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Environ Sci Technol. 2012 Oct 16;46(20):11384-92. doi: 10.1021/es302484r. Epub 2012 Sep 25.

Contribution of water-soluble and insoluble components and their hydrophobic/hydrophilic subfractions to the reactive oxygen species-generating potential of fine ambient aerosols.

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School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.


Relative contributions of water- and methanol-soluble compounds and their hydrophobic/hydrophilic subfractions to the ROS (reactive oxygen species)-generating potential of ambient fine aerosols (D(p) < 2.5 μm) are assessed. ROS-generating (or oxidative) potential of the particulate matter (PM) was measured by the dithiothreitol (DTT) assay. Particles were collected on quartz filters (N = 8) at an urban site near central Atlanta during January-February 2012 using a PM(2.5) high-volume sampler. Filter punches were extracted separately in both water and methanol. Hydrophobic and hydrophilic fractions were then subsequently segregated via a C-18 solid phase extraction column. The DTT assay response was significantly higher for the methanol extract, and for both extracts a substantial fraction of PM oxidative potential was associated with the hydrophobic compounds as evident from a substantial attenuation in DTT response after passing PM extracts through the C-18 column (64% for water and 83% for methanol extract; both median values). The DTT activities of water and methanol extracts were correlated with the water-soluble (R = 0.86) and water-insoluble organic carbon (R = 0.94) contents of the PM, respectively. Brown carbon (BrC), which predominantly represents the hydrophobic organic fraction (referred to as humic-like substances, HULIS), was also correlated with DTT activity in both the water (R = 0.78) and methanol extracts (R = 0.83). Oxidative potential was not correlated with any metals measured in the extracts. These findings suggest that the hydrophobic components of both water-soluble and insoluble organic aerosols substantially contribute to the oxidative properties of ambient PM. Further investigation of these hydrophobic organic compounds could help identify sources of a significant fraction of ambient aerosol toxicity.

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