Contaminants in Biscayne Bay - UF/IFAS OCI · PDF fileContaminants in Biscayne Bay. ... BICY-9...

Contaminants in Biscayne BayEverything else but nutrients

Piero R. Gardinali, Adolfo Fernandez, Valentina G-Caccia, Luis Arroyo, Melissa Fernandez, Jianhong Wu, Simrat Singh, Chengtao Wang, Cesar Ramirez, Mark Cejas, Ingrid Ley.

Department of Chemistry & BiochemistrySoutheast Environmental Research Center

Turgeon, D.D., J. Hameedi, M.R. Harmon, E.R. Long, K.D. McMahon, and H.H. White. 1998. Sediment toxicity in U.S. coastal waters. Silver Spring, MD: NOAA, National Ocean Service, ORCA, 20 pp.

North Biscayne Bay / Miami River

E. R. LONG, M. J. HAMEEDI, G. M. SLOANE, and L. B. READEstuaries Vol. 25, No. 4A, p. 622–637 August 2002

MEAN ERM QUOTIENTS

Biscayne Bay Sediments: H4IIE Assay

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

120

140

160

180

EROD

(pmo

l/m*m

i)

0

50

100

150

200

250

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

120

140

160

DMSOBaP

(5x1

0-8M)

TCDD (5

x10-1

1M)

Origina

l'1/

10'1/

100

'1/10

00'1/

1000

0'1/

1000

00

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

120

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

120

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

120

140

160

DMSOBaP

(5x1

0-8M)

TCDD (5

x10-1

1M)

Origina

l'1/

10'1/

100

'1/10

00'1/

1000

0'1/

1000

00

EROD

(pmo

l/m*m

i)

0

20

40

60

80

100

MIAMI RIVER BISCAYNE BAY

WHOLE SEDIMENT

F2 AROMATICS(1:1 MeCl2:Pentane)

F3 SLIGHTLY POLAR(100% MeCl2)

F4 POLAR FRACTION(100 %Methanol)

Some candidates for toxicity: Aromatic fractionPhenanthrene

Chrysene

LC50 µ-tox 0.5 ppmERM ~ 1.0 ppm

LC50 µ-tox 1.0 ppmERM ~ 1.0 ppm

Tetra- and pentacyclic aromatic triterpenoidsisolated from Everglades sediments

Estimated concentrations ~ 0.5 -5 ppm

Some candidates for toxicity: Polar fraction

OH O

OH O

OH O

OH O

Roburic Acid

Nyctanthic acid

Isolated from sediments in mangrove areas

Traditional contaminant monitoring

South Florida CARE Monitoring

50 sitesWaterSedimentFish 3 yearsENPBISCBICYSpecial areas

South Florida CARE Monitoring

Copper: two analytical techniquesCopper (Laser)

Station

BIC

Y9C

111-

1TS

3B

ICY1

SRS1

C11

1-2

BIC

Y7B

ICY6 TS

4B

ICY3 FB

1B

ICY5

BB

9 E6 S18

TS1

WB

2B

B16

C11

1-4 E7

BIC

Y2B

ICY4

BIC

Y8SR

S2B

B15 TT

1TS

2TT

2B

B8

BB

6TT

4B

B4 E2

WB

3B

B13

BB

11B

B3

BB

14B

B12

BB

5 E4B

B2

TT3

BB

7 E5B

B1 E1

BB

10

Cop

per (

ppm

)

0

50

100

150

200

250

TEL

PEL

Copper (Solution)

Station

BIC

Y-9

C-1

11-1

BIC

Y-1

C-1

11-2

TS3

BB

-9B

ICY-

3B

ICY-

6TS

1B

B-1

6S

18C

E-6

WB

2B

ICY-

5TS

4TS

2S

RS

-1FB

-1S

RS

-2E

-7TT

1B

ICY-

8E

-2B

ICY-

7B

ICY-

2B

ICY-

4TT

2TT

4C

-111

-4W

B3

BB

-8B

B-1

5B

B-2

BB

-4B

B-1

4TT

3B

B-7

BB

13 E-4

BB

-5E

-5B

B-1

1B

B-3

BB

-12

BB

-6B

B-1

E-1

BB

-10

Cop

per (

ppm

)

0

50

100

150

200

250

TEL

PEL

Copper (Laser)

