Point Source Deposition of Mercury in Northern Florida ”A Tale of 2B (or not 2B)”

Point Source Point Source Deposition of Mercury Deposition of Mercury

in Northern Floridain Northern Florida

”A Tale of 2B (or not 2B)””A Tale of 2B (or not 2B)”Kathleen J. GosnellKathleen J. Gosnell

William M. LandingWilliam M. LandingJane CaffreyJane Caffrey

Quicksilver: The Quick and the DeadQuicksilver: The Quick and the Dead Mercury = hopefully what’s not for dinnerMercury = hopefully what’s not for dinner Harmful effects of Hg have been know for Harmful effects of Hg have been know for

centuries centuries Methyl mercury is lethal for most organismsMethyl mercury is lethal for most organisms

accidental poisoning has become more accidental poisoning has become more prominent with increasing anthropogenic input prominent with increasing anthropogenic input to the environmentto the environment Minamata disease brought the problem to light for Minamata disease brought the problem to light for

the public after 1950the public after 1950• acetaldehyde production company released waste acetaldehyde production company released waste

containing high amounts of mercury into the baycontaining high amounts of mercury into the bay• Local fisherman and villagers consumed large amounts of Local fisherman and villagers consumed large amounts of

fish -> got really sick -> Neurological disordersfish -> got really sick -> Neurological disorders

Compliments to the DEP website

What are the Point Sources of Hg?What are the Point Sources of Hg?

Numerous studies have been done to Numerous studies have been done to determine global and regional deposition determine global and regional deposition influences on Florida watershedsinfluences on Florida watersheds

Few studies have attempted to determine Few studies have attempted to determine point source effect of known Hg emitters to point source effect of known Hg emitters to the local watershedthe local watershed

How does local point sources influence How does local point sources influence local and global atmospheric mercury local and global atmospheric mercury deposition?deposition?

This study looks at the influence of one large This study looks at the influence of one large coal-fired power plant (Gulf Power’s Crist plant) coal-fired power plant (Gulf Power’s Crist plant) in northeast Pensacolain northeast Pensacola Coal combustion releases Hg into the atmosphere, Coal combustion releases Hg into the atmosphere,

primarily as vaporprimarily as vapor Elemental Hg can have an atmospheric half-life Elemental Hg can have an atmospheric half-life

or ½ to 2 years in the atmosphere before being or ½ to 2 years in the atmosphere before being released to the biospherereleased to the biosphere

What are other trace metal factors that can point What are other trace metal factors that can point to where mercury actually coming from?to where mercury actually coming from?

3 sample sites 3 sample sites located at different located at different distances from main distances from main point sourcepoint source

1 mile1 mile 2 miles2 miles 7 miles (pristine?)7 miles (pristine?)

Annual sampling of Annual sampling of individual rain events individual rain events since 2004…since 2004…

MolinoMolino

PacePace

EllysonEllyson

Rain events Rain events sampled sampled episodicallyepisodically

Each sample ran for Hg…Each sample ran for Hg… Each sample treated with 0.045 M HCl and Each sample treated with 0.045 M HCl and

0.048 M HNO0.048 M HNO33, than UV Oxidized for 24 hr., than UV Oxidized for 24 hr. Analyzed by cold vapor atomic fluorescence Analyzed by cold vapor atomic fluorescence

spectrometry (CVAFS)spectrometry (CVAFS)

As well as a sweep of other trace elements, As well as a sweep of other trace elements, including alkaline metals and earth including alkaline metals and earth elements, rare earth elements, and all three elements, rare earth elements, and all three lines of transition metalslines of transition metals Analyzed via “Element” ICP-MS and “Quad” Analyzed via “Element” ICP-MS and “Quad”

ICP-MSICP-MS

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

Monthly Mercury Deposition

0

100

200

300

400

500

N-04 M-05 O-05 M-06 O-06 A-07 O-07

Month beginning Nov 2004

ng/c

m2/

wee

k

EllysonMolinoPace

Regional Mercury deposition

0

5000

10000

15000

20000

25000

LA28

MS22AL0

2AL2

4

Molino

Ellyso

nPac

eFL0

5GA09

Mer

cury

dep

ositi

on n

g/m

2

200520062007

Factor Analysis:Factor Analysis:

