9/10/2012. SOA Formation through Aqueous Chemistry: atmospheric evidence, chemistry, partitioning and prediction. Organics: 30-70% of PM 2.

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Grant Hood
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Professor Dept. of Environmental Sciences Rutgers University Zhang GRL 27 rganic PM is less well understood Why?

scattering/absorbing cloud condensation nuclei Chemical and thermodynamic complexity Measurement, predict behavior b sp (M m -1 ) b sp

1 9/1/212 rganics: 3-7% of PM 2.5 SA Formation through Aqueous Chemistry: atmospheric evidence, chemistry, partitioning and prediction NASA image Barbara Turpin, Professor Dept. of Environmental Sciences Rutgers University Zhang GRL 27 rganic PM is less well understood Why? Atmospheric Aerosol Los Angeles Smog Dept of Environmental Sciences Visibility Degradation Adverse Health Effects Global Climate scattering/absorbing cloud condensation nuclei Chemical and thermodynamic complexity Measurement, predict behavior b sp (M m -1 ) b sp (M m -1 ) Western U.S. Visibility Visibility Degradation Adverse Health Effects New Particle Growth Global Climate scattering/absorbing cloud condensation nuclei Jimenez et al Science 21; Goldstein and Galbally, EST 27; Turpin et al., AE 2 Zhang et al., 1994; McMurry et al.,

9/1/212 Atmospheric Aerosol Dept of Environmental Sciences Atmospheric Aerosol Dept of Environmental Sciences Myocardial infarction Visibility Degradation Adverse Health Effects New Particle Growth

traffic PM (metals and carbonaceous species) Secondary organics largely unstudied The effect of PM on MI s is believed to be linked to: oxidative stress, systemic inflammation, cardiovascular effects

2 9/1/212 Atmospheric Aerosol Dept of Environmental Sciences Atmospheric Aerosol Dept of Environmental Sciences Myocardial infarction Visibility Degradation Adverse Health Effects New Particle Growth Global Climate scattering/absorbing cloud condensation nuclei Visibility Degradation Adverse Health Effects New Particle Growth Global Climate scattering/absorbing cloud condensation nuclei Fresh traffic PM (metals and carbonaceous species) Secondary organics largely unstudied The effect of PM on MI s is believed to be linked to: oxidative stress, systemic inflammation, cardiovascular effects (e.g., Brauer EHP 28; Hoek Lancet 22) More rapid with the aid of organics (e.g., Riipinen ACP 211; Smith PNAS 21; Kulmala ACP 24) Atmospheric Aerosol Dept of Environmental Sciences Visibility Degradation Adverse Health Effects New Particle Growth Global Climate scattering/absorbing cloud condensation nuclei Important contributor to scattering (urban, rural, marine) Light absorbing brown carbon (e.g., Gelencser 23; Sareen 21) Alters aerosol hygroscopicity and CCN activity (e.g., Suda JGR 212; Petters ACP 27) Earth s atmosphere is an oxidizing environment Photochemical reactions produce atmospheric oxidants (e.g., ozone,, N 3, H 2 2 ). Sulfate Nitrate S 2 Nitric acid Nx NH 3 Water rganic PM (SA) rganic gases 2

/C ranges: Aiken EST 28; Jimenez Science 29; Ng ACP 21 Zhang et al.

3 9/1/212 Atmospheric chemistry high atmos. /C /C vs Vapor Pressure Atmospheric rganic Aerosol Atmospheric organic PM - oxidized, hygroscopic SA Aerosol Mass Spectrometer (AMS) /C ranges: Aiken EST 28; Jimenez Science 29; Ng ACP 21 Zhang et al., GRL 27 SA Formation: Traditional Theory (SA gas ) Atmospheric chemistry high atmos. /C Precursors >C7 1-2 oxidation steps Produces SA :C <.5 Intermediate H 2 solubility SA gas SA RH 15 % dum et al, ES&T 1996 Aerosol Mass Spectrometer (AMS) /C ranges: Aiken EST 28; Jimenez Science 29; Ng ACP 21 3

9/1/212 Water is the most abundant condensed phase species Aerosol water is 2-3 times dry particle mass, also clouds Dry sulfate/nitrate/ammonium aerosols Water associated with

Angeles, Sept 9, 1993 Pankow 1994 Primary PM 2.

