courtney giles, phd candidate school of engineering ...gdrusche/classes/geol 235 - geochem of...
TRANSCRIPT
Organic Phosphorus Solid phase interactions
Courtney Giles, PhD Candidate School of Engineering, Environmental Engineering Geochemistry of Natural Waters (GEOL235) Tuesday 25 October 2011, 2:30-3:45pm Delehanty 219
What I Study:
Organic P: PHYTATE
What I Study:
Organic P: PHYTATE
How can soil bacteria do this?
What I Study:
Organic P: PHYTATE
Siderophores/Organic Anions
What I Study:
Organic P: PHYTATE
Result: Plant availability INCREASES
How does Organic P get there in the first place?
Organic P: PHYTATE
How is it removed?
How is it removed? DESORPTION
Today Soil Organic P Forms/Sources Behavior in Soils Measurement DESORPTION (e.g. phytate) Mechanisms Kinetics
Soil Phosphorus
Total Soil P
Soil Phosphorus
Inorganic Organic
Total Soil P
Inorganic Phosphorus
Inorganic
Total Soil P
Inorganic Phosphorus
Inorganic Mono-Phosphate
Pyro-Phosphate
Poly-Phosphate
= P O
O-
O-
-O
= P O
O-
O-
O = P O
O-
O-
= P O
O-
O-
O = P O
O-
O-
n
FORMS
Total Soil P
Inorganic Phosphorus
Inorganic
= P O
O-
O-
-O
= P O
O-
O-
O = P O
O-
O-
= P O
O-
O-
O = P O
O-
O-
n
Fertilization Mineral P
Organic breakdown
Microbial storage
SOURCES
Total Soil P
Organic Inorganic
Organic Phosphorus
Total Soil P
Organic Inorganic
Organic Phosphorus Orthophosphate
Diesters
1
2
Total Soil P
Organic Inorganic
Organic Phosphorus
Nucleic Acids (0.2 – 2.4% Organic P) DNA, RNA Phospholipids (0.5 – 7% Organic P) phosphatidylcholine (lecithin) Phosphatidylethanolamine (cephalin) Fatty Acids Teichoic acids
Orthophosphate
Diesters
FORMS
Total Soil P
Organic Inorganic
Organic Phosphorus
Nucleic Acids (0.2 – 2.4% Organic P) Biological Phospholipids (0.5 – 7% Organic P) Cell membrane Cell membrane Fatty Acids Microbial cell wall/membrane
Orthophosphate
Diesters
SOURCES
Organic Phosphorus
Nucleic Acids (0.2 – 2.4% Organic P) DNA, RNA Phospholipids (0.5 – 7% Organic P) phosphatidylcholine (lecithin) Phosphatidylethanolamine (cephalin) Fatty Acids Teichoic acids (Microbial cell wall/membrane)
Orthophosphate
Diesters Find the phospho-di-ester bonds…..
Organic Phosphorus
Nucleic Acids (0.2 – 2.4% Organic P) DNA, RNA Phospholipids (0.5 – 7% Organic P) phosphatidylcholine (lecithin) Phosphatidylethanolamine (cephalin) Fatty Acids Teichoic acids (Microbial cell wall/membrane)
Find the phospho-di-ester bonds…..