Station

BIC

Y9C

111-

1TS

3B

ICY1

SRS1

C11

1-2

BIC

Y7B

ICY6 TS

4B

ICY3 FB

1B

ICY5

BB

9 E6 S18

TS1

WB

2B

B16

C11

1-4 E7

BIC

Y2B

ICY4

BIC

Y8SR

S2B

B15 TT

1TS

2TT

2B

B8

BB

6TT

4B

B4 E2

WB

3B

B13

BB

11B

B3

BB

14B

B12

BB

5 E4B

B2

TT3

BB

7 E5B

B1 E1

BB

10

Cop

per (

ppm

)

0

50

100

150

200

250

TEL

PEL

Copper (Solution)

Station

BIC

Y-9

C-1

11-1

BIC

Y-1

C-1

11-2

TS3

BB

-9B

ICY-

3B

ICY-

6TS

1B

B-1

6S

18C

E-6

WB

2B

ICY-

5TS

4TS

2S

RS

-1FB

-1S

RS

-2E

-7TT

1B

ICY-

8E

-2B

ICY-

7B

ICY-

2B

ICY-

4TT

2TT

4C

-111

-4W

B3

BB

-8B

B-1

5B

B-2

BB

-4B

B-1

4TT

3B

B-7

BB

13 E-4

BB

-5E

-5B

B-1

1B

B-3

BB

-12

BB

-6B

B-1

E-1

BB

-10

Cop

per (

ppm

)

0

50

100

150

200

250

TEL

PEL

Regardless of the differencesbetween the methods, similar TEL/ PEL rankings were obtained

Laser ablation – ICP/MS(exhaustive)

Acid digestion– ICP/MS(bioavailable)

Copper/ Aluminum (Laser)

Aluminum (ppm)101 102 103 104 105

Cop

per (

ppm

)

10-2

10-1

100

101

102

103

C-111-1

C-111-2

C-111-4

E1

E2

E4E5

E6E7FB-1

SRS1

SRS2S18

TT1TT2

TT3

TT4

TS1

TS2

TS3

TS4

WB2

WB3

BICY1

BICY2

BICY3

BICY4

BICY5BICY6BICY7

BICY8

BICY9

BB1

BB2BB3

BB4BB5

BB6

BB7

BB8

BB9

BB10

BB11BB12BB13

BB14

BB15BB16

Copper/ Aluminum

Aluminum (ppm)101 102 103 104 105

Cop

per (

ppm

)

10-2

10-1

100

101

102

103

C-111-1C-111-2

C-111-4

E-1

E-2

E-4E-5

E-6E-7 FB-1SRS-1 SRS-2

S18C

TT1TT2

TT3

TT4

TS1TS2

TS3

TS4WB2

WB3

BICY-1

BICY-2

BICY-3

BICY-4

BICY-5BICY-6

BICY-7BICY-8

BICY-9

BB-1

BB-2

BB-3

BB-4BB-5

BB-6

BB-7BB-8

BB-9

BB-10

BB-11BB-12BB13

BB-14BB-15

BB-16

Copper/ Aluminum (Laser)

Aluminum (ppm)101 102 103 104 105

Cop

per (

ppm

)

10-2

10-1

100

101

102

103

C-111-1

C-111-2

C-111-4

E1

E2

E4E5

E6E7FB-1

SRS1

SRS2S18

TT1TT2

TT3

TT4

TS1

TS2

TS3

TS4

WB2

WB3

BICY1

BICY2

BICY3

BICY4

BICY5BICY6BICY7

BICY8

BICY9

BB1

BB2BB3

BB4BB5

BB6

BB7

BB8

BB9

BB10

BB11BB12BB13

BB14

BB15BB16

Copper/ Aluminum

Aluminum (ppm)101 102 103 104 105

Cop

per (

ppm

)

10-2

10-1

100

101

102

103

C-111-1C-111-2

C-111-4

E-1

E-2

E-4E-5

E-6E-7 FB-1SRS-1 SRS-2

S18C

TT1TT2

TT3

TT4

TS1TS2

TS3

TS4WB2

WB3

BICY-1

BICY-2

BICY-3

BICY-4

BICY-5BICY-6

BICY-7BICY-8

BICY-9

BB-1

BB-2

BB-3

BB-4BB-5

BB-6

BB-7BB-8

BB-9

BB-10

BB-11BB-12BB13

BB-14BB-15

BB-16

Copper enrichment in sediments

Biscayne National Park

BB10BB1

Biscayne National ParkBB10

CARE results: p,p’-DDE

CARE results: PAHs (a hot item these days)

