Organic Carbon Chemistry in the Valley Atmosphere: Quinones and - PowerPoint PPT Presentation

Organic Carbon Chemistry in the Valley Atmosphere: Quinones and Peroxides Alam Hasson Department of Chemistry California State University, Fresno

Quinones and Peroxides are minor components of PM Polyaromatic Hydrocarbons (PAH) O O O Quinones O Hydrogen Peroxide (H 2 O 2 ) ~25  g.m ‐ 3 Annual Average PM 2.5 and PAH < 1 ng.m ‐ 3 (0.004% of PM Typical mass loading for quinones mass) Typical mass loading for H 2 O 2 * < 30 ng.m ‐ 3 (0.1% of PM mass) (* for Southern California)

Quinones and Hydrogen Peroxide Cell . OH Fe 3+ Damage Reducing Agent Also present in PM Fe 2+ H 2 O 2 O 2 . ‐ . ‐ O 2 O 2 Atmos. OH O O Ox. ? Primary OH O O Emissions Reducing Agent Reducing Agent Key Questions to address: 1. Do all quinones behave the same? 2. What is the relative importance of emissions vs. chemistry? 3. What is the relative importance of H 2 O 2 production in atmosphere vs. in lung?

Hydrogen Peroxide Generation in the Atmosphere

Hydrogen Peroxide in PM • Fine aerosols contain high concentrations of liquid water, so H 2 O 2 may partition between the gas phase and the aerosol according to Henry’s law: (g)  H 2 H 2 O 2 O 2 (l) H A .P H2O2 = [H 2 O 2 ] aq Oxidation Organics HO 2 + Other Products Self Reaction H 2 O 2 Emissions Uptake into Aqueous Aerosol

Hydrogen Peroxide 2 2 • H 2 O 2 levels are up to 100 3.0 14 times higher in PM than 12 2.5 Gas Phase H 2 O 2 / ppb expected in LA basin. -3 Aerosol H 2 O 2 / ng m 10 2.0 8 ( Hasson and Paulson, J. Aerosol Sci, 1.5 6 459 ‐ 68, 2003. ) 4 1.0 2 -3 0.5 3.0x10 0 5/8 5/13 5/18 5/23 5/28 6/2 6/7 Date Gas Phase H 2 O 2 Aerosol Phase H 2 O 2 [H 2 O 2 ] aerosol / M -3 2.0x10 • Measurements imply that H 2 O 2 is generated within the particles themselves. -3 1.0x10 H A x [H 2 O 2 ] gas = [H 2 O 2 ] liquid • Metals and/or organics (including quinones) may undergo reactions to form H 2 O 2 in particles. 0.0 -9 -9 2.0x10 4.0x10 [H 2 O 2 ] gas / atm.

Endo ‐ vs. Exo ‐ ROS Generation Approximate Range of Ambient Quinone Measurements Approximate -1 1E-3 Range of H 2 O 2 Production Rate / M hr Ambient H 2 O 2 Measurements 1E-4 1E-5 1E-6 1E-7 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 [Quinone] aerosol / M (Ascorbate ‐ only Chemistry) Lower Limit Upper Limit Hydrogen peroxide in PM may be as important as hydrogen peroxide formed by PM.

Quinones Identified in Fresno Air: Do they all behave in the same way? O O O O O O O O Anthraquinone 5,12 ‐ Naphthacenequinone Acenaphthenequinone Phenanthraquinone O O O O O O O O 1,4 ‐ Naphthoquinone 1,2 ‐ Naphthoquinone 1,4 ‐ Chrysenequinone 2,6 ‐ Dtb ‐ 1,4 ‐ Benzoquinone O O O H 3 C H 3 C H 3 C O O O 2 ‐ Methyl Anthraquinone 2,3 ‐ Dimethyl Anthraquinone Benz[a]anthracene ‐ 7,12 ‐ dione

DTT (Dithiothreitol) Assay • Provides information on the potential of PM extracts to cause cell injury. • Quinones/PM oxidize DTT, generating H 2 O 2 . • The reaction rate is correlated with bronchial epithelial cell injury by ROS ( Li et al., Environ. Health Perspect. 2003 ). HO HO HO SH S S S S SH HO HO HO O O O 2 O 2 O O R 4 R 1 R 4 R 1 R 4 R 1 R 4 R 1 R 3 R 2 R 3 R 2 R 3 R 2 R 3 R 2 O O O O O 2. ‐ O 2. ‐ H 2 O 2 O 2

DTT (Dithiothreitol) Assay Rate = k’ PQ [PQ] 0 + k’ 1,4 ‐ NQ [1,4 ‐ NQ] 0 + k’ 1,2 ‐ NQ .[1,2 ‐ NQ] 0 -1 Slope = 0.75 +/- 0.15 min 2 = 0.74 R -6 -4 5.0x10 P = 6 x 10 -1 Measured Rate / M.min -6 4.0x10 -6 3.0x10 -6 2.0x10 -6 1.0x10 0.0 -6 -6 -6 0.0 2.0x10 4.0x10 6.0x10 -1 Calculated Rate / M.min Measured quinones account for all of the reactivity of the PM samples collected. Phenanthraquinone dominates the reactivity of these samples.

Origins of Atmospheric Quinones: Emissions vs. Chemistry

Sources of Quinones and PAH • Samples Collected at Fresno State (November 2005 – June 2006). • Lundgren Impactor with four size cuts (10, 3, 1 and 0.3  m). • ~50 chemical compounds monitored.