Total Soil P
Organic Inorganic
Organic Phosphorus
Orthophosphate Monoesters
Organic Phosphorus
Inositol phosphates
glycerophosphates
AMP
FORMS Orthophosphate Monoesters
Organic Phosphorus
Seed/grain, eukaryotes
Biological
Phospholipid break-down
Biological
SOURCES Orthophosphate Monoesters
Total Soil P
Organic Inorganic
Organic Phosphorus
Orthophosphate
Monoesters
Orthophosphate
Diesters
Inorganic
= P O
O-
O-
-O
= P O
O-
O-
O = P O
O-
O-
Organic Phosphorus ORIGINS in SOIL
The Phytate Story
Manures
Feed Digestion
Animal Feed
Plant Seeds
Today Soil Organic P Forms/Sources
Behavior in Soils Measurement DESORPTION (e.g. phytate) Mechanisms Kinetics
Today Soil Organic P Forms/Sources
Behavior in Soils Measurement DESORPTION (e.g. phytate) Mechanisms Kinetics
PHYTATE
GOETHITE
Today Soil Organic P Forms/Sources
Behavior in Soils Measurement DESORPTION (e.g. phytate) Mechanisms Kinetics
PHYTATE
GOETHITE
Abiotic Biotic
PROCESSES
PHYTATE
GOETHITE Celi et al. 2001a
Abiotic
Sorption and Desorption influenced by: P Concentration Mineral surface characteristics pH Ionic strength Temperature
PHYTATE
GOETHITE Celi et al. 2001a
Abiotic
Sorption and Desorption influenced by: P Concentration Mineral surface characteristics pH Ionic strength Temperature
PHYTATE
GOETHITE
1. Depends on aqueous CHARGE SPECIES
Celi et al. 2001a
Abiotic
PHYTATE
GOETHITE
2. Depends on mineral surface CHARGE
Celi et al. 2001a
Abiotic
3. Depends on electrostatic INTERACTIONS
Celi et al. 2001a
Abiotic
GOETHITE
3. Depends on electrostatic INTERACTIONS
Celi et al. 2001a
Abiotic
Celi et al. 2001a CALCITE
Abiotic
Celi et al. 2000
Phytate and Phosphate on Calcite Abiotic
Biotic
InsP6
Biotic DEGRADATION
InsP5
InsP6
Biotic DEGRADATION
= P O
O-
O-
-O
InsP5
InsP6
InsP4
Biotic DEGRADATION
= P O
O-
O-
-O
= P O
O-
O-
-O
InsP5
InsP6
InsP4
InsP3
Biotic DEGRADATION
= P O
O-
O-
-O
= P O
O-
O-
-O
= P O
O-
O-
-O
InsP6
Biotic DEGRADATION
= P O
O-
O-
-O = P O
O-
O-
-O
= P O
O-
O-
-O
= P O
O-
O-
-O = P O
O-
O-
-O
= P O
O-
O-
-O
InsP0
Enzyme Hydrolysis
InsP6
Biotic DEGRADATION
InsP0
Enzyme Hydrolysis
PHYTASES Fungus Bacteria Plants
ABIOTIC PROCESSES
RECAP: Behavior in Soils
GOETHITE – phytate
ABIOTIC PROCESSES
RECAP: Behavior in Soils
GOETHITE – InsP6
BIOTIC PROCESSES
ABIOTIC PROCESSES
RECAP: Behavior in Soils
ABIOTIC PROCESSES
GOETHITE – InsP6
BIOTIC PROCESSES
RECAP: Behavior in Soils
ABIOTIC PROCESSES
BIOTIC PROCESSES
PHYSICAL PROCESSES
RECAP: Behavior in Soils
Section 1
The Inositol Phosphates in
Soils and Manures ABIOTIC PROCESSES
BIOTIC PROCESSES
PHYSICAL PROCESSES
Today Soil Organic P Forms/Sources Behavior in Soils
Measurement
DESORPTION (e.g. phytate) Mechanisms Kinetics
Today Soil Organic P Forms/Sources Behavior in Soils
Measurement
DESORPTION (e.g. phytate) Mechanisms Kinetics
Aqueous Extraction
31P-NMR Enzymatic Hydrolysis
METHODS
Extraction Soil
WATER
SODIUM
BICARBONATE
NaOH EDTA
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Aqueous Extraction
Extraction Soil
WATER
SODIUM
BICARBONATE
NaOH EDTA
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Aqueous Extraction
Total Soil P
Inorganic Organic
Extraction Soil
WATER
SODIUM
BICARBONATE
NaOH EDTA
Aqueous Extraction
Total Soil P
Inorganic Organic
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Aqueous Extraction
Spectroscopy
Enzyme
Hydrolysis
Extraction Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Solution 31P
NMR
NaOH-EDTA Soil
Solution 31P Nuclear Magnetic Resonance Spectroscopy
Aqueous Extraction
Solution 31P
NMR
NaOH-EDTA Soil
Barbara J. Cade-Menun 2007
Solution 31P Nuclear Magnetic Resonance Spectroscopy
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
5 0 -5 PPM
Pyrophosphate
Orthophosphate
Other Diesters
Phosphate Diester
Orthophosphate Monoesters
Solution 31P Nuclear Magnetic Resonance Spectroscopy
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Total Soil P
Organic Inorganic
Enzymatic Hydrolysis
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Total Soil P
Organic Inorganic
Enzymatic Hydrolysis
PHOSPHATASES
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Enzymatic Hydrolysis
PHOSPHATASES Diesterases
Total Soil P
Organic Inorganic
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Enzymatic Hydrolysis
PHOSPHATASES
Monoesterases
Total Soil P
Organic Inorganic
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Enzymatic Hydrolysis
PHOSPHATASES
Monoesterases
Total Soil P
Organic Inorganic
Phytases
Enzyme
Hydrolysis
NaOH-EDTA Soil
‘The Inositol Phosphates in Soils and Manures: Abundance, Cycling, and Measurement’. Giles, CD, BJ Cade-Menun, JE Hill, 2011, Can. J. Soil Sci., in press.
