[1] A particle-into-liquid sampler (PILS) was coupled to a total organic carbon (TOC) analyzer for 3 s integrated measurements of water-soluble organic carbon (WSOC) in PM 1 ambient particles. The components of the instrument are described in detail. The PILS-TOC was deployed on the NOAA WP-3D aircraft during the NEAQS/ITCT 2004 program to investigate WSOC sources over the northeastern United States and Canada. Two main sources were identified: biomass burning emissions from fires in Alaska and northwestern Canada and emissions emanating from urban centers. Biomass burning WSOC was correlated with carbon monoxide (CO) and acetonitrile (r 2 > 0.88). These plumes were intercepted in layers at altitudes between 3 and 4 km and contained the highest fine particle volume and WSOC concentrations of the mission. Apart from the biomass burning influence, the lowest WSOC concentrations were recorded in rural air masses that included regions of significant biogenic emissions. Highest concentrations were at low altitudes in distinct plumes from urban centers. WSOC and CO were highly correlated (r 2 > 0.78) in these urban plumes. The ratio of the enhancement in WSOC relative to CO enhancement was found to be low ($3 mg C/m 3 /ppmv) in plumes that had been in transit for a short time, and increased with plume age, but appeared to level off at $32 ± 4 mg C/m 3 /ppmv after $1 day of transport from the sources. The results suggest that the production of WSOC in fine particles depends on compounds coemitted with CO and that this process is rapid with a time constant of $1 day.Citation: Sullivan, A. P., R. E. Peltier, C. A. Brock, J. A. de Gouw, J. S. Holloway, C. Warneke, A. G. Wollny, and R. J. Weber (2006), Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources,

[1] Aircraft measurements of water-soluble organic carbon (WSOC) aerosol over NE North America during summer 2004 (ITCT-2K4) are simulated with a global chemical transport model (GEOS-Chem) to test our understanding of the sources of organic carbon (OC) aerosol in the free troposphere (FT). Elevated concentrations were observed in plumes from boreal fires in Alaska and Canada. WSOC aerosol concentrations outside of these plumes average 0.9 ± 0.9 mg C m À3 in the FT (2-6 km). The corresponding model value is 0.7 ± 0.6 mg C m À3 , including 42% from biomass burning, 36% from biogenic secondary organic aerosol (SOA), and 22% from anthropogenic emissions. Previous OC aerosol observations over the NW Pacific in spring 2001 (ACE-Asia) averaged 3.3 ± 2.8 mg C m À3 in the FT, compared to a model value of 0.3 ± 0.3 mg C m À3 . WSOC aerosol concentrations in the boundary layer (BL) during ITCT-2K4 are consistent with OC aerosol observed at the IMPROVE surface network. The model is low in the boundary layer by 30%, which we attribute to secondary formation at a rate comparable to primary anthropogenic emission. Observed WSOC aerosol concentrations decrease by a factor of 2 from the BL to the FT, as compared to a factor of 10 decrease for sulfate, indicating that most of the WSOC aerosol in the FT originates in situ. Despite reproducing mean observed WSOC concentrations in the FT to within 25%, the model cannot account for the variance in the observations (R = 0.21). Covariance analysis of FT WSOC aerosol with other measured chemical variables suggests an aqueous-phase mechanism for SOA generation involving biogenic precursors.

Abstract. Organic carbon (OC) comprises a large fraction of fine particulate matter (PM2.5) in Mexico City. Daily and select 12-h PM2.5 samples were collected in urban and peripheral sites in Mexico City from 17–30 March 2006. Samples were analyzed for OC and elemental carbon (EC) using thermal-optical filter-based methods. Real-time water-soluble organic carbon (WSOC) was collected at the peripheral site. Organic compounds, particularly molecular markers, were quantified by soxhlet extraction with methanol and dichloromethane, derivitization, and gas chromatography with mass spectrometric detection (GCMS). A chemical mass balance model (CMB) based on molecular marker species was used to determine the relative contribution of major sources to ambient OC. Motor vehicles, including diesel and gasoline, consistently accounted for 47% of OC in the urban area and 31% on the periphery. The daily contribution of biomass burning to OC was highly variable, and ranged from 5–30% at the urban site and 11–50% at the peripheral site. The remaining OC unapportioned to primary sources showed a strong correlation with WSOC and was considered to be secondary in nature. Comparison of temporally resolved OC showed that contributions from primary aerosol sources during daylight hours were not significantly different from nighttime. This study provides quantitative understanding of the important sources of OC during the MILAGRO 2006 field campaign.

[1] The sources, abundance and nature of atmospheric particles that serve as ice nuclei (IN) for cold cloud formation remain some of the most important, yet poorly-characterized, features of aerosol-cloud interactions that indirectly affect climate. Although a great deal of effort has focused on characterizing the ice nucleating ability of mineral dusts, less is known about carbonaceous particles. A primary source for carbonaceous IN is from biomass combustion. Here we report new measurements of IN activity at À30 C and above water saturation from biomass burning generated particles from prescribed burns and wildfires in the western US. These measurements suggest a range of IN activity, with variability largely dependent on the intensity of the fire. Although the fraction of particles generated during burns which serve as IN is quite small, the large numbers of particles generated in fires make biomass burning a potentially important source of IN to the atmosphere. Citation: Prenni, A.

Abstract. Given significant challenges with available measurements of aerosol acidity, proxy methods are frequently used to estimate the acidity of atmospheric particles. In this study, four of the most common aerosol acidity proxies are evaluated and compared: (1) the ion balance method, (2) the molar ratio method, (3) thermodynamic equilibrium models, and (4) the phase partitioning of ammonia. All methods are evaluated against predictions of thermodynamic models and against direct observations of aerosol-gas equilibrium partitioning acquired in Mexico City during the MILAGRO study. The ion balance and molar ratio methods assume that any deficit in inorganic cations relative to anions is due to the presence of H+; and that a higher H+ loading and lower cation/anion ratio both correspond to increasingly acidic particles (i.e., lower pH). Based on the MILAGRO measurements, no correlation is observed between H+ levels inferred with the ion balance and aerosol pH predicted by the thermodynamic models and ammonia–ammonium (NH3–NH4+) partitioning. Similarly, no relationship is observed between the cation / anion molar ratio and predicted aerosol pH. Using only measured aerosol chemical composition as inputs without any constraint for the gas phase, the Extended Aerosol Inorganics Model (E-AIM) and ISORROPIA-II thermodynamic equilibrium models tend to predict aerosol pH levels that are inconsistent with the observed NH3–NH4+ partitioning. The modeled pH values from both models run with gas + aerosol inputs agreed well with the aerosol pH predicted by the phase partitioning of ammonia. It appears that (1) thermodynamic models constrained by gas + aerosol measurements, and (2) the phase partitioning of ammonia provide the best available predictions of aerosol pH. Furthermore, neither the ion balance nor the molar ratio can be used as surrogates for aerosol pH, and published studies to date with conclusions based on such acidity proxies may need to be reevaluated. Given the significance of acidity for chemical processes in the atmosphere, the implications of this study are important and far reaching.