Sources of Quinones and PAH: 11/2005 – 7/2006 Quinones PAH 0.35 0.35 1.0 1.0 0.30 0.30 0.8 0.25 0.8 0.25 0.20 0.6 R-Value P-Value 0.6 0.20 P-Value R-Value 0.15 0.15 0.4 0.4 0.10 0.10 0.2 0.2 0.05 0.05 0.0 0.00 0.0 0.00 s n l n t g s n l n t g e s e s e e o o n o o n s u s u l i i i l i i i c t e t D k c t e t D k s a s a i i o i i o h D h D Wood Combustion Gasoline vehicles Vegetation Diesel Road Dust Meat Wood Combustion Gasoline vehicles Vegetation Diesel Road Dust Meat u t u t d o d o e e e e b b a a g C g C v m v m e o e o e e o V R t o V R t a a n n C C e e i i l l o M o M d d s s o o a a o o G G W W Wood combustion correlation is strongly dependent on a few data points. mass loadings are strongly correlated (R 2 = 0.98; P = 2 x 10 ‐ 4 ). PAH and quinone

Some Quinones Expected From PAH Oxidation Chemistry • PAH oxidation chemistry is complicated. • Quinones have been observed in low yield (a few percent or less) from several PAHs. • Because PAH emissions are much greater than quinone emissions, chemical formation of quinones in the atmosphere may exceed primary emissions. (Lee and Lane, Atmospheric Environment, 43, 4886 ‐ 93, 2009. )

Evidence for Photochemistry from Southern California • Role of photochemistry estimated from relative levels of phenanthrene, phenanthraquinone and benzo[g,h,i]perylene. • ~90% of phenanthraquinone is from phenanthrene oxidation. (Eiguren ‐ Fernandez et al, Atmospheric Environment, 42, 2312 ‐ 19, 2008. )

PM in Southern and Central California not the same San Joaquin Valley Los Angeles Basin 50 50 -3 Average PM 2.5 Mass Loading /  g.m 40 40 30 30 20 20 10 10 0 0 n b y e l g p t n b y e g p t r l v c r l l v c u u a i c a i c a e r a n u e o e a e r a n o e u e M p J O M p J O F M u A S N D F M N D J J u A S A A J J Mass Loadings for 2009 (California Air Resources Board)

Field Data – Summer 2008 5 2.0x10 Phenanthrene / AU 5 1.5x10 5 1.0x10 4 5.0x10 0.0 5 6.0x10 Levogllucosan / AU 5 4.0x10 5 2.0x10 0.0 80 60 -3 PM 2.5 /  g.m 40 20 0 8 8 8 8 8 8 8 8 8 8 8 - - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 2 2 2 2 2 2 2 2 / / / / / / / / / / / 7 0 3 6 9 2 5 8 1 4 7 1 2 2 2 2 / / / 1 1 1 7 7 7 / / / / / / / / 6 6 6 6 6 7 7 7 No Phenanthraquinone observed: Not present or all in the gas phase?

Field Data – Summer 2004 Summer A A A 10 Anthraquinone 9 Naphthacenequinone 8 7 -3 Mass Loading / ng.m 6 A 5 A 4 3 Summer B 2 A A 1 B B B B B B B 0 6/8/2004 6/14/2004 6/16/2004 6/18/2004 6/20/2004 6/22/2004 6/24/2004 6/26/2004 6/28/2004 6/30/2004 7/2/2004 7/4/2004 7/6/2004 Date

Daytime vs. Nighttime Chemistry • OH and O 3 are the major daytime oxidants; NO 3 is the main nighttime oxidant. Gas Phase Phenanthraquinone from Phenanthrene Gas Phase Reaction with OH NO 3 O 3 Yield 3% 33% 2% Reaction Rates 3.2 x 10 ‐ 11 1.2 x 10 ‐ 13 4.0 x 10 ‐ 19 (cm 3 .mol ‐ 1 .s ‐ 1 ) Formation Rate 80 800 0.2 (pg.m ‐ 3 .hr ‐ 1 ) (Wang et al, Atmospheric Environment, 41, 2025 ‐ 35, 2007. )

Daytime vs. Nighttime Quinone Levels 25 Fresno State Chrysenequinone 20 -3 Mass Loading / ng.m 15 10 5 0 r r r r r r r r r r r r r r a a a a a a a a a a a a a a M M M M M M M M M M M M M M - - - - - - - - - - - - - - 6 7 8 9 2 3 4 5 6 9 0 1 2 3 1 1 1 1 1 1 2 2 2 2 Central Fresno Central Fresno (Day) Fresno State (Day) Fresno State (Night) • Samples collected at both sites 6:00 am – 6:00 pm. Samples also collected at Fresno State site 6pm – 6 am. • Chrysenequinone, Phenanthraquinone and 1,2 ‐ Naphthoquinone levels were higher during day (although not statistically significant).

Conceptual Model for Secondary PM Formation Photooxidation Photooxidation Products (e.g., Nitrate) Products (e.g., Nitrate) Inversion Layer Primary Emissions Primary Emissions e.g., NOx (Watson and Chow, Atmospheric Environment, 36, 177 ‐ 201, 2002. )

Summary • Certain quinones such as phenanthraquinone likely play a greater role in ROS production than others. • Some evidence for quinone production from chemical reactions, but more work is needed to understand this. • Hydrogen Peroxide in atmospheric particles may play an important role in particle chemistry and health effects, but levels and origins are not well understood.

Acknowledgements Akihiro Ikeda Kennedy Vu Akiteru Ikeda Julie Lyon Enrique Lopez Rick Lazaro Dora Rendulic Mark Sorenson Christina Sabado Dianne Lim Joscelyn Jackson Saddam Muthana Rodhelen Paluyo Denise Soria Juan Camacho Dr. Myeong Chung Dr. Thomas Cahill (UC Davis) Tim Tyner (UCSF ‐ Fresno) Funding San Joaquin Valley Air Pollution Control District College of Science and Mathematics and the Provost’s Office, California State University, Fresno