Reduce the number of variablesReduce the number of variables Detect Structure in the Relationship Detect Structure in the Relationship

between variablesbetween variables Classify variablesClassify variables

1 2 3 4Hg 0.328 0.826 -0.074 -0.015As 0.227 0.835 0.219 0.257Sn 0.122 0.632 0.415 0.298Se -0.009 0.791 -0.009 -0.035Sr 0.292 0.363 0.143 0.825Cd 0.045 0.124 0.902 0.017Sb 0.244 0.849 0.235 0.195Pb 0.412 0.696 0.303 0.325Bi 0.217 0.624 0.589 0.115Na 0.010 0.024 -0.002 0.760Mg 0.068 0.300 0.091 0.884Al 0.874 0.136 0.074 0.013Si 0.829 -0.010 0.072 0.043P 0.276 0.362 0.724 0.203V 0.592 0.559 0.089 0.202Cr 0.538 0.122 0.180 0.117Mn 0.940 0.228 0.145 0.117Fe 0.901 0.157 0.071 0.028Co 0.899 0.195 0.076 0.129Ni 0.387 0.397 0.223 0.254Cu 0.291 0.664 0.227 0.164Zn 0.066 0.185 0.880 0.025

Component

Extraction Method: Principal Component Analysis.

11stst Factor: Land-Ho! Factor: Land-Ho! Al, Si, Mn, Fe, Co (REE, Rb, Cs, Th, U)Al, Si, Mn, Fe, Co (REE, Rb, Cs, Th, U)

Indicates land (crust or dust) sourcesIndicates land (crust or dust) sources

Pensacola Rainfall (3 sites combined)

10

100

1000

10000

100000

10 100 1000 10000

Al Deposition (ug/m2)

Si d

epos

ition

(ug

/m2)


10

100

1000

10000

10 100 1000 10000

Al Deposition (ug/m2)

Fe d

epos

ition

(ug

/m2)

Factor 4: Sea salt aerosolsFactor 4: Sea salt aerosolsSr, Na, MgSr, Na, Mg

Indicates Indicates Marine Marine SourceSource


0.1

1

10

100

1000

1 100 10000 1000000

Mg Deposition (ug/m2)

Sr

depo

sitio

n (u

g/m

2)

Factor 3: Plants, Fire or Cement?Factor 3: Plants, Fire or Cement?

Elements Elements associated associated with plants with plants (P, Zn, Cd) (P, Zn, Cd)

Byproduct Byproduct of Cement of Cement production?production?


1

10

100

1000

10000

1 10 100 1000

Zn Deposition (ug/m2)

P d

epos

ition

(ug

/m2)


0.1

1

10

100

0.01 0.1 1 10

Hg Deposition (ug/m2)

As

depo

sitio

n (u

g/m

2)

Pollution factor: Pollution factor: Hg, As, Sn, Se, Sb, Pb, Bi, Cu?Hg, As, Sn, Se, Sb, Pb, Bi, Cu?Pensacola Rainfall (3 sites combined)

0.1

1.0

10.0

100.0

0.01 0.10 1.00 10.00Hg Deposition (ug/m2)

Pb

depo

sitio

n (u

g/m

2)


0.01

0.1

1

10

100

0.01 0.1 1 10


Se

depo

sitio

n (u

g/m

2)


0.1

1.0

10.0

100.0

0.01 0.10 1.00 10.00


Cu

depo

sitio

n (u

g/m

2)

R2 = 0.30R2 = 0.45

R2 = 0.54 R2 = 0.40

Coal combustion in the southeastern US Coal combustion in the southeastern US pollutes regionally with volatile elements pollutes regionally with volatile elements such as mercury, arsenic, antimony and such as mercury, arsenic, antimony and lead…lead… Factor analysis: Hg, As, Sn, Se, Sb, Pb, Bi, CuFactor analysis: Hg, As, Sn, Se, Sb, Pb, Bi, Cu

Different Factor Analysis components link Different Factor Analysis components link Hg to other sources…Hg to other sources…

can it be narrowed down?can it be narrowed down? Some factor analysis correlations don’t make Some factor analysis correlations don’t make

much sense…much sense… What about other factors?What about other factors?

