1. Atmospheric Deposition of Mercury, Trace Metals and Major Ions in the Pensacola Bay Watershed Jane Caffrey Center for Environmental Diagnostics and Bioremedation University of West Florida and William M. Landing Department of Oceanography Florida State University

2. Acknowledgements EPA PERCH project Melissa Overton, Autumn Dunn, Nathaniel Davila, Tanner Martin, Fran Aftanas, Elizabeth Gaige, Brad Kuykendall for their dedication in the field Sara Cleveland, Kati Gosnell, and Nishanth Krishnamurthy at FSU Dr. Sikha Bagui and Jessie Brown at UWF Computer Science for database development Dr. Subhash Bagui and Arup Sinha at UWF Mathematics and Statistics

3. Escambia County 9th in total toxic emissions nationwide, 16th in air emissions Coal fired power plant Papermill (coal for some power generation) Other industrial activities (Solutia, Air Products, etc.) 8 Superfund sites Partnership for Environmental Research and Community Health (PERCH) – EPA funded –Human health effects –Environmental effects

4. From Mark Cohen, NOAA ARL Mercury emissions sources in the Gulf of Mexico region, based on the 1999 National Emissions Inventory (U.S. EPA)

5. Generally higher mercury deposition in the SE, most driven by higher rainfall along the Gulf Coast

6. Mercury deposition is an international problem Worldwide emission estimates US coal fired power plants represent about 1% of Hg emissions globally 53% of emissions come from Asia, 18% from Africa, 11% from Europe, 9% from North America

8. What is the atmospheric wet deposition of mercury, trace metals and major ions to the lower Pensacola Bay Watershed? Are there seasonal patterns in deposition? How do prior weather conditions affect deposition? Are there hot spots? How important are Local sources?

9. Sampling Locations

10. Sample collection began in November 2004 and will continue through March 2010 Hurricane Dennis ~ 565 samples from 225 rain events to Feb 2008 2004 2005 2006 2007 2008

11. Analyses UWF -WRL pH Sulfate Nitrate+nitrite Chloride Ammonium Sodium Calcium Phosphate FSU - Oceanography Mercury Trace metals –mineral/crustal elements: Al, Si, Sc, Ti, Mn, Fe, Rb, Y, Nb, Cs, La and all rare earth elements, Th, U –Sea Salt aerosols: Li, Na, Mg, Sr –urban pollution, fossil fuel combustion: V, Ga, Sb, Pb, Bi, P, Cu, Zn –As, Se, Sn

12. Rain is generally acidic, sometimes highly acidic 2004 2005 2006 2007 2008

13. Sulfate Flux

14. Sulfate fluxes are higher in Pensacola and AL sites Highest fluxes at Ellyson Lowest at FL14 and FL23

15. Counties with higher sulfate emissions have higher sulfate deposition Based on EPA TRI estimates for 2002

16. Nitrate flux Fluxes were similar at Pensacola Bay sites Higher fluxes in spring and summer

17. Regional Nitrate Flux Higher nitrate fluxes at Pensacola sites than at any NADP sites

18. Counties with higher nitrate emissions had higher nitrate deposition Based on EPA TRI estimates for 2002

19. Chloride Flux

20. Sodium and Chloride fluxes are high relative to other sites P

21. Higher sodium and chloride fluxes when closer to Gulf of Mexico

22. Conclusions Low pH in some rain events (pH usually < 5, sometimes less than 4) –Ellyson and Pace sites had significantly higher H+ fluxes than NADP sites Sulfate and nitrate fluxes higher at Pensacola Bay sites than most NADP sites Sulfate and Nitrate fluxes are highest in counties that have high SO 2 or NO x emissions Sodium and Chloride fluxes higher at Pensacola Bay sites. Sea salt aerosols are important component of rain in the region

