Beneficial Land Application Uses of FGD Products

9/10/2014
History of Gypsum Use and Research Results
On Crop Performance
Warren Dick, PhD
Soil Scientist and Professor
School of Environment and Natural Resources
The Ohio State University
KANSAS STATE UNIVERSITY ALUMNI CENTER, AUGUST 13, 2014
AUGUST 13, 2014
What is Gypsum?
∂
∂
Background, Role and Potential Crop
Benefits in Using Gypsum
Dr. Warren A. Dick
Professor, School of Environment and Natural Resources,
The Ohio State University
[email protected], 330-263-3877
Gypsum is a very soft mineral composed of calcium sulfate dihydrate, with the
chemical formula CaSO4·2H2O. The word gypsum is derived from a Greek word
meaning "chalk" or "plaster". Because the gypsum from the quarries of the
Montmartre district of Paris has long furnished burnt gypsum, this material has
often been called plaster of Paris. Gypsum is moderately water-soluble. The source
of gypsum is both mined and synthetic.
Gypsum from New South
Wales, Australia
Gypsum Powder
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History of Gypsum in Agriculture


Early Greek and Roman times
Fertilizer value discovered in Europe in last
half of 18th century



Germany (1768) – Reverend A. Meyer
France (date?) – Men working with alabaster
(plaster of paris) noted better grass growth in
areas they shook dust from clothing
Early History
Benjamin Franklin
“This hill has been
land plastered”
Extensive use in Europe in 18th century
Early History
Doctor William Crocker was born
in Medina County, OH on
January 27, 1876. He received
his A.B. degree in 1902 and an
A.M degree in 1903 from the
University of Illinois. From 1904 1906 he was a Fellow at the
University of Chicago from which
he obtained his PhD.
Early History
History of the Use of Agricultural
Gypsum. 1922. Gypsum Industries
Association, Chicago, IL (p. 7-36)
I. The Early Use of Gypsum as a
Fertilizer
II. Recent Studies on the Function
and Quantity of Calcium and Sulphur
in Crops and the Supply of Sulphur
in our Agricultural Soils.
III. Calcium in the Nutrition of Plants
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Early History
History of the Use of Agricultural
Gypsum. 1922. Gypsum Industries
Association, Chicago, IL (p. 7-36)
IV. Gypsum as a Stimulant
V. Gypsum as Specific for Black Alkali
VI. Gypsum as a Preserver of
Manure
VII. Effect of Gypsum on the Nitrogen
Available for Crops
VIII. Gypsum Not a Substitute for
Agricultural Lime
Gypsum Sources



Mined Gypsum
FGD gypsum - 24% of total U.S. gypsum in 2005
Phosphogypsum – phosphoric acid production




4.5 tons gypsum for each ton of phosphoric acid produced
Titanogypsum – TiO2 production
Citrogypsum – citric acid production
Biotech gypsum
History of Gypsum in Agriculture
Gypsum as a Preserver of Nitrogen – In pioneering
work by Heiden:
“Gypsum has great power in preserving the volatile nature of manure.
It does this in large part by transforming the volatile ammonium
carbonate into the non-volatile ammonium sulfate with the formation of
calcium carbonate.”
Further work on this topic was done by Ames and Richmond at The
Ohio State Agricultural Experiment Station (Soil Science, 4:78-89,
1917). Using gypsum to preserve nitrogen for a 20 cow herd could
provide $152 benefit in one year.
Summary of Gypsum Benefits
in Agriculture
 Ca and S source for plant nutrition
 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm fields
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Relative Numbers of Atoms
Required by Plants
Benefit #1
 Ca and S source for plant nutrition

 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm fields







Amino acids methionine and cysteine




Proteins
Precursors of other sulfur-containing compounds
Sulfolipids (fatty compounds) in membranes,
especially chloroplast membranes
Nitrogen-fixing enzyme (nitrogenase)

28 S atoms in active site
1
100
300
1,000
2,000
2,000
3,000
30,000








P
Mg
Ca
K
N
O
C
H
60,000
80,000
125,000
250,000
1,000,000
30,000,000
35,000,000
60,000,000
Causes of Sulfur Deficiencies
in Crops
Sulfur in Plant Physiology