Sulfate can be a coal plant by-productSulfate can be a coal plant by-product

Analysis: Analysis: Inter-Element Relationships: Inter-Element Relationships:

4-factors4-factors = = Hg - Sb - Pb Hg - Sb - Pb As Se Sn Bi V As Se Sn Bi V (Cu)(Cu)

(no major ions)(no major ions)

6 factors6 factors = = Hg - Sb - (Pb) Hg - Sb - (Pb) (Ga) NO(Ga) NO33 SO SO44 NH NH44 (no As, Se, Sn)(no As, Se, Sn)

7 factors7 factors = = Hg - Sb - Pb Hg - Sb - Pb SOSO44

(all data)(all data)

5 factors5 factors = = Hg – Sb - Pb (V) NOHg – Sb - Pb (V) NO33 SO SO44 NH NH44

(all data)(all data)

Conclusions:Conclusions: Factor analysis successfully yields information Factor analysis successfully yields information

regarding possible point source categories for regarding possible point source categories for trace elements in rainfalltrace elements in rainfall

Alumino-silicate (dust), sea salt (marine) and P, Alumino-silicate (dust), sea salt (marine) and P, Cd and Zn (plants?) factors appear consistent Cd and Zn (plants?) factors appear consistent across all analysesacross all analyses

Number of components and allowed factors has Number of components and allowed factors has dramatic influence on factor loading and inter-dramatic influence on factor loading and inter-element relationships for Hg element relationships for Hg

consistent relationships emerges from analysis consistent relationships emerges from analysis for Hg - Sb - Pb - SOfor Hg - Sb - Pb - SO44

Future Plans?Future Plans? Set up a fourth sampling siteSet up a fourth sampling site

‘‘more pristine’ background sitemore pristine’ background site More MeteorologyMore Meteorology What is the reasoning behind the P - Cd – Zn What is the reasoning behind the P - Cd – Zn

factor analysis relationship? And Why do Hg factor analysis relationship? And Why do Hg sources sometimes change with different sources sometimes change with different factors?factors?

How will the future ‘coal scrubber’ affect Hg How will the future ‘coal scrubber’ affect Hg samples?samples? Estimated to start up late 2009…Estimated to start up late 2009…

Keep on keeping on…Keep on keeping on…

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

Thank You!Thank You!That’s All Folks…That’s All Folks…

Major ion analysisMajor ion analysisco

ncen

tratio

n (m

g/L)

0.001

0.01

0.1

1

10

100

1000

Compliments of UWF

Full Data set:Full Data set:7 factors7 factors

Factor 1: Dust / LandFactor 1: Dust / Land Factor 2: Sea saltFactor 2: Sea salt Factor 3: Bi, Cd, P, ZnFactor 3: Bi, Cd, P, Zn Factor 4: SOFactor 4: SO44, Hg, Pb, , Hg, Pb,

SbSb Factor 5: As, Se, SnFactor 5: As, Se, Sn Factor 6: NOFactor 6: NO33, NH, NH44 Factor 7: Cr, NiFactor 7: Cr, Ni

Rotated Component Matrix(a)

