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Title: Lability of Secondary Organic Particulate Matter

Abstract

Accurate simulations of the consenctrations of atmospheric organic particulate matter (PM) are needed for predicting energy flow in the Earth’s climate system. In the past, simulations of organic PM widely assume equilibrium partitioning of semivolatile organic compounds (SVOCs) between the PM and surrounding vapor. Herein, we test this assumption by measuring evaporation rates and associated vapor mass concentration of organic films representative of atmospheric PM. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH), indicating equilibrium partitioning above a transition RH but not below. In contrast for films representing biogenic PM, no threshold was observed, indicating equilibrium partitioning at all RHs. The results suggest that the mass lability of atmospheric organic PM can differ in consequential ways among Earth’s natural biomes, polluted regions, and regions of land-use change, and these differences need to be considered when simulating atmospheric organic PM.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1340828
Report Number(s):
PNNL-SA-115585
Journal ID: ISSN 1091-6490; KP1701000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal Volume: 113; Journal Issue: 45
Country of Publication:
United States
Language:
English

Citation Formats

Liu, Pengfei, Li, Yong Jie, Wang, Yan, Giles, Mary K., Zaveri, Rahul A., Bertram, Allan K., and Martin, Scot T.. Lability of Secondary Organic Particulate Matter. United States: N. p., 2016. Web. doi:10.1073/pnas.1603138113.
Liu, Pengfei, Li, Yong Jie, Wang, Yan, Giles, Mary K., Zaveri, Rahul A., Bertram, Allan K., & Martin, Scot T.. Lability of Secondary Organic Particulate Matter. United States. doi:10.1073/pnas.1603138113.
Liu, Pengfei, Li, Yong Jie, Wang, Yan, Giles, Mary K., Zaveri, Rahul A., Bertram, Allan K., and Martin, Scot T.. 2016. "Lability of Secondary Organic Particulate Matter". United States. doi:10.1073/pnas.1603138113.
@article{osti_1340828,
title = {Lability of Secondary Organic Particulate Matter},
author = {Liu, Pengfei and Li, Yong Jie and Wang, Yan and Giles, Mary K. and Zaveri, Rahul A. and Bertram, Allan K. and Martin, Scot T.},
abstractNote = {Accurate simulations of the consenctrations of atmospheric organic particulate matter (PM) are needed for predicting energy flow in the Earth’s climate system. In the past, simulations of organic PM widely assume equilibrium partitioning of semivolatile organic compounds (SVOCs) between the PM and surrounding vapor. Herein, we test this assumption by measuring evaporation rates and associated vapor mass concentration of organic films representative of atmospheric PM. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH), indicating equilibrium partitioning above a transition RH but not below. In contrast for films representing biogenic PM, no threshold was observed, indicating equilibrium partitioning at all RHs. The results suggest that the mass lability of atmospheric organic PM can differ in consequential ways among Earth’s natural biomes, polluted regions, and regions of land-use change, and these differences need to be considered when simulating atmospheric organic PM.},
doi = {10.1073/pnas.1603138113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 45,
volume = 113,
place = {United States},
year = 2016,
month =
}
  • We report 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 representativemore » 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 compared with 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 10 3 times greater than that of the anthropogenic case. In conclusion, these differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth’s atmosphere.« less
  • To improve predictions of air quality, visibility, and climate change, knowledge of the viscosities and diffusion rates within organic particulate matter consisting of secondary organic material (SOM) is required. Most qualitative and quantitative measurements of viscosity and diffusion rates within organic particulate matter have focused on SOM particles generated from biogenic volatile organic compounds (VOCs) such as α-pinene and isoprene. In this study, we quantify the relative humidity (RH)-dependent viscosities at 295±1K of SOM produced by photo-oxidation of toluene, an anthropogenic VOC. The viscosities of toluene-derived SOM were 2 × 10 ₋1 to ~6 ×10 6Pa s from 30 tomore » 90%RH, and greater than ~2 × 10 8 Pa s (similar to or greater than the viscosity of tar pitch) for RH ≤ 17%. These viscosities correspond to Stokes–Einstein-equivalent diffusion coefficients for large organic molecules of ~2 ×10 ₋15cm 2s ₋1 for 30 % RH, and lower than ~3 × 10 ₋17cm 2s ₋1 for RH ≤ 17 %. Based on these estimated diffusion coefficients, the mixing time of large organic molecules within 200 nm toluene-derived SOM particles is 0.1–5 h for 30% RH, and higher than ~100 h for RH ≤ 17%. As a starting point for understanding the mixing times of large organic molecules in organic particulate matter over cities, we applied the mixing times determined for toluene-derived SOM particles to the world's top 15 most populous megacities. If the organic particulate matter in these megacities is similar to the toluene-derived SOM in this study, in Istanbul, Tokyo, Shanghai, and São Paulo, mixing times in organic particulate matter during certain periods of the year may be very short, and the particles may be well-mixed. On the other hand, the mixing times of large organic molecules in organic particulate matter in Beijing, Mexico City, Cairo, and Karachi may be long and the particles may not be well-mixed in the afternoon (15:00–17:00 LT) during certain times of the year.« less