CH3

CH3

12

3

4567

8

910

1112

Benzene

2,6-DMNPhenanthrene

Benzo(b)fluoranthene

Anthracene

Benzo(a)pyreneBenzo(ghi)perylene Coronene

Fluoranthene

Naphthalene

0

500

1000

1500

2000

2500

3000

3500

4000

BICY

4 BI

CY1 E7

FB1

BICY

9 BI

CY5

C111

2 BI

CY1

BICY

7 S1

8C

E7

C111

1BI

CY7

TS3

BB09

BI

CY4

BICY

3 W

B1

TS4

E4

FB2

FB1

BICY

8 TS

1 TS

4 W

B2 E4BB

08

SRS2

BICY

2 BB

02

WB2 E6

BB04

FB

2 TT

1 BI

CY6

BB06

BICY

3 E5

E4SR

S1

SRS1

SR

S3BI

CY8

BB07

TS

2SR

S3

TT2

WB3 E5

BB12

W

B3

E7

BB05

E1

C1

114

SRS2

E2 E2

E3

BB

11C1

113

S178

BB03

E3

TT2

TT3 E5

TT4

BB01

E1

BB10

Total PAHs (ng/g)

0

100

200

300

400

500

600

BB 1

0 BI

CY 3

TS

4 FB

2 BI

CY 5

TT

3 BI

CY 5

TS

1BB

10

BB 1

2 BB

07

WB1

BB

02

TS

4 BB

09

TS1

WB2

BB

12

TS1

BB 0

6BB

07

E4

C111

3 SR

S1

E5

TS1

BICY

2

SRS4

BB

05

TT2

FB1

BICY

4SR

S4

BB 0

6W

B3BB

05

WB3

BB

07 E2

WB3

S1

8C

S178

BB 1

1 E5

E4

TT4

WB1

E2

E7

SRS1

E6

FB1

BI

CY 8

TT

4 W

B3

BICY

3BB

06

TS3 E7

TS3

TT4

C111

2W

B1C1

114

FB2

BB 0

5 BB

01

BB 0

7 BB

10

BB 0

1BB

04

Total PAHs (ng/L)

SEDIMENTS

WATER

NITROGEN PESTICIDES IN WATER

BB01

BB

02BB

03BB

04

BB05

BB

06BB

07

BB09

BB

10BB

11

BB12

BICY

1BI

CY2

BICY

3BI

CY4

BICY

5BI

CY6

BICY

7BI

CY8

BICY

9 C1

11-1

C111

-2C1

11-3

C111

-4 E1

E2

E3

E4

E5

E6 E7

FB1

FB2

SRS1

SR

S2

SRS3

SR

S4 TS1

TS2

TS3

TS4

TT1

TT2

TT3

TT4

WB1

W

B2W

B3

S178

S1

8C

CONC

ENTR

ATIO

N (ng

/L)

0

25

50

400

Atrazine Prometon Simetryne Metolachlor Metribuzin

Levels are low but Atrazine is all over the placeNITROGEN PESTICIDES IN WATER

CONCENTRATION (ng/L)

0 25 50 300 400

Prometon

Atrazine

Metribuzin

Alachlor

Simetryne

Metolachlor

Non traditional (exotic) pollutants chemicals

“Caffeine is the most widely consumed and excreted psychoactive drug in the world. It is a ubiquitous tracer of urban wastewater, but its ecological effects are not well understood”.

“We hypothesized that caffeine exposure is associated with coral bleaching”.

Proteomic Assessment of Caffeine Effects on Coral SymbiontsKelly Pollack†, Kimberly Balazs‡ and Oladele Ogunseitan*†§

Environ. Sci. Technol., 2009, 43 (6), pp 2085–2091

http://pubs.acs.org/doi/abs/10.1021/es802617f�





What is in your water?

LANDFILL

SOUTH DADE WWTP

813

910

1112

Coprostanol

Agricultural Area Residential Area Landfill Area

Conc

entra

tion

(ng/

L)

0

2

4

6

8

10

Estrone


Conc

entra

tion

(ng/

L)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Bisphenol-A


Conc

entra

tion

(ng/

L)

0

20

40

60

80

100

120

140

What is in your water?G

roun

d W

ater

UI

Gro

und

Wat

er

Surf

ace

Wat

er U

I

Surf

ace

Wat

er

Rec

limed

Wat

er

Key

Lar

go

Mia

mi R

iver

Bla

ck C

reek

Can

al

Littl

e Ve

nice

Looe

Key

Ger

man

y

Switz

erla

nd

Bos

ton

Har

bor

* Oth

er U

S St

ream

s

Caf

fein

e co

ncen

trat

ion

(ng/

L)