23. Mercury and trace elements in rainfall from the Pensacola airshed: local, regional, and distant sources William M. Landing Department of Oceanography Florida State University Jane Caffrey Center for Environmental Diagnostics and Bioremedation University of West Florida

24. Acknowledgements EPA PERCH project (2005-2008) EPRI funding for 2008-present. FSU Graduate students: Sara Cleveland, Kati Gosnell, Nishanth Krishnamurthy UWF students: Nathaniel Davila, Tanner Martin, Brad Kuykendall, Fran Aftanas, Elizabeth Gaige

25. Geographic Distribution of Largest Anthropogenic Mercury Emissions Sources in the U.S. (1999) and Canada (2000); from Mark Cohen NOAA/ARL Gulf coast is not loaded with Hg point sources

26. Generally higher mercury deposition in the Southeastern US and along the Gulf coast. Is this due to long-range transport of GEM and GEM-> RGM conversion during summer months? (Yes)

27. Escambia County: Coal fired power plant International Paper mill (coal for some power generation) Other industrial activities (Solutia, Air Products, Sacred Heart medical waste incinerator, etc.)

28. EPA National Emissions Inventory shows that Plant Crist is the largest air emitter of mercury in the region. -- Need reliable mercury speciation profile for each source (RGM, GEM, Hg-p)

29. What is the atmospheric wet deposition of mercury, trace metals and major ions to the lower Pensacola Bay Watershed? Rainfall chemistry in the Pensacola region is impacted by multiple local and regional emission sources. Rainfall mercury deposition in the southeastern US and along the Gulf of Mexico coast is already elevated due to long-range transport and transformation of Gaseous Elemental Mercury (GEM) to Reactive Gaseous Mercury (RGM); can we reliably quantify the impacts from individual local and regional sources of RGM (and particulate Hg-p)? What is the seasonal pattern in mercury and trace element deposition? (Completed) What are the relationships to local and regional meteorology? (On-going) Are there hot spots? (Not apparent)

30. What is the atmospheric wet deposition of mercury, trace metals and major ions to the lower Pensacola Bay Watershed? Can we use other trace elements to “fingerprint” specific emissions sources? Installation of Hg emission control technology on the local CFPP (Plant Crist) in late 2009 may change local rainfall chemistry and trace element deposition. Project is monitoring rain events at multiple sites for multiple years to obtain a statistically-significant number of such events both before and after new Hg emission control technology is installed. Rainfall impact from a point-source plume requires simultaneous presence of the plume and rainfall.

31. Sampling Locations: 1. Ellyson 2. Pace 3. Molino

32. a. b. Modified AerochemMetrics Wet/Dry samplers: 1. Plexiglas splash guard on leading edge of roof to eliminate splash contamination. 2. Foam seal inside FEP Teflon film bag. 3. Three replicate “nested” funnel/bottle sets (one for pH, N- species and major ions; two for Hg and trace elements).

33. Analyses: Samples collected on an “event” basis (within 24 hours). UWF -WRL pH Sulfate Nitrate+nitrite Chloride Ammonium Sodium Calcium Phosphate FSU - Oceanography Mercury Trace metals –mineral/crustal elements: Al, Si, Sc, Ti, Mn, Fe, Rb, Y, Nb, Cs, La and all rare earth elements, Th, U –Sea Salt aerosols: Li, Na, Mg, Sr –urban pollution, fossil fuel combustion: V, Ga, Sb, Pb, Bi, P, Cu, Zn, As, Se, Sn

34. Duplicate receiving bottles allows evaluation of analytical reliability. As concentrations approach the detection limit, scatter increases (Ba).