Enzymatic Hydrolysis
PHOSPHATASES
Total Soil P
Organic Inorganic
Phytases
Monoesterases
Diesterases P
P
P
Enzymatic Hydrolysis
P Concentration
Ab
sorb
ence
Beer-Lambert A = e l c
Enzyme
Hydrolysis
NaOH-EDTA Soil
Enzymatic Hydrolysis
Total Soil P
Organic Inorganic
ESTIMATES Enzyme-Labile P
MEASURES Specific P classes
Today Soil Organic P Forms/Sources Behavior in Soils Measurement
DESORPTION (e.g. phytate) Mechanisms Kinetics
Today Soil Organic P Forms/Sources Behavior in Soils Measurement
DESORPTION (e.g. phytate) Mechanisms Kinetics
Negligible under environmental conditions…
Today Soil Organic P Forms/Sources Behavior in Soils Measurement
DESORPTION (e.g. phytate) Mechanisms Kinetics
Possible with Organic Anions/Siderophores…
Mechanisms….
Mechanisms….
Chelation
P Fe (III)
Mechanisms….
Chelation
P Fe (III)
- Bacterial Siderophores
- Citrate - Oxalate
Mechanisms….
Competitive Displacement
P
Mechanisms….
Competitive Displacement
P
Depends on the DISSOCIATION CONSTANTS (K) metal-organic anion metal-siderophore
Mechanisms….
Competitive Displacement
P
Citrate
Mechanisms….
Reductive Dissolution
P Fe (III) Fe (II)
Electron Donor
Mechanisms….
Reductive Dissolution
P Fe (III) Fe (II)
Ascorbate
Electron Donor
Mechanisms….
Chelation
Competitive Displacement
Reductive Dissolution
P Fe (III)
P
P Fe (III) Fe (II)
Fe
Organic Anions/ Siderophores Incubate
phytate
goethite
Measure P, Fe in supernatant
t = 0 t = 1 t = 2
.
.
. t = n
Desorption Kinetics
Methods….
Desorption Kinetics
Average Rate of Desorption in 0-4 h
(mmol L-1 h-1 )
InsP6 0.01
Fe 0.49
Average Rate of Desorption in 6-37 h
(mmol L-1 h-1 )
InsP6 0.004
Fe 0.74
Ascorbate Example….
Desorption Kinetics
Ascorbate Example….
Influence of pH and Oxalate Concentration
Oxalate Example….
0
2
4
6
8
10
0 10 20 30
InsP
6 (
uM
)
hour
100 mM pH 3.5
10 mM pH 3.5
1 mM pH 3.5
0
1
2
3
4
5
6
7
8
9
10
0 10 20 30
InsP
6 (
uM
)
hour
100 mM pH 5.5
10 mM pH 5.5
1 mM pH 5.5
Influence of pH and Oxalate Concentration
Oxalate Example….
-1
1
3
5
7
9
11
100 10 1
InsP
6 (
uM
)
mM Oxalic Acid
pH 5.5
pH 3.5
0
2
4
6
8
10
0 10 20 30
InsP
6 (
uM
)
hour
100 mM pH 3.5
10 mM pH 3.5
1 mM pH 3.5
0
1
2
3
4
5
6
7
8
9
10
0 10 20 30
InsP
6 (
uM
)
hour
100 mM pH 5.5
10 mM pH 5.5
1 mM pH 5.5