Mo
Cu
Zn
Mn
B
Fe
Cl
S





Shift from low-analysis to high-analysis
fertilizers
High-yielding crop varieties use more S
Reduced atmospheric S deposition
Decreased use of S in pesticides
Declining S reserves in soil due to loss of
organic matter (erosion and tillage), leaching,
and crop removal
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Reduction in Atmospheric S
Deposition
Soil Sulfur Content (ppm)

Increasing in importance as cause for crop S deficiencies
Loss of soil organic matter
Reduced annual sulfate deposition
 34 kg sulfate/ha in 1971
(10 lb S/A)
 19 kg sulfate/ha from
2000 onward
(5.7 lb S/A)
40
30
Y = 28.6** - 1.74**
R2 = 0.86
20
10
0
0
1
2 3 4
5
6 7
8 9 10 11 12
Year (20yy)
Average Corn Yields from
2002 to 2005 (Ohio)
) -1
170
9.0
8.5
S
No S
150
8.0
7.5
130
7.0
6.5
110
6.0
Y=5.80+0.029x-0.00009x2 (R2=0.85)
2
2
Y=5.19+0.021x-0.00003x (R =0.96)
5.5
Average Corn Yield (Mg ha
90
5.0
00
45
50
90
100
135
150
-1
Rate(kg
(lbs/A)
NNRate
ha )
180
200
225
250
Corn Yields in 2003
(Wooster, Ohio)
Corn Yield (Bu/acre)

Corn Grain Yield (Bu/A)

Soil Test Values - Sulfur
200
195
190
185
Yield of corn (at 120 lbs N/A) at
Wooster, Ohio in 2003 was
increased by addition of gypsum
due to its ability to correct this
soil’s S deficiency.
A
B
180
175
170
Control
FGD gypsum-S
(30/lb/acre)
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Effect of Gypsum on Cumulative Alfalfa
Yields at Wooster, OH (2000 - 2002)
Corn (Sulfur Nutrition)
t/ac
Minnesota Soils
1985
1986
25
22
19
16
13
10
A
B
Control
+ Gypsum
Different letters over each bar represent a significant
difference at p ≤ 0.05.
(Rehm, Commun. Soil Sci. Plan Anal., 24:285-294, 1993)
Forage Quality and Fertilizer N
Interaction

Daily Sheep Gain (g/day)
200
180
160
Calcium in Plant Physiology
(Wang et al., Nutr. Cycl.
Agroecosystem, 62:195–202
(2002)
N (0)
N (138)
140

120
100
80

60
Required for proper functioning of cell
membranes and cell walls
Needed in large amounts at tips of growing
roots and shoots and in developing fruits
Relatively little Ca is transported in phloem

40
Ca needed by root tips comes from soil solution
20
0
S (0)
S (60)
Treatment
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Amelioration of Subsoil Acidity
and Al3+ Toxicity
Benefit #2
 Ca and S source for plant nutrition

 Source of S and exchangeable Ca to
ameliorate subsoil acidity and Al3+
toxicity


 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm fields


Ca from lime
will not reach
the subsoil
Soil Surface
Surface-applied gypsum leaches down to
subsoil
Ca2+ exchanges with Al3+
SO42- complexes with Al3+ ion to form
AlSO4+
AlSO4+ is not toxic to plant roots
Results in increased root growth in the subsoil
Gypsum applied to surface of soil with acidic subsoil
SO4
Ca
Ca
Ca
SO4
Ca
Toxic
Ca
Ca
Ca
Ca
Non-toxic
Soil Acidity
Soil Acidity
Soil Acidity
Soil Acidity
Ca
Ca
Al
H+
Al
Al
Al
Al
Al
H+
H
Al
H
Clay platelet in subsoil
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Increased Root Growth
into Subsoil

pH
Increased water absorption
Increased recovery of N from subsoil


Demonstrated in Brazilian soils
Improved N-use efficiency, Ohio, USA
3
4
5
6
7
pH
10
Depth (cm)