4 9/1/212 Water is the most abundant condensed phase species Aerosol water is 2-3 times dry particle mass, also clouds Dry sulfate/nitrate/ammonium aerosols Water associated with sulfate/nitrate/ammonium aerosols mg m -2 Liao and Seinfeld, JGR 25 rganics mostly emitted in the gas phase CP fom 76 RT K P = = o 6 CGTSP MWom ζ om pl 1 Carbon Balance Central Los Angeles, Sept 9, 1993 Pankow 1994 Primary PM % of primary A evaporates lipid soluble /C -.1 AMS: HA Fraser et al., EST 1996 Normalized rganic Aerosol Emission Factor (A) Dilution Ratio 1, 1, 1 1 Ambient Conditions Measured Fit of data 95% CI 2 1 rganic Aerosol Emission Factor (g kg-fuel -1 ) C A (µg m -3 ) Robinson et al, Science 27 4

5 9/1/212 Gas-phase photochemistry fragments and oxidizes /C vs. Log P for n-butane Thus, water-soluble vapors are ubiquitous and abundant 1. Example: n-butane + radicals.8 Gas-phase photochemistry fragments and oxidizes Example: isoprene + radicals Recycling Glycolaldehyde 2 nd G Products GLY 1-3 days /C nd G Products 1 st G Products 28.4 days + 6. days + Lifetime = 2.2 days /C days H Epoxide rgperox C5 Hydroxy carbonyl MGLY 3hrs 1 st G Products (Fragmentation) 1 st G Products H 1-14hrs MVK Methacrolein (xidation) (Fragmentation) 3hrs Isoprene Log [P (atm)] Log [P o atm] Photochemistry fragments and oxidizes Compound abundance (ppt) Henry's Constant (M/atm) glyoxal E+5 methylglyoxal 1,4 3.71E+3 formaldehyde 5,3 3.E+3 acetic acid 6,57 5.5E+3 Phenol? 3.E+3 Methanol 3,76 2.2E+2 acetone MEK 2 3, 2 Acetaldehyde 5 7, 14 propanal 8 2, 13 MVK (?) butanal Methacrolein 8 5 benzene 4,.18 toluene 3 8,.15 isoprene 3.28 ethane propane 3, 19,.15 n-butane 1,3 11,.11 isopentane 1, - 11,363 2 most abundant measured organic gases (2 studies) Los Angeles and Pittsburgh Lurmann et al Grosjean et al Millet et al. 25 Nolte et al Fraser et al secondary primary Water-soluble vapors are ubiquitous and abundant CMAQ model result (Carlton, in preparation) 5

6 9/1/212 aqueous SA (SAaq) Water-soluble vapors are ubiquitous and abundant SA Cloud evaporation Potential Precursors Products Aldehydes Diacids Ketones HMWC Monoacids ligomers Alcohols N and S containing Nx Epoxides Isoprene CMAQ model result (Carlton, in preparation) 3 Nx, alkenes, aromatics rganic peroxides N and S containing Blando and Turpin, AtmosEnv, 2 Gelencser and Varga, ACP, 25 SA through Aqueous Chemistry: Partitioning driven by water solubility Implications different precursors Goal: Validate/Refine Aqueous Chemistry Model rate constants known in many cases (Herrmann, Monod, Stefan, Ervens) (Volkamer, ACP, 29) higher /C organic PM loading vertical distribution SA oligomerization Cloud droplet Cloud Droplet Evaporation low volatility products Wet aerosol ~µm Partitioning glyoxal evaporation Glyoxal (C2) Volatile but Highly water soluble /C = 1 glyoxal uptake Partitioning ~.11M rganic/ inorganic oligomerization SA constituents Aerosol water (LWC) isoprene Modeling: Warneck AE 23; Ervens et al. JGR 24; Lim et al. EST 25 6

