Journal Article

Lability of secondary organic particulate matter

Li, Yong Jie, Bertram, Allan K., Gilles, Mary K., Zaveri, Rahul A., Martin, Scot T., Liu, Pengfei, Wang, Yan

2016

Overview

The energy flows in Earth’s natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic comparedwith biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate D org for the biogenic case is at least 10³ times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PMin Earth’s atmosphere.

• Publisher: National Academy of Sciences,National Academy of Sciences, Washington, DC (United States)
• Subject: Airborne particulates / Anthropogenic factors / atmospheric chemistry / BASIC BIOLOGICAL SCIENCES / Climate system / Earth, Atmospheric, and Planetary Sciences / ENVIRONMENTAL SCIENCES / Evaporation / Evaporation rate / Humidity / INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY / Organic compounds / Particulate matter / Physical Sciences / Quartz / Relative humidity / secondary organic aerosol / VOCs / Volatile organic compounds