Jiang Wenqing, Ma Lan, Niedek Christopher, Anastasio Cort, Zhang Qi
Department of Environmental Toxicology, University of California, 1 Shields Avenue, Davis, California 95616, United States.
Agricultural and Environmental Chemistry Graduate Program, University of California, 1 Shields Avenue, Davis, California 95616, United States.
ACS Earth Space Chem. 2023 Apr 24;7(5):1107-1119. doi: 10.1021/acsearthspacechem.3c00022. eCollection 2023 May 18.
Atmospheric brown carbon (BrC) can impact the radiative balance of the earth and form photooxidants. However, the light absorption and photochemical properties of BrC from different sources remain poorly understood. To address this gap, dilute water extracts of particulate matter (PM) samples collected at Davis, CA over one year were analyzed using high resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectroscopy. Positive matrix factorization (PMF) on combined AMS and UV-vis data resolved five water-soluble organic aerosol (WSOA) factors with distinct mass spectra and UV-vis spectra: a fresh and an aged water-soluble biomass burning OA (BBOA and BBOA) and three oxygenated OA (OOAs). BBOA is the most light-absorbing, with a mass absorption coefficient (MAC) of 1.1 m g, while the OOAs are the least (MAC = 0.01-0.1 m g). These results, together with the high abundance of BBOAs (∼52% of the WSOA mass), indicate that biomass burning activities such as residential wood burning and wildfires are an important source of BrC in northern California. The concentrations of aqueous-phase photooxidants, i.e., hydroxyl radical (·OH), singlet molecular oxygen (O*), and oxidizing triplet excited states of organic carbon (C*), were also measured in the PM extracts during illumination. Oxidant production potentials (PP) of the five WSOA factors were explored. The photoexcitation of BrC chromophores from BB emissions and in OOAs is a significant source of O* and C*. By applying our PP values to archived AMS data at dozens of sites, we found that oxygenated organic species play an important role in photooxidant formation in atmospheric waters.
大气棕碳(BrC)会影响地球的辐射平衡并形成光氧化剂。然而,不同来源的BrC的光吸收和光化学性质仍知之甚少。为了填补这一空白,使用高分辨率气溶胶质谱(HR-AMS)和紫外-可见光谱对加利福尼亚州戴维斯市一年内收集的颗粒物(PM)样品的稀水提取物进行了分析。对AMS和紫外-可见数据进行正矩阵分解(PMF),解析出五个具有不同质谱和紫外-可见光谱的水溶性有机气溶胶(WSOA)因子:一个新鲜的和一个老化的水溶性生物质燃烧有机气溶胶(BBOA和BBOA)以及三个氧化有机气溶胶(OOA)。BBOA的光吸收最强,质量吸收系数(MAC)为1.1 m g,而OOA的光吸收最弱(MAC = 0.01-0.1 m g)。这些结果,再加上BBOA的高丰度(约占WSOA质量的52%),表明诸如居民燃木和野火等生物质燃烧活动是加利福尼亚州北部BrC的重要来源。在光照期间,还测量了PM提取物中液相光氧化剂的浓度,即羟基自由基(·OH)、单线态分子氧(O*)和有机碳的氧化三线态激发态(C*)。探讨了五个WSOA因子的氧化剂生成潜力(PP)。BB排放物和OOA中BrC发色团的光激发是O和C的重要来源。通过将我们的PP值应用于数十个站点的存档AMS数据,我们发现氧化有机物种在大气水体中的光氧化剂形成中起着重要作用。