9/1/212 Aqueous-Phase Reactions with Product Analysis Goal: Validate/Refine Aqueous Chemistry Model Goal: Validate/Refine Aqueous Chemistry Model rate constants known in many cases (Herrmann, Monod,

RG+Prod+H 2 2 ±H 2 S 4, UV+H 2 2 Catalase to stop reactions ESI-MS; IC-ESI-MS; FT-ICR MS; ESI-MS-MS, UV or IC for organic acids, DC for mass balance, H22 Dilute aqueous chemistry model (Lim et al 25)

7 9/1/212 Aqueous-Phase Reactions with Product Analysis Goal: Validate/Refine Aqueous Chemistry Model Goal: Validate/Refine Aqueous Chemistry Model rate constants known in many cases (Herrmann, Monod, Stefan, Ervens) Experiments 1-5 µm RG H 2 2 +hν ( M) 2-5 ph ±H 2 S 4, HN 3,(NH 4 ) 2 S 4 RG: glyoxal, methylglyoxal, glycolaldehyde, pyruvic acid, acetic acid Controls RG+Prod+UV ±H 2 S 4, RG+Prod+H 2 2 ±H 2 S 4, UV+H 2 2 Catalase to stop reactions ESI-MS; IC-ESI-MS; FT-ICR MS; ESI-MS-MS, UV or IC for organic acids, DC for mass balance, H22 Dilute aqueous chemistry model (Lim et al 25) reproduces oxalic, pyruvic acid and total organic carbon at 3 µm in presence and absence of sulfuric acid, nitric acid, ammonium sulfate xalate (µm) Total Carbon (µm) Concentration (µm-c) xalic Acid Concentration (µm) (a) Glyoxal + 3 µm glyoxal (b) 3 µm glyoxal 3 µm 5 glyoxal (c) Time (min) Model Prediction No H 2 S 4 28 µm H 2 S 4 84 µm H 2 S 4 TC measured by TCAN Expected TC Expected TC + larger acids Time (min) xalic acid (µm) Methylglyoxal + 3 µm methylglyoxal +.15 mm H 2 2 Cloud relevant ~3 µm 3 µm methylglyoxal mm H 2 2 Tan et al., EST 29; AE 21 without H 2 S 4 Time (min) H But not at higher concentrations Conductivity (µs) F unknown 2 E unknown 3 I A+B+C Abundance 4x1 4 2x1 4 6x1 5 3x1 5 6x1 5 3x1 5 1x1 5 5x1 4 2x1 4 1x1 4 2x1 5 1x1 5 6x1 4 3x1 4 3 mm methylglyoxal unknown unknown A+B+C m/z - E F H I Formation of products with higher C# than precursors Higher-MW ions Tan AE, 21 7

8 9/1/212 2 H 2 H H + H glyoxal glyoxal (hydrated) H 2 H + H 2 H glyoxylic 1 acid (hydrated) (hydrated) H 2 + H 2 H 3 oxalic acid oxalic acid H 2 Glyoxal Aqueous Mechanism H H H H H R* 3 R* H H decomposition H H decomposition decomposition R 2 R 2 + C 2 H 4 R* 4 2 H 2 C 4 2 H H H + H R* 2 2 H 2 H H H H + H 4 (hydrated) 4 (hydrated) 2formic acid + 2 decomposition + 2 decomposition R* 4 2 H 2 C 2 C 4 2 Gly YB Lim et al ACP 21 radical-radical rates from Guzman et al JPC 26 Ion abundance Signal Key Radical Radical Products Glyoxal (3mM) Glyoxal m/z - m/z- Signal Methylglyoxal (2mM) Methylglyoxal m/z- - FTICR-MS (Negative (negative Mode: mode) Acid products only) Glyoxal, Methylglyoxal Can explain formation of higher carbon number products and reproduce some prominent higher C# products Tartaric acid production from glyoxal + Measured Tartaric + Malonic Acids Modeled Tartaric Acid Model produces oxalate, pyruvate in clouds oligomers in wet aerosols ( radical = 1-12 M) Clouds: /C 1 2 Aerosols: /C ~ 1 PA - Guzman et al JPC 26 Gly YB Lim et al ACP 21 MG YB Lim et al, in prep Gly YB Lim et al ACP 21 MG YB Lim et al, in prep 8