Typical pH profile for a
Blount soil
20
30
Al3+
40
50
60
70
CaSO4 + Al3+
(toxic)
Al(SO4)+ + Ca2+
(non-toxic)
Forages (Subsoil Acidity)
Corn Root Density m/1000 cm3
1
2
3
8.8
Production Phase
20
Depth
(cm)
limestone
limestone + gypsum
40
Yield (Mg/ha)
8.6
8.4
8.2
8.0
Yield attributed to calcium carbonate
equivalency due to impurity in the
gypsum
7.8
60
80
Modified from Farina &
Channon, SSSAJ (1988)
Gypsum can ameliorate
aluminum toxicity,
especially in the subsoil,
by forming soluble
complexes with Al3+.
7.6
0
10
20
30
Gypsum (Mg/ha)
(Ritchey and Snuffer, Agron. J., 94:830–839 (2002)
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Increased Root Growth
into Subsoil
Forages (Long-Term Effect)
115
4.5
(Farina and Channon, Soil Sci. Soc. Am. J.,
52:175-180, 1988)
116
110
105
100
95
98
Alfalfa Yield (tons/A)
Corn Grain Yield (Bu/acre)
120
Control
Gypsum (15 tons/A)
4.1
3.6
3.0
2.7
2.4
1.8
1.7
0.9
90
0
85
Lime
Lime + Gypsum
Experiment 1
(16 yrs prior)
Experiment 2
(15 yrs prior)
Treatments
Toma et al., Soil Sci. Soc. Am. J., 63:891-895, 1999)
Conclusions