  • The effect of organic matter (pig manure, sus scrofa) addition on solubility and free Cd(II) and Zn(II) speciation was studied in two mineral soils. The soils were extracted with ultra pure 0.01 M KNO{sub 3}, and the extracts were analyzed for total dissolved Cd and Zn by graphite furnace AAS and ICP, respectively, and for labile Cd and Zn by differential pulse anodic stripping voltammetry (DPASV). Based on the assumption that the non-ASV-labile fraction of the total dissolved Cd and Zn was organically bound to fulvic acid (FA), the relative fraction of labile to total dissolved Cd and Zn wasmore » used to estimate conditional stability constants (log K) for the formation of Cd-Fulvate (CdFA) and Zn-Fulvate (ZnFA). Species of organically and inorganically associated Cd and Zn, as affected by the addition of pig manure to the two different soil types, were calculated. The addition of organic matter increased the solubility of Cd and Zn in both soils by the formation of organo-metallic complexes. The lability of Zn was, however, reduced substantially, whereas for Cd it was unaffected. The conditional log K values calculated indicate that the stability of organo-metallic complexes with Cd and Zn may be more important than reported previously. This implies that increasing concentrations of dissolved organic acids can increase their solubility, thus leading to the leaching of Cd and Zn into ground water.« less
  • Fine particulate matter (PM2.5) concentrations associated with 202 24-hr samples collected at the National Energy Technology Laboratory (NETL) particulate matter (PM) characterization site in south Pittsburgh from October 1999 through September 2001 were used to apportion PM2.5 into primary and secondary contributions using Positive Matrix Factorization (PMF2). Input included the concentrations of PM2.5 mass determined with a Federal Reference Method (FRM) sampler, semi-volatile PM2.5 organic material, elemental carbon (EC), and trace element components of PM2.5. A total of 11 factors were identified. The results of potential source contributions function (PSCF) analysis using PMF2 factors and HYSPLIT-calculated back-trajectories were used tomore » identify those factors associated with specific meteorological transport conditions. The 11 factors were identified as being associated with emissions from various specific regions and facilities including crustal material, gasoline combustion, diesel combustion, and three nearby sources high in trace metals. Three sources associated with transport from coal-fired power plants to the southeast, a combination of point sources to the northwest, and a steel mill and associated sources to the west were identified. In addition, two secondary-material-dominated sources were identified, one was associated with secondary products of local emissions and one was dominated by secondary ammonium sulfate transported to the NETL site from the west and southwest. Of these 11 factors, the four largest contributors to PM2.5 were the secondary transported material (dominated by ammonium sulfate) (47%), local secondary material (19%), diesel combustion emissions (10%), and gasoline combustion emissions (8%). The other seven factors accounted for the remaining 16% of the PM2.5 mass. The findings are consistent with the major source of PM2.5 in the Pittsburgh area being dominated by ammonium sulfate from distant transport and so decoupled from local activity emitting organic pollutants in the metropolitan area. In contrast, the major local secondary sources are dominated by organic material.« less
  • Fine particulate matter (PM2.5) concentrations associated with 202 24-hr samples collected at the National Energy Technology Laboratory (NETL) particulate matter (PM) characterization site in south Pittsburgh from October 1999 through September 2001 were used to apportion PM2.5 into primary and secondary contributions using Positive Matrix Factorization (PMF2). Input included the concentrations of PM2.5 mass determined with a Federal Reference Method (FRM) sampler, semi-volatile PM2.5, organic material, elemental carbon (EC), and trace element components of PM2.5. A total of 11 factors were identified. The results of potential source contributions function (PSCF) analysis using PMF2 factors and HYSPLIT-calculated back-trajectories were used tomore » identify those factors associated with specific meteorological transport conditions. The 11 factors were identified as being associated with emissions from various specific regions and facilities including crustal material, gasoline combustion, diesel combustion, and three nearby sources high in trace metals. Three sources associated with transport from coal-fired power plants to the southeast, a combination of point sources to the northwest, and a steel mill and associated sources to the west were identified. In addition, two secondary-material-dominated sources were identified, one was associated with secondary products of local emissions and one was dominated by secondary ammonium sulfate transported to the NETL site from the west and southwest. Of these 11 factors, the four largest contributors to PM2.5, were the secondary transported material (dominated by ammonium sulfate) (47%), local secondary material (19%), diesel combustion emissions (10%), and gasoline combustion emissions (8%). The other seven factors accounted for the remaining 16% of the PM2.5 mass. The findings are consistent with the major source of PM2.5 in the Pittsburgh area being dominated by ammonium sulfate from distant transport and so decoupled from local activity emitting organic pollutants in the metropolitan area. In contrast, the major local secondary sources are dominated by organic material.« less