9/1/212 Glyoxal + : Aqueous xidation Products 2.5 Methylglyoxal + : Aqueous Products 2.5 xalic acid /C 2. 1.5 1..5. Tartaric acid Ammonium xalate ligomers 6.

9 9/1/212 Glyoxal + : Aqueous xidation Products 2.5 Methylglyoxal + : Aqueous Products 2.5 xalic acid /C Tartaric acid Ammonium xalate ligomers 6.7 days H xalic acid Cloud Wet aerosol and Non-radical Wet aerosol; cloud droplet aqueous-phase evaporation gas-phase GLY 6 min n-heptane 1.7 days /C H ligomers Ammonium Salt H H Pyruvic acid Acetic acid Photolysis ~2 hrs Wet aerosol H Wet aerosol Cloud and Non-radical 1 min Wet aerosol; cloud droplet aqueous-phase evaporation MGLY n-heptane gas-phase Mesoxalic acid 2-7 hrs 1.7 days Log [P o atm] Log [P o atm] Aqueous chemistry helps explain ambient /C Condensed (aqueous) chemistry leads to higher /C ratios ligomers (aerosols), organic salts (clouds) low volatility SA aq SA SA gas Aerosol Mass Spectrometer (AMS) /C ranges: Aiken EST 28; Jimenez Science 29; Ng ACP 21 SA: rxn with radicals in clouds/aerosols Compound Henry's Constant (M/atm) Aqueous-phase reaction rate (M/s) SAaq HMWC/ ligomer formation glyoxal 3.5E+5 1 E9 yes yes methylglyoxal 3.71E+3 6 E8 yes yes acetic acid 5.5E+3 2 E7 yes no acetone 3 2 E8 yes yes methacrolein 5 2 E9 yes yes MVK 1-1 (?) 8 E8 yes yes phenol 3.E+3 7 E9 no no formaldehyde 3.E+3 no no acetaldehyde 14 3 E9 no no methanol 2.2E+2 9 E8 MEK 2 1 E8 propanal 13 4 E9 butanal E9 ALS STUDIED glycolaldehyde 2 E9 yes yes pyruvic acid 6 E7 yes yes Guaiacol and Syringol yes yes THERS T STUDY epoxides organic peroxides 2 MST ABUNDANT WS MEASURED 9

10 9/1/212 Also. ther oxidants: ozone, nitrate radical? Droplet Evaporation: glyoxal Formation of acetal and aldol condensation oligomers Wet aerosols: Non-radical chemistry: acid and ammonium catalyzed oligomerization orgn formation (ammonium, amines) light absorbing (brown) carbon (incl. from formaldehyde, MG) rgs formation in wet aerosols: radical rxns, esterification, adducts Including with IEPX + acidic sulfate Questions and Challenges: How important is aqsa? In cloud and/or aerosol water? Modeling chemistry or yields Smog chamber or flow tube experiments How do the products partition; volatility of aqsa? What are the major precursors in the real atmosphere? Abbatt, Anastasio, Claeys, Cocker, Cordova, De Haan, Flagan, Galloway, Grgic, Guzman, Herrmann, Hoffmann, Jimenez, Kamens, Keutsch, Lee, Liu, Maenhaut, Michaud, McNeill, Monod, Noziere, Perri, Sareen, Seinfeld, Shapiro, Sun, Surratt, Tolbert, Volkamer, Wortham, Yasmeen, Q. Zhang, and. Questions and Challenges: How important is aqsa? In cloud and/or aerosol water? Modeling chemistry or yields Smog chamber or flow tube experiments How do the products partition; volatility of aqsa? What are the major precursors in the real atmosphere? Edney and Cocker papers no effect of RH on aromatic SA yields Zhou: toluene SA yield depends on liquid water Liquid water, not RH, is the important variable Zhou et al AE, 211 Gas + condensed phase smog chamber experiments several challenges 1

