber in concert with PFBHA derivatization and mass spectrometry to measure pptv concentrations of water-soluble organics with a sampling time of 10 min.

Light extinction by fine atmospheric particles in the White Mountains region of New Hampshire and its relationship to air mass transport.

Chemical, optical, and physical measurements of fine aerosols (aerodynamic diameter < or = 2.5 microm) have been performed at a mountaintop location adjacent to the White Mountain National Forest in northern NH, USA. A 1-month long sampling campaign was conducted at Cranmore Mountain during spring 2000. We report on the apportionment of light extinction by fine aerosols into its major chemical components, and relationships between variations in aerosol parameters and changes in air mass origin. Filter-based, 24-h integrated samples were collected and analyzed for major inorganic ions, as well as organic (OC), elemental (EC), and total carbon. Light scattering and light absorption coefficients were measured at 5-min intervals using an integrating nephelometer and a light absorption photometer. Fine particle number density was measured with a condensation particle counter. Air mass origins and transport patterns were investigated through the use of 3-day backward trajectories and a synoptic climate classification system. Two distinct transport regimes were observed: (1) flow from the north/northeast (N/NE) occurred during 9 out of 18 sample-days; and (2) flow from the west/southwest (W/SW) occurred 8 out of 18 sample-days. All measured and derived aerosol and meteorological parameters were separated into two categories based on these different flow scenarios. During W/SW flow, higher values of aerosol chemical concentration, absorption and scattering coefficients, number density, and haziness were observed compared to N/NE flow. The highest level of haziness was associated with the climate classification Frontal Atlantic Return, which brought polluted air into the region from the mid-Atlantic corridor. Fine particle mass scattering efficiencies of (NH4)2SO4 and OC were 5.35 +/- 0.42 m2 g(-1) and 1.56 +/- 0.40 m2 g(-1), respectively, when transport was out of the N/NE. When transport was from the W/SW the values were 4.94 +/- 0.68 m2 g(-1) for (NH4)2SO4 and 2.18 +/- 0.91 m2 g(-1) for OC. EC mass absorption efficiency when transport was from the N/NE was 9.66 +/- 1.06 m2 g(-1) and 10.80 +/- 1.76 m2 g(-1) when transport was from the W/SW. Results from this work can be used to predict visual air quality in the White Mountain National Forest based on a forecasted synoptic climate classification and its associated visibility.