0

25

50

75

100

125

150

175

200

225

250

*Caf

fein

e co

ncen

trat

ion

in o

ther

US

stre

ams

(ug/

L)

0

1

2

3

4

5

6

South FloridaThis Project Europe US

Gro

und

Wat

er U

I

Gro

und

Wat

er

Surf

ace

Wat

er U

I

Surf

ace

Wat

er

Rec

laim

ed W

ater

Key

Lar

go

Mia

mi R

iver

Bla

ck C

reek

can

al

Littl

e Ve

nice

Looe

Key

Fran

ce UK

Net

herla

nds

Ger

man

y

Japa

n

* US

stre

ams

Estr

one

conc

entr

atio

n (n

g/L)

0

2

4

6

8

10

12

14

16

18

20

*Est

rone

con

cent

ratio

n in

oth

er U

S St

ream

s (n

g/L)

0102030405060708090100110120

WorldThis project South Florida

CaffeineA harmless drug…

EstroneA powerful hormone!

Vegetation management: Glyphosate

Is not as easy as it sounds: keep it simple!

Use fluorescence for low level and LC/MS for ID

Vegetation management practices: glyphosateC:\Xcalibur\data\10857 3/24/2010 7:11:09 PM CAL 11

RT: 0.00 - 25.04 SM: 3G

0 2 4 6 8 10 12 14 16 18 20 22 24Time (min)

0

50

1000

50

1000

50

1000

500

1000

mill

iVol

ts

7.59 13.899.32 11.25

12.65

14.24 23.328.01 21.2119.3618.0917.496.475.483.963.00 23.622.311.327.50

7.70 8.149.89

10.86

11.62 12.4911.11

10.57 11.65 12.73

NL: 1.50E3A/D Card Ch. 1 A/D card 10857

NL: 4.20E5TIC F: - c ESI Full ms2 [email protected] [145.00-175.00] MS 10857

NL: 1.27E5TIC F: - c ESI Full ms2 [email protected] [120.00-170.00] MS 10857

NL: 9.11E5TIC F: - c ESI SIM ms [663.00-667.00] MS 10857

Glyphosate-FMOCMS/MSm/z 390 168

Aspartic Acid-FMOC (ISTD)MS/MSm/z 354 158

AMPA-FMOCSIM, m/z 665

FluorescenceEx. λ = 270 nmEm. λ = 315 nm

10.76

Lessons learned?Anthropogenic activities are common along Biscayne Bay

•Urban•Agricultural•Municipal•Recreational•Industrial

Chemical signatures are evident

Effects may be stubble enough that won’t raise a red flag

We must keep an eye on many chemicals at once

Sweetwater? Really, there is Splenda in it!

Irgarol 1051 an antifoulant booster herbicide

N

NN

NHNH

Cl

N

NN

NHNH

SH3

N

NN

NHNH

OMe

Atrazine

Prometon

Prometyne

N

NN

NHNH

SCH3

N

NN

NHNH

SCH3

N

NN

NHNH

Cl

N

NN

NHNH

ClAmetryneSimetryn

Simazine Propazine

N

NN

NHNH

SCH3

IRGAROL 1051

Distributions along Biscayne Bay

COCONUT GROVE MARINA

CHICKEN KEY

0

2000

4000

6000

8000

10000

12000

14000

16000

Halodule Syringodium Thalassia Halimeda

Irga

rol B

CF

20072008

10

9

3

2

16

16

5

5

WATER

BCF

Ha Sy T H

SAV as a monitoring tool?

Transplant photos.(a) CG Halodule plugs stored in cooler(b) CKCG04 Thalassia transplant(c) CG Halodule control(d) CGCK Halodule transplant

a b c

d

SAV a target?

Uptake Time (days)

0 5 10 15 20 25 30

Tiss

ue C

once

ntra

tion

(ng/

g)

0

50

100

150

200

0 5 10 15 20 25 30

Tiss

ue C

once

ntra

tion

(ng/

g)

0

100

200

300

400

500

Depuration Time (days)

CHICKEN KEY TO COCONUT GROVE

Thallassia testudinum Halodule wrightii

COCONUT GROVE TO CHICKEN KEY

teI grass12.0423][ −∗=teI grass

167.0][ =r2=0.887 r2=0.921

Contaminants in Biscayne Bay - UF/IFAS OCI · PDF fileContaminants in Biscayne Bay. ... BICY-9...

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Transcript of Contaminants in Biscayne Bay - UF/IFAS OCI · PDF fileContaminants in Biscayne Bay. ... BICY-9...