11 9/1/212 Volkamer suggests faster with Questions and Challenges: SA formation faster with radical (light) SA yields increased with seed LWC not M Volume (µm 3 cm -3 ) WSC photochemistry of CHCH How important is aqsa? In cloud and/or aerosol water? Modeling chemistry or yields Smog chamber or flow tube experiments How do the products partition; volatility of aqsa? 1<RH<9% Time (min) Seed: ammonium bisulfate + humic acid salt; dark reaction acetylene; hydrogen peroxide Volkamer ACP 29 What are the major precursors in the real atmosphere? **Galloway et al properties of SA were same with/without (starting from glyoxal not acetylene) Volatility of SA aq mixture after cloud evaporation Standards and samples, with dilutions Droplet Composition: Simulated MG + ; 1 min reaction time Assumed: Continuous replacement of MG Samples, ph 7 Samples, ph 3 Also, with other approaches: El Haddad, Anne Monod, David DeHaan, Alex Lee, Jon Abbatt rtiz et al., 212; rtiz et al. in prep rtiz et al., 212; rtiz et al. in prep 11

9/1/212 Effective vapor pressure: ~ 1-6 1-7 2.

12 9/1/212 Effective vapor pressure: ~ Cloud-relevant MG + and evaporation Effective vapor pressure (3-6 x 1-7 atm) xalic acid Slopes QC Check: Malonic Acid Measured 6 x 1-8 atm Pankow & Asher: 2 x 1-7 atm MG + ph 7 MG + ph 3 3 x 1-7 atm 6 x 1-7 atm rtiz et al., 212; rtiz et al. in prep /C H ligomers Ammonium Salt H H Log [P o atm] Mesoxalic acid Pyruvic acid Acetic acid Photolysis ~2 hrs Wet aerosol H Wet aerosol Cloud Non-radical 1 min aqueous-phase MGLY gas-phase 2-7 hrs n-heptane 1.7 days Questions and Challenges: How important is aqsa? In cloud and/or aerosol water? Modeling chemistry or yields ther precursors? Experiments with cloudwater surrogates Smog chamber or flow tube experiments How do the products partition; volatility of aqsa? What are the major precursors in the real atmosphere? Filtered rainwater + radicals Camden ~ heavily industrialized city Pinelands ~ 3 miles east of Camden Rainwater heavily influenced by aged pollutants from W and SW 12

13 9/1/212 Experiments with cloudwater surrogates: PEGASS: Po Valley, Italy July 212 Ambient watersoluble gases Methylglyoxal + radical cloud chemistry Tan et al., AE 21 13

9/1/212 Precursors are mostly in ESI-MS positive mode (aldehydes, alcohols,

Products in negative mode (organic acids) X 1 3 Relative ion abundance IC

9 min (xalic(po Acid) Valley) Results Conductivity Conductivity (µs) Abundance 1.

