Point Source Deposition of Mercury in Northern Florida ”A Tale of 2B (or not 2B)” Kathleen J. Gosnell William M. Landing Jane Caffrey

Quicksilver: The Quick and the Dead  Mercury = hopefully what’s not for dinner  Harmful effects of Hg have been know for centuries Methyl mercury is lethal for most organisms Methyl mercury is lethal for most organisms  accidental poisoning has become more prominent with increasing anthropogenic input to the environment Minamata disease brought the problem to light for the public after 1950 Minamata disease brought the problem to light for the public after 1950 acetaldehyde production company released waste containing high amounts of mercury into the bayacetaldehyde production company released waste containing high amounts of mercury into the bay Local fisherman and villagers consumed large amounts of fish -> got really sick -> Neurological disordersLocal fisherman and villagers consumed large amounts of fish -> got really sick -> Neurological disorders

Compliments to the DEP website

What are the Point Sources of Hg?  Numerous studies have been done to determine global and regional deposition influences on Florida watersheds  Few studies have attempted to determine point source effect of known Hg emitters to the local watershed  How does local point sources influence local and global atmospheric mercury deposition?

 This study looks at the influence of one large coal-fired power plant (Gulf Power’s Crist plant) in northeast Pensacola Coal combustion releases Hg into the atmosphere, primarily as vapor Coal combustion releases Hg into the atmosphere, primarily as vapor  Elemental Hg can have an atmospheric half-life or ½ to 2 years in the atmosphere before being released to the biosphere  What are other trace metal factors that can point to where mercury actually coming from?

 3 sample sites located at different distances from main point source 1 mile 1 mile 2 miles 2 miles 7 miles (pristine?) 7 miles (pristine?)  Annual sampling of individual rain events since 2004… Molino Pace Ellyson

 Rain events sampled episodically

 Each sample ran for Hg… Each sample treated with M HCl and M HNO 3, than UV Oxidized for 24 hr. Each sample treated with M HCl and M HNO 3, than UV Oxidized for 24 hr. Analyzed by cold vapor atomic fluorescence spectrometry (CVAFS) Analyzed by cold vapor atomic fluorescence spectrometry (CVAFS)  As well as a sweep of other trace elements, including alkaline metals and earth elements, rare earth elements, and all three lines of transition metals Analyzed via “Element” ICP-MS and “Quad” ICP-MS Analyzed via “Element” ICP-MS and “Quad” ICP-MS

 Monthly average total-Hg concentrations measured for 3 rain sampling sites

Regional Mercury deposition

Factor Analysis:  Reduce the number of variables  Detect Structure in the Relationship between variables Classify variables Classify variables

1 st Factor: Land-Ho! Al, Si, Mn, Fe, Co (REE, Rb, Cs, Th, U)  Indicates land (crust or dust) sources

Factor 4: Sea salt aerosols Sr, Na, Mg  Indicates Marine Source

Factor 3: Plants, Fire or Cement?  Elements associated with plants (P, Zn, Cd)  Byproduct of Cement production?

Pollution factor: Hg, As, Sn, Se, Sb, Pb, Bi, Cu? R 2 = 0.30 R 2 = 0.45 R 2 = 0.54R 2 = 0.40

 Coal combustion in the southeastern US pollutes regionally with volatile elements such as mercury, arsenic, antimony and lead… Factor analysis: Hg, As, Sn, Se, Sb, Pb, Bi, Cu Factor analysis: Hg, As, Sn, Se, Sb, Pb, Bi, Cu  Different Factor Analysis components link Hg to other sources…  can it be narrowed down? Some factor analysis correlations don’t make much sense… Some factor analysis correlations don’t make much sense…  What about other factors? Sulfate can be a coal plant by-product Sulfate can be a coal plant by-product

Analysis: Inter-Element Relationships: 4-factors = Hg - Sb - Pb As Se Sn Bi V (Cu) (no major ions) 6 factors = Hg - Sb - (Pb) (Ga) NO 3 SO 4 NH 4 (no As, Se, Sn) 7 factors = Hg - Sb - Pb SO 4 (all data) 5 factors = Hg – Sb - Pb (V) NO 3 SO 4 NH 4 (all data)

Conclusions:  Factor analysis successfully yields information regarding possible point source categories for trace elements in rainfall  Alumino-silicate (dust), sea salt (marine) and P, Cd and Zn (plants?) factors appear consistent across all analyses  Number of components and allowed factors has dramatic influence on factor loading and inter- element relationships for Hg  consistent relationships emerges from analysis for Hg - Sb - Pb - SO 4

Future Plans?  Set up a fourth sampling site ‘more pristine’ background site ‘more pristine’ background site  More Meteorology  What is the reasoning behind the P - Cd – Zn factor analysis relationship? And Why do Hg sources sometimes change with different factors?  How will the future ‘coal scrubber’ affect Hg samples? Estimated to start up late 2009… Estimated to start up late 2009…  Keep on keeping on…

Acknowledgements:  Dr. William Landing, FSU  Dr. Jane Caffrey, UWF  EPA  Sikha Bagui – UWF (Computer Science)  Subhas Bagui – UWF (Statistics)  Jessie Brown – UWF (Computer Science)  Thalassic Society Officers and Helpers  Student Samplers, delivery man, etc…  Student Symposium 2008 attendees

Thank You! That’s All Folks…

Major ion analysis Compliments of UWF

Full Data set: 7 factors  Factor 1: Dust / Land  Factor 2: Sea salt  Factor 3: Bi, Cd, P, Zn  Factor 4: SO 4, Hg, Pb, Sb  Factor 5: As, Se, Sn  Factor 6: NO 3, NH 4  Factor 7: Cr, Ni Compliments of UWF

5 Factors:  Factor 1: Al/Si - Dust looks like F1 of 7 looks like F1 of 7  Factor 2: NO3, SO4, NH4, Hg, Pb, Sb, V looks like F4+F6 looks like F4+F6  Factor 3: Sea salt looks like F2 of 7 looks like F2 of 7  Factor 4: Bi, Cd, P, Zn looks like F3 looks like F3  Factor 5: As, Se, Sn looks like F5 of 7 looks like F5 of 7 Compliments of UWF