Component 1 2 3 4 5 6 7 Cl -.102 .869 -.035 .377 .033 .011 .093 NO3 .165 .115 .001 .246 -.217 .733 .202 SO4 .037 .397 .031 .834 .032 -.012 .063 NH4 .232 .166 .205 .270 .171 .662 -.217 NaUWF -.012 .953 .027 .076 .096 .105 -.051 Al .951 -.078 .008 .048 -.141 .007 .127 As -.124 .063 -.005 -.029 .964 -.015 .068 Ba .863 .011 .154 .191 -.059 .057 .331 Bi .063 .059 .821 .193 -.154 .163 .119 Cd -.041 -.007 .907 .004 .089 -.069 .032 Ce .939 -.005 .055 .118 -.016 .134 -.067 Co .900 .080 .063 .163 -.018 .059 .060 Cr .618 -.017 .178 -.020 -.004 -.079 .615 Cs .950 .040 .121 .111 -.058 .092 .082 Cu .436 .020 .339 .490 -.094 .019 -.076 Fe .956 -.067 .003 .068 -.133 .017 .141 Hg .289 .079 .032 .819 .062 .234 .063 Ga .630 .346 .231 .268 .001 .104 .146 La .936 -.001 .054 .165 -.046 .189 -.021 Li .859 .272 .010 .109 .028 .062 .075 Mg .093 .971 .032 .068 .036 .047 .037 Mn .941 .048 .108 .149 -.025 .135 -.034 Ni .371 .192 .129 .227 .138 .205 .676 P .241 .051 .610 .112 .040 .177 -.165 Pb .482 .249 .305 .532 -.167 .361 -.034 Rb .920 .187 .149 .090 -.045 .100 .036 Se -.013 .163 .129 .207 .573 -.488 -.253 Sb .242 .151 .358 .641 -.151 .461 .110 Si .918 -.062 -.038 -.055 -.122 -.091 .200 Sn -.135 .036 -.061 -.073 .958 -.018 .070 Sr .390 .879 .109 .122 .020 .069 .044 U .795 .211 .107 .196 .060 .229 -.137 V .574 .286 .093 .474 -.013 .169 .094 Zn .110 .024 .918 .023 .005 -.062 .159

Extraction Method: Principal Component Analysis. Rotation Method: Varimax with Kaiser Normalization. a Rotation converged in 8 iterations.

Compliments of UWF

Restricted to 5 components Rotated Component Matrix(a)

Component 1 (1) 2 (4+6) 3 (2) 4 (3) 5 (5) Cl -.098 .319 .881 -.029 .071 NO3 .158 .604 .087 -.022 -.333 SO4 .022 .685 .425 .031 .100 NH4 .174 .638 .107 .134 .075 NaUWF -.022 .146 .937 .012 .099 Al .955 .076 -.075 .007 -.146 As -.106 -.001 .035 -.023 .945 Ba .890 .217 .022 .167 -.064 Bi .069 .277 .057 .820 -.153 Cd -.032 .004 -.010 .906 .118 Ce .913 .225 -.022 .025 -.036 Co .893 .212 .076 .049 -.021 Cr .697 -.059 .011 .229 -.006 Cs .945 .189 .034 .108 -.071 Cu .407 .450 .027 .322 -.054 Fe .962 .099 -.063 .002 -.139 Hg .263 .820 .088 .014 .076 Ga .633 .318 .346 .225 .005 La .913 .291 -.017 .025 -.073 Li .856 .169 .264 -.003 .021 Mg .095 .105 .965 .028 .048 Mn .919 .252 .033 .080 -.041 Ni .445 .295 .208 .167 .102 P .210 .244 .026 .575 .030 Pb .446 .677 .237 .272 -.184 Rb .910 .182 .176 .131 -.057 Se -.033 -.058 .171 .116 .677 Sb .221 .804 .145 .336 -.180 Si .939 -.071 -.052 -.026 -.119 Sn -.116 -.042 .008 -.077 .935 Sr .388 .177 .871 .100 .030 U .758 .349 .184 .064 .034 V .562 .515 .288 .079 -.009 Zn .134 .022 .028 .928 .032

Extraction Method: Principal Component Analysis. Rotation Method: Varimax with Kaiser Normalization. a Rotation converged in 6 iterations.

5 Factors:5 Factors: Factor 1: Al/Si - DustFactor 1: Al/Si - Dust

looks like F1 of 7looks like F1 of 7

Factor 2: NO3, SO4, Factor 2: NO3, SO4, NH4, Hg, Pb, Sb, VNH4, Hg, Pb, Sb, V looks like F4+F6looks like F4+F6

Factor 3: Sea saltFactor 3: Sea salt looks like F2 of 7looks like F2 of 7

Factor 4: Bi, Cd, P, ZnFactor 4: Bi, Cd, P, Zn looks like F3looks like F3

Factor 5: As, Se, SnFactor 5: As, Se, Sn looks like F5 of 7looks like F5 of 7

Compliments of UWF

Documents

Point Source Deposition of Mercury in Northern Florida ”A Tale of 2B (or not 2B)”