Benefits for corn and forages are associated with
increased sulfur nutrition and reduced subsoil
acidity.
Benefits of gypsum use may persist for several
years after application to soil.
Inappropriate use of high rates of gypsum can
decrease yield (due to nutrient imbalances).
Benefit #3
 Ca and S source for plant nutrition
 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil
structure and reclaim sodic and high
magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm fields
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Gypsum applied to surface of sodic soil
Benefit #3
SO4
Ca2+
Ca2+ Ca2+
SO4
Ca2+
Soil Crusts
Na+
Na+ H+
Na+
Mg2+ K+
Al3+
Clay platelet in sodic soil
Gypsum and Sodic Soil
Reclamation (Colorado)
Gypsum and Sodic Soil
Reclamation (China)
Comparison of field with (background) and
without (foreground) FGD by-product gypsum
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Benefit #4
 Ca and S source for plant nutrition
 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in
soil
Benefit #4
CaSiO3 + 2CO2 + 3H2O = Ca2+ + 2HCO3- + H4SiO4
Ca2+ + 2HCO3- = CaCO3 + H2O + CO2
NET: CaSiO3 + CO2 + 2H2O = CaCO3 + H4SiO4
Passive Sequestration of Atmospheric CO2 Through Coupled PlantMineral Reaction in Urban Soils. Manning and Renforth, Environ
Sci. Tech, 47:135-141, 2012.
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm fields
Benefit #4
The cationic bridging effect of the
calcium ion (Ca2+) and the
flocculating ability of clay and
organic matter are crucial in the
formation and stability of soil
aggregates. (Wuddivira and CampsRoach, Eur. J. Soil Sci., 2006).
The stability of microaggregates is
enhanced by multivalent cations
which act as bridges between organic
colloids and clay. (Oades, Plant & Soil,
1984)
Benefit #5
 Ca and S source for plant nutrition
 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use
efficiency
 Reduce phosphorus runoff from farm fields
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Benefit #5
Benefit #5
Precipitating liquid
manure solids
Calcium for precipitating
organic matter when
measuring enzyme
activity in soil
2014 All Ohio Chapter of the Soil & Water Conservation Society (Columbus, OH)
Benefit #6
Water Quality - The Great Lakes
 Ca and S source for plant nutrition
 Source of S and exchangeable Ca to ameliorate
subsoil acidity and Al3+ toxicity
 Flocculate clays to improve soil structure and
reclaim sodic and high magnesium soils
 Ca-humate and CaCO3 formation in soil
 Treat liquid manure to enhance use efficiency
 Reduce phosphorus runoff from farm
fields
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2014 All Ohio Chapter of the Soil & Water Conservation Society (Columbus, OH)
Water Quality - The Great Lakes
2014 All Ohio Chapter of the Soil & Water Conservation Society (Columbus, OH)
Water Quality - Lake Erie
Dissolved Reactive
P is the Problem
Water Quality - Agriculture
Phosphorus and Soil
Management
580 (Wooster)
867 (Hoytville)
45 (Wooster)
38 (Hoytville)
609 (Wooster)
868 (Hoytville)
160 (Wooster)
282 (Hoytville)
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Water Soluble P in 0.5 in soil layer
(4 T/A gypsum, 1:3 w/v soil:water)
10.000
10
Hoytville Samples
8
7.000
6
6.000
+ Gypsum
- Gypsum
5.000
4
4.000
Wooster Samples
7.000
8.000
3.000
2
2.000
1.000
Soluble P (ppm)
9.000
Soluble P (ppm)
Water Soluble P in 0.5 in soil layer
(4 T/A gypsum, 1:3 w/v soil:water)
7
6
5
4
3
2
1
0
6.000
5.000
4.000
+ Gypsum
- Gypsum
3.000
2.000
1.000
0.000
0
0.000
CS - C
CC
CS – S
Crop Rotation
Water Quality Benefits
CS – C
CS – S
Crop Rotation
CC
Tile Drain
Effect of Gypsum on Water Runoff, Soil Erosion
and Soluble Reactive Phosphorus (SRP)
Samples were collected
from the Rolland
Wolfrum Hale Farm
(Hicksville, OH) on
December 20, 2012.
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9/10/2014
Tile Drainage Samples (1)
Conservation Innovation Grant
(2011-July 2013)
Soluble Reaction (mg L-1)
0.12
0.10
58 samples
62% reduction
0.107 ppm
0.08
0.06
0.041 ppm
0.04
0.02
0.00
Gypsum(1
(1ton/acre)
ton/acre)
Treated
Samples collected from the Ken Hahn Farm (Antwerp, OH) on
January 6, 2013.
Tile Drainage Samples (2)
Conservation Innovation Grant
(2011-present)
No Gypsum
Rolland Wolfrum
farm samples 20
months after
gypsum application
Soluble Reaction (mg L-1)
0.12
Plus Gypsum
Untreated
Treatments
0.10
80 samples
55% reduction
0.104 ppm
0.08
0.06
0.047 ppm
0.04
0.02
0.00
Gypsum(1
(1ton/acre)
ton/acre)
Treated
Untreated
Treatments
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Summary of Results (to Date)
Summary of Results (to Date)
1. 43 total sampling events (126 total samples)
from May 2012 through April 2014. P
reductions in tile drainage water persist at
least 20 months after gypsum treatment.
3. Average reductions for all gypsum-treated
areas combined was 37%, with median
reduction of 46% and a range from 0 to 93%.
2. Reduction in P concentrations for individual
gypsum-treated areas varied from 0 to 69%.
4. P concentrations (mg/L) in drain water for
individual sampling events ranged from 0.01
to 0.11 (mean = 0.042) in gypsum-treated
areas and from <0.01 to 0.43 (mean = 0.085)
in areas without gypsum.
Effects of Gypsum on Trace Metals
in Soils and Earthworms
Special Section – Sustainable Use of FGD Gypsum for
Agricultural Uses
Other Comments
Journal of Environmental Quality 43:263-272 (2014)
10 papers – all focused on gypsum use and in this
case primarily, but not exclusively, environmental
impacts.
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Heavy Metal Impacts
Bioaccumulation Factors
Amending Soil Properties With
Gypsiferous Products
CONSERVATION PRACTICE
STANDARDS (DRAFT)
NATURAL RESOURCES CONSERVATION SERVICE
AMENDING SOIL PROPERTIES WITH GYPSIFEROUS
PRODUCTS
(Ac.)
CODE XXX
17
9/10/2014
Development of Network for FGD
Gypsum Use in Agriculture
http://www.oardc.ohio-state.edu/
agriculturalfgdnetwork
Workshop sponsored by:
Combustion ByProducts Recycling Consortium
(CBRC)
http://ohioline.osu.edu/b945/b945.pdf
Electric Power Research Institute (EPRI)
The Ohio State University
U.S. Department of Energy/National Energy
Technology Laboratory
November 17-19, 2009
Indianapolis, IN
November 4 (afternoon), Pittsburgh, PA
https://www.acsmeetings.org/
Increasing National Interest at the
Scientific Level
THANK
YOU!
18

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