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Organic compounds in the atmosphere play a pivotal role in atmospheric chemistry, and clouds are significant in the genesis and alteration of these compounds. Di-carboxylic organic anions such as oxalate serve as tracers for aqueous processing. This poster details our findings from summer measurements of three major organic acids (formic acid, acetic acid, oxalic acid), as well as inorganic anions (sulfate, chloride, nitrate) and cations (sodium, potassium, ammonium, calcium, magnesium) in cloud water, aerosol, and cloud droplet residual samples collected at the summit of Whiteface Mountain (WFM) in the Adirondack Mountains, northern New York State. We also evaluate the contribution of these organic acids to water-soluble organic carbon (WSOC) concentrations. Previous studies have explored the oxalate: WSOC ratio with ozone levels, aiming to deduce the influence of biogenic Volatile Organic Compounds (VOCs) on Secondary Organic Aerosol (SOA) formation from nearby forest ecosystems. Our poster presents new observations that significantly broaden this understanding by comparing to diverse global environments and analyzing both cloud water and aerosol phases. Additionally, we introduce oxalate: sulfate ratios from our dataset, proposed by other researchers as a key indicator of aqueous processing due to the enhanced production rates of these ions by liquid water content (sulfate ion) or droplet surface area (oxalate ion). We compare the observed range of oxalate: sulfate ratios with those from field campaigns conducted in other regions. Moreover, for the first time, we examine the relationship between ammonium and organic acids across cloud water, aerosol, and droplet residual samples collected in 2023, and discuss the influence of wildfire smoke on these dynamics.
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This content will become publicly available on November 6, 2025
Exploring the Increasing Trend of Organic Carbon in the Atmospheric Aqueous Phase
Organic carbon (OC) is a highly diverse class of compounds that represents a small but critical fraction of the atmosphere’s chemical composition. Volatile organic compounds (VOCs), when combined with nitrogen oxides (NOx), can produce tropospheric ozone (O3), a regulated air pollutant. OC also represents a large and growing fraction of aerosol mass, either through direct emissions from sources like fossil combustion and biomass burning, or through secondary chemistry by the oxidation and subsequent reduction of vapor pressure of VOCs leading to condensational growth. Clouds droplets and precipitation can contain additional OC due to the dissolution of soluble organic gases to the aqueous phase. OC has abundantly been found in aqueous samples of clouds, fog, and precipitation, exposing these compounds to unique aqueous chemical reactions and wet deposition. However, the concentrations and controlling factors of atmospheric aqueous organic carbon remain highly unconstrained. Cloud water measurements at Whiteface Mountain in the Adirondack Mountains in upstate New York have revealed an increasing trend of Total Organic Carbon (TOC), with annual median concentrations doubling in 14 years, possibly signaling a growing trend in atmospheric OC. However, the causes and potential consequences of this trend remain unclear. Another question that has yet to be explored is if this trend in OC extends beyond WFM. To answer this question, this work explores the trends of WFM cloud water and 4 additional long-term cloud water and wet deposition datasets that have measured TOC or dissolved OC (DOC) throughout the Northeast US. These sites include Mt Washington, NH, Hubbard Brook NH, Thompson Farm NH, and Sleepers River Vermont. This work will also discuss potential hypotheses driving this increasing trend including increased biomass burning influence and increased biogenic emissions in the region.
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- Award ID(s):
- 1945563
- PAR ID:
- 10570968
- Publisher / Repository:
- National Atmospheric Deposition Program
- Date Published:
- Format(s):
- Medium: X
- Location:
- Duluth MN
- Sponsoring Org:
- National Science Foundation
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null (Ed.)Cloud cycling plays a key role in the evolution of atmospheric particles and gases, producing secondary aerosol mass and transforming the optical properties and impacts of aerosols globally. In this study, bulk cloud water samples collected at Whiteface Mountain (Wilmington, NY) in the summer of 2017 were aerosolized, dried to 50% RH, and analyzed for the evaporative loss of water soluble organic carbon (WSOC) and for brown carbon (BrC) formation. Systematic WSOC evaporation occurred in all cloud water samples, while no evidence for drying induced BrC formation was observed. On average, 11% (±3%) of WSOC evaporated when the aerosolized cloud droplets were dried to 50% RH, though this represents a lower bound on the WSOC reversibly partitioned to clouds due to experimental constraints. To our knowledge, this represents the first direct measurements of organic evaporation from actual cloud water undergoing drying. Formate and acetate contributed 19%, on average, to the evaporated WSOC, while no oxalate evaporation occurred. GECKO-A model simulations were carried out to predict the production of WSOC compounds that reversibly partition to cloud water from photooxidation of an array of VOCs. The model results suggest that precursor VOC identity and oxidation regime (VOC:NO x ) have a dramatic effect on the reversible partitioning of WSOC to cloud water and the abundance of aqSOA precursors, though the higher abundance of reversibly partitioned WSOC predicted by the model may be due to aqueous production of low-volatility material in the actual cloud samples. This study underscores the importance of the large fraction of unidentified compounds that contribute to WSOC in cloud water and their aqueous processing.more » « less
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