35. Sample collection: November 2004 through December 2007; ~ 500 samples from 175 rain events at three sites. Hg concentrations consistent with regional MDN sites. Generally higher in summer; small-volume winter events have concentrations up to 55 ng/L. 200520062007

36. Mercury deposition per month: summertime deposition dominates due mostly to higher rainfall Hg concentrations.

37. Pensacola sites are not significantly different from each other, and not significantly higher than regional MDN sites

38. Plant Crist Units and In-Service Dates: 94 MW (1959), 94 MW (1961), 370 MW (1970), 578 MW (1973) The increase in Hg sedimentation since 1965 (-45 years) also coincides with increased industrialization and coal-fired electricity generation throughout the southeast, nationally, and globally. Need better local coring sites to define deposition history over the past 150 years.

39. Should we expect to be able to measure significant differences in Hg rainfall deposition due to Plant Crist? 1. “Background” rainfall Hg deposition is already elevated along the gulf coast (15-20 ug/m2/year). 2. RGM from CFPP may convert to GEM in near-field plume. 3. Individual CFPP impact from RGM emissions typically <15% of existing rainfall Hg deposition within 50 km in the southeastern US (Mark Cohen at NOAA/ARL). So, rainfall Hg deposition may not be significantly elevated from Plant Crist. What other tools do we have?

40. Can we use multi-element analysis to “fingerprint” various sources of mercury and other trace elements in Pensacola Bay rainfall? Simple correlation and multi-variate statistical analysis used to examine relationships among mercury and trace metals data (Factor Analysis and Positive Matrix Factorization). Important to convert to “deposition” (Conc. x Rain depth) since small volume events have high concentrations of all tracers and skew regression analysis.

42. Crustal Factor: alumino-silicate aerosols (mineral dust) Al, Si, Mn, Fe, Co, REE, Rb, Cs, Th, U

43. Cd/Zn Factor: P, Cr, Zn, Cd Sea Salt Factor: Na, Mg, Sr

44. “Pollution” Factor: Hg vs. As, Sn, Se, Sb (volatiles in coal) R 2 = 0.46 R 2 = 0.54R 2 = 0.45 R 2 = 0.27

45. Using volatile trace element concentrations to estimate Hg input from regional coal combustion (assumes volatile TE comes only from coal combustion): 1. Use Hg/TE vaporization ratios from CFPPs and “excess” rainfall TE and Hg deposition (adjust for RGM+Hg-p fraction (74%); assumes Hg/TE ratio is maintained until deposition): %Hg from coal = Annual XS-TE deposition x (Hg/TE)coal x 100 Annual XS-Hg deposition 2. Or, use minimum observed XS-Hg/XS-TE ratios for volatile elements in rain samples to approximate Hg/TE from coal burning (average of 10-14 lowest ratios for each element). %Hg in rainfall from regional coal combustion: TECFPP Hg/TE ratiosObserved min. Hg/TE ratios As29%23% Se38%22% Sn30%14% Sb40%14%

46. Future Goals: Use of meteorological data to understand the chemistry of individual rain events

47. 43

48. Tags in Florida, updated simulation 35

49. 44 Total Hg deposition (2001)= 25 ug/m 2 /yr Wet Deposition (2005-2007)= 14-19 ug/m 2 /yr Inferred Dry Deposition = 6-11 ug/m 2 /yr 78% of total Hg deposition from “background” 7.2% Plant Crist 8.2% from CFPP in Florida

50. 45 REMSAD results courtesy of Dwight Atkinson (EPA) and Tom Myers (ICF)

51. Conclusions and Future research Rainfall mercury deposition in the Pensacola Bay watershed is similar to deposition across the northeastern Gulf of Mexico. Factor Analysis and other statistical tests can be used to identify source “types”, but not individual point sources. Pensacola rainfall Hg deposition appears to be impacted by coal combustion sources (14- 40%). Is this true along the entire Gulf coast? Need trace element analyses at MDN sites. New Gulf Breeze site will help. We will conduct detailed meteorological analysis of individual storms affecting all four monitoring sites within the region (includes EPRI/OLF site). –Back trajectories –Cloud-top heights (indicator of tall convection) –Prior meteorological history –Hg isotopes in large-volume samples (Summer 2010)