14 9/1/212 Precursors are mostly in ESI-MS positive mode (aldehydes, alcohols, organic peroxides). Products in negative mode (organic acids) X 1 3 Relative ion abundance IC Realtime Preliminary PEGASS Retention Time = 22.9 min (xalic(po Acid) Valley) Results Conductivity Conductivity (µs) Abundance PV-MC-1269JK Cuvette Exp Real-Time Pre 1 ESI-MS 2 3 negative 4 6 mode Time (min) Reaction Time Time vs 22.9 min (A) ESI-MS m/z- 89 Aqueous SA helps to explain: (Lim et al., ACP 21) High atmospheric /C Aiken 28; Jimenez 29; Ng 21 Atmospheric abundance of oxalate Kawamura 1993; Rogge 1993; Myriokefalitakis 211 HMWC largest component of M Ambient /C LV-A SV-A Zappoli 1999; Fuzzi 21; Kiss 22; Kalberer 24 Pre Time (min) Reaction Time 14

9/1/212 SA above clouds oxalate/sulfate, C/EC, WSC/C, GoMACCS Increased SA with LWC MASE I/II, ICARTT, GoMACCS Atlanta Sorooshian et al, GRL 21 Sorooshian et al, GRL 21 Hennigan

, GRL 28; ACP 29 Highest A when organics in droplet mode Regime II marine clouds, sunny afternoons highest M droplet mode Regime III hot and dry condensation mode Conclusions

15 9/1/212 SA above clouds oxalate/sulfate, C/EC, WSC/C, GoMACCS Increased SA with LWC MASE I/II, ICARTT, GoMACCS Atlanta Sorooshian et al, GRL 21 Sorooshian et al, GRL 21 Hennigan et al., GRL 28; ACP 29 Highest A when organics in droplet mode Regime II marine clouds, sunny afternoons highest M droplet mode Regime III hot and dry condensation mode Conclusions (SAaq through oxidation): SA forms through reactions in atmospheric waters SA aq precursors: aldehydes, ketones, alcohols, organic peroxides, and/or epoxides Products in clouds: organic acid/salts Products in wet aerosols: HMWC, oligomers, orgs, orgn Droplet mode Condensation mode Hersey et al, ACP 211 Where? photochemical activity, high liquid water conc. 15

9/1/212 Acknowledgements: EPA STAR 28 Students and Postdocs - Yong Bin Lim, Natasha Hodas, Jeff Kirkland, Diana rtiz, Anjuli Ramos, Katye Altieri, Mark Perri, Yi Tan, Mary Moore Collaborators -

16 9/1/212 Acknowledgements: EPA STAR 28 Students and Postdocs - Yong Bin Lim, Natasha Hodas, Jeff Kirkland, Diana rtiz, Anjuli Ramos, Katye Altieri, Mark Perri, Yi Tan, Mary Moore Collaborators - Cristina Facchini, Stefano Decesari, Frank Keutsch, Jeff Collett, Amy Sullivan, Sybil Seitzinger, Annmarie Carlton, Barbara Ervens Funding - NSF, NAA, EPA STAR Effect of water on semivolatile partitioning Does SA have access to M at high LWC? Into a single aerosol phase: 1. reduces MW om increasing K p 2. hydrophilic reduces ζ i, increasing K p Microscopic Mixing: 3. hydrophobic increases ζ i, decreasing K p Seinfeld and Pankow, 23 1.Between particle heterogeneity External to internal mixture with aging Close to sources Downwind (well aged) 2. Within particle heterogeneity Pankow, 1994 Liquid organic water+electrolyte phase separation to high RH for organics with :C<.7. Substantial overestimation of α- pinene SA at high RH if assume ideal mixture. (Zuend ACP 212) (e.g., Clegg 21; Bertram 211; Song 212; Zuend 212) 16

17 9/1/212 17

Aqueous-Phase Chemistry in TM4-ECPL: SOA Formation via Cloud Processes Stelios Myriokefalitakis 1 Kostas Tsigaridis 2,3 Maria Kanakidou 1

TM meeting, Heraklion, June 2010 Aqueous-Phase Chemistry in TM4-ECPL: SOA Formation via Cloud Processes Stelios Myriokefalitakis 1 Kostas Tsigaridis 2,3 Maria Kanakidou 1 1 Environmental Chemical Processes