Slide 1

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 2

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 3

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 4

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 5

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 6

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 7

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 8

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 9

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 10

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 11

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 12

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 13

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 14

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 15

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 16

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 17

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 18

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 19

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 20

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 21

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 22

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris


Slide 23

CHARACTERIZATION OF SORPTION
AND DEGRADATION OF ORGANIC
PESTICIDES APPLIED TO
CARBONATIC SOILS

Gabriel Nuffield Kasozi

Source: usda.gov

Outline


Introduction



Hypothesis



Objective of the study



Materials and Methods



Preliminary results

Introduction


Carbonatic soils are composed of
more than 40% Carbonates



Over 500 carbonatic soils in USA and
12 are in South Florida



85% of Florida vegetables and
Tropical fruits grown on Carbonatic
soils
Source: BMP project report, 2002

Pesticide use


Estimated Annual Total Pesticides Use in SFWMD
14,590 tons .
Pesticides Detected in Water Resources in South FL and PR

1

Pesticide

Chemical class

Where detected

Atrazine

S-triazine

Ground, surface water (FL; PR) 1,2,4

Ametryne

S-triazine

Ground, surface water (FL; PR) 3,4

Diuron

Substituted urea

Surface water (FL) 1

Endosulfan

Organochlorine

Surface water (FL)

Enthroprop

Organophosphate

Surface, ground water (PR) 3

Diazinon

organophosphate

Surface, ground water (PR) 3

Lindane

organochlorine

Surface, ground water (PR) 3

Miles and Pfeuffer (1997); 2 Potter et al., (2002); 3 Dumas and Rosario (2003); 4 CondeCostas and Rodriguez (1997); FL= Florida; PR = Puerto Rico

Dade Hydrogeologic Cross-section

Introduction


Sorption and degradation determine the fate
of an applied organic pesticide

Source: SFWMD

Hypothesis


Organic pesticides are adsorbed less
on carbonatic soils as compared to
non-carbonatic soils



The nature of soil organic matter affects
the degree of pesticide sorption



Pesticides degrade faster in Carbonatic
soils than in non-carbonatic soils

Objective of the study


Characterize and compare chemical and
physical properties of carbonatic soils
with those of associated non-carbonatic
soils and soils from other areas



Characterize sorption and degradation of
selected pesticides and create a database
for sorption and transformation of these
pesticides on carbonatic soils

Objective of the study


Characterize organic matter (formation,
composition and functionality)



Identify the dominant component
controlling sorption of pesticides

Materials and Methods


Soils
• Soil samples will be taken from South Florida,
Puerto Rico and Uganda
• Biscayne, Perrine, Pennsuco, Chekika, Krome,
Lauderhill, Tamiami



Proposed Pesticides
• Atrazine, Ametryne, Oxamyl, Diuron,
Endosulfan, Lindane, Carbaryl, Enthroprop,
Diazinon

Materials


Experiment 1
• Characterization of soil physical and
chemical properties
• pH, TOC, CEC, Clay Minerals, CaCO3
• Determination of organic carbon
• Walkley-Black method
• Thermogravimetry

• Sorption isotherms determination (Batch
slurry method)

Methods


Experiment 2
• Characterization of organic matter
• Stable isotope δ 13C, δ 15N, and C/N
ratios
• n-Alkanes by GC-FID
13

1

• Liquid and Solid state C and H
NMR
• Pyrolysis GC-MS

Materials and Methods
Experiment 3
 Characterization of the nature of binding
existing between OM and pesticides
• 13C NMR
• NanoESI-GC-MS

• Flow Calorimetry

Materials and Methods
Experiment 4
 Characterization of degradation of pesticides
in carbonatic soils


Solvent extractable disappearance of the
parent pesticide



Degradation rate coefficients and halflife (t1/2) will be determined

Materials and Methods
Data Analysis
 Sorption data will be fit using the
Freundlich model


Degradation data will be fit using first
order kinetics

Preliminary Results
Table of results
Soil

ε

% CaCO3

Π

% OC

ε

% OM

Biscayne
Perrine

80
87

5.82
2.79

9.82
4.75

Pennsuco
Krome
Chekika
LauderHill

67
87
-

2.37
1.45
1.9
35.78

3.45
3.94
-

Tamiami

-

36.25

-

Matecumbe

-

28.13

-

= Walkley and Black ; Π = Thermogravimetry

Π

Preliminary Results


TG % OM vs WB % OC
12.00

TG (%OM)

10.00

y = 1.755x
R2 = 0.9514

8.00
6.00



4.00
2.00
0.00
0.00

1.00

2.00

3.00

4.00

5.00

WALKLEY-BLACK (%OC)

6.00

7.00

Comparison of
TG with
Walkley-Black
for OC
determination
Literature
Conversion
factor: 1.724

Preliminary Results
Table of results
Soil

Biscayne
Perrine
Krome
Chekika
Lauderhill
Soil solution ratio: 1:2

pH (KCl)
(1 M)
7.66
7.78
7.59
7.72
6.98

pH (H2O)

8.11
8.00
8.51
8.29
7.39

Preliminary Results
Linear Sorption Isotherm for Biscayne
Diuron Isotherm (Biscayne)

ADSORBED CONC. (μg/g) )

40
y = 5.84x
R2 = 0.9805

35
30
25
20
15
10
5
0
0

1

2

3

4

SOLUTION CONC. (μg/m l)

5

6

7

Preliminary Results
Linear Sorption Isotherm for Krome
Diuron Isotherm (Krome)

ADSORBED CONC. (μg/g) )

25
y = 3.11x
R2 = 0.9516

20
15
10
5
0
0

1

2

3

4

5

SOLUTION CONC. (μg/m l)

6

7

8

Preliminary Results
Sorption coefficients of Diuron
Soil series

Sorption coefficient
KD

Koc

Biscayne

5.84

101

Perrine

2.6

92

Chekika

2.6

136

Krome

3.11

222

Lauderhill

139.49

390

Iowa

11.09

240

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

400 †

Preliminary Results
Sorption coefficients of Atrazine
Soil series

Sorption ceofficient
KD

Koc

Biscayne

2.16

37

Perrine

0.71

29

Chekika

0.76

40

Krome

0.82

57

Lauderhill

45.20

101

Iowa

4.06

88

† Literature
†(Wauchope et al., 1992, and Nkedi-Kizza et al., 1985)

100 †

Advisory Committee:
Dr. Peter Nkedi-Kizza
Dr. Yucong Li
Dr. David Hodell
Dr. David Powell
Dr. Willie Harris