Tethered balloon system and High-Resolution Mass Spectrometry Reveal Increased Organonitrates Aloft Compared to the Ground Level.

Atmospheric particles play critical roles in climate. However, significant knowledge gaps remain regarding the vertically resolved organic molecular-level composition of atmospheric particles due to aloft sampling challenges. To address this, we use a tethered balloon system at the Southern Great Plains Observatory and high-resolution mass spectrometry to, respectively, collect and characterize organic molecular formulas (MF) in the ground level and aloft (up to 750 m) samples. We show that organic MF uniquely detected aloft were dominated by organonitrates (139 MF; 54% of all uniquely detected aloft MF). Organonitrates that were uniquely detected aloft featured elevated O/C ratios (0.73 ± 0.23) compared to aloft organonitrates that were commonly observed at the ground level (0.63 ± 0.22). Unique aloft organic molecular composition was positively associated with increased cloud coverage, increased aloft relative humidity (∼40% increase compared to ground level), and decreased vertical wind variance. Furthermore, 29% of extremely low volatility organic compounds in the aloft sample were truly unique to the aloft sample compared to the ground level, emphasizing potential oligomer formation at higher altitudes. Overall, this study highlights the importance of considering vertically resolved organic molecular composition (particularly for organonitrates) and hypothesizes that aqueous phase transformations and vertical wind variance may be key variables affecting the molecular composition of aloft organic aerosol.

Using soil records with atmospheric dispersion modeling to investigate the effects of clean air regulations on 60 years of manganese deposition in Marietta, Ohio (USA).

Atmospheric emissions of metals from anthropogenic activities have led to deposition and contamination of soils worldwide. We quantified addition of manganese (Mn) to soils around the largest emitter of Mn in the United States (U.S.) using chemical analyses and atmospheric dispersion modeling (Second-Order Closure Integrated Puff (SCIPUFF)). Concentrations of soil-surface Mn were enriched by 9-fold relative to that of the parent material within 1 km of the facility. Elevated concentrations of Mn and chromium (Cr), another potentially toxic element that was emitted, document contamination only within 1 m of the soil surface. Total mass of Mn added per unit land area integrated over 1 m, mMn, equals ~80 mg Mn cm(-2) near the facility. Values of mMn remained above background up to tens of kilometers from the source. Air concentrations of Mn particles of 7.5-micron diameter simulated with SCIPUFF using available data for the emission rate and local meteorological conditions for 2006 were consistent with measured air concentrations. However, the Mn deposition calculated for 2006 with SCIPUFF yielded a cumulative value over the lifetime of the refinery (60 years) that is a factor of 15 lower than the Mn observed to have been added to the soils. This discrepancy can be easily explained if Mn deposition rates before 1988 were more than an order of magnitude greater than today. Such higher emissions are probable, given the changes in metal production with time and the installation of emission controls after the Clean Air Act (1970). This work shows that atmospheric dispersion models can be used with soil profiles to understand the changes in metal emissions over decadal timescales. In addition, the calculations are consistent with the Clean Air Act accounting for a 15-fold decrease in the Mn deposition to soils around the refinery per metric ton of Mn alloy produced.