Trace Metals in fine and coarse aerosols: Emerging Results from SPARTAN. Graydon Snider CSC June 8, 2016

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1 Trace Metals in fine and coarse aerosols: Emerging Results from SPARTAN Graydon Snider CSC June 8,

2 Global significance of PM2.5 Dhaka Edmonton Rehovot Hanoi *Forouzanfar et al.: Lancet, Beijing WHO target of PM2.5 = 10 μg m-3 often exceeded Adverse lung, cardiovascular effects 3 million* annual deaths worldwide (3% of all deaths) 2

3 Fine aerosol sizes and their content Respirable fraction (long-lived, unhealthy to breathe) Dust fraction SO 4, NH 4, BC, K, tr. metals, PM 2.5 Crustal: Al, Fe, Ca, Salt: Cl, Na Other salts: Mg, NO 3 publiclab.org/wiki/pm

4 Hazards of trace metals in PM2.5 Coherence and public health implications DOI: / Cardiovascular Hospitalizations* lhousie University] at 05:52 17 May 2016 *Lippmann, M. Crit. Rev. Toxicol., 44(4), , Excess PM2.5 Hospitalizations may be associated with specific species (e.g. NO3, SO4, Ni, V, and Cu) Variance in mortality may be explained by PM2.5 emission source 325 IQR = Inter-quartile range CVD = cardiovascular disease 4 Figure 3. The influence of specific constituents on the associations of PM2.5 mass concentrations on total daily mortality (left panel) and CVD hospitalizations (right panel) in the second-stage analysis in 150 US communities. From Ito et al. (2013). In contrast to the combined estimates from the multi-city mortality analysis, Seattle mortality analysis showed associations between multiple PM2.5 components (Al, K, Si, Zn, EC, CO, and NO2) in the cold season. Consistent with the multi-city analysis, Detroit mortality analysis showed associ- Appendix F on the HEI Final Report on their Web site and Zhou et al., 2011). Having daily data allowed us to examine the effects of distributed lags for these city-specific data sets. Sub-categories of CVD and respiratory hospitalizations were examined in this analysis.

5 SPARTAN = Surface PARticulate matter Network SPARTAN Headquarters: Dalhousie U., Halifax 12 1 Ongoing PM 2.5 evaluation at various sites worldwide Average of 12 months sampling per site (4 26 months) Current Sites: 1. Buenos Aires 2. Ilorin 3. Pretoria 4. Rehovot 5. Kanpur 6. Dhaka 7. Hanoi 8. Bandung 9. Beijing 10. Manila 11. Singapore 12. Atlanta and Mammoth Cave (temporary sites) 5

6 SPARTAN: Physical Aerosol Sampling Fine-mode (PM 2.5 ) 20 µg ** µg material** 9-day intermittent sampling (per filter) Coarse-mode (PM c ) Filter Weighing (Cleanroom facility) 6

7 Fine/Coarse Aerosol Forensics Ion Chromatography (water-soluble ions) ICP-MS (acid-digested metals) Surface reflectance (Black Carbon) Species Relative Composition Element ng m -3 Trace Elements = {Ti, V, Cr, Mn, K, Zn, Cu, As, Ba, and Pb} < 1 % Soil = {Mg, Al, Fe} 8 23% Fe Zn Sea Salt = {Na} 1 10% Pb 40 Ammonium nitrate = {NO 3 } 2 10% Mn 10 Ammonium sulfate = {SO 4, NH 4 } 5 26% As 2 Effective Black Carbon = {Reflectance} 2 13% 7

8 Combining Aerosol Components Particle-bound water (PBW) Residue Matter (RM*) = Total [Inorg.] [PBW] ASO 4 Trace elements: low in mass, rich in information (Ti, V, Cr, Mn, K, Zn, Cu, As, Ba, and Pb) ANO 3 Crustal Materials: Mg, Al, Fe Salt Equivalent BC 8

9 PM 2.5 Collocated studies: Correlation 20 aerosol species with established networks Mammoth Cave, KY Atlanta, GA IMPROVE Network SPARTAN major species EPA Network SPARTAN (parts per thousand) 9

10 Trace element distribution: Enrichment Factors Enrichment EF(X)= [X] [Al] PM2.5 [X] [Al] Crust. EF > < EF < 100 EF < 10 Highly Anthropogenic (Zn, As, Pb, Cd) Mixed-sourced (K, Cr, V) Natural (Fe, Ti, Mg) Element (X) Crustal Average via Taylor and McLennan, Rev. Geophys., 33(2),

11 Trace metals in PM 2.5 : signatures for traffic and wood burning Tire Wear (Zinc) Wood smoke Kanpur Singapore High dust + Zn concentrations 11

12 PM 2.5 relative to Mammoth Cave Elevated crustal PM Site [x] / PM Mammoth Relative Abundance 12

13 Fine/Coarse Relative Abundance (All-site mean) Relative Abundance Heavy metals reside mostly in PM 2.5 Crustal elements found mostly in PM c 13

14 Enrichment correlates with PM 2.5 fractioning All-Site Average 14

15 0 9 Cluster analysis Bandung: Composition Time series Dendrogram for PM 2.5 Correlation matrix for PM 2.5 Industrial Correlation (r) Road dust 15

16 Connectivity of PM 2.5 species (All-site average): Industrial Combustion Correlation (r) Natural dust Road dust 16

17 Connectivity of PM c species (All-site average): Industrial Natural dust Combustion Correlation (r) Road dust 17

18 Summary Ongoing aerosol measurements in urban areas: - trace metals measured on seasonal/annual time spans 20+ aerosol components match well with collocated studies Pb > 100x higher in developing cities than Mammoth Cave Trace components show meta-site correlations Three to four aerosol component groupings Zn:Al = road dust marker? Pb, Cd, and Zn linked to same sources 18

19 Thank you Our Co-op Students Me: Graydon Snider ca Crystal Weagle, PhD Candidate Funded by Prof. Randall Martin SPARTAN Site Collaborators Clement Akoshile, Nguyen Xuan Anh, Fatimah D. Qonitan, Jinlu Dong, Derek Griffith, Kebin He, Ralph Kahn, Nofel Lagrosas, Puji Lestari, Zongwei Ma, Amit Misra, Eduardo J. Quel, Abdus Salam, Bret Schichtel, Lior Segev, S.N. Tripathi, Chien Wang, Chao Yu, Qiang Zhang, Yuxuan Zhang, Yang Liu, Yinon Rudich Endorsed by 19

20 Extras: PMF 20