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Controlled Release FertilizersControlled Release FertilizersAvi Shaviv
Faculty of Civil & Environmental Engineering Technion-IIT, Haifa, Israel.
agshavivagshaviv@@txtx..techniontechnion.ac..ac.ilil
IFA International Workshop: Enhanced-Efficiency Fertilizers27-30 June 2005, Frankfurt, Germany
CRFCRF’’s s -- ““High Agronomic Use Efficiency High Agronomic Use Efficiency while minimizing Environmnetal Impact ,,, in while minimizing Environmnetal Impact ,,, in one single applicationone single application””
Conventional fertilization goes with high N (and Conventional fertilization goes with high N (and other) losses to GW (NOother) losses to GW (NO33) and to air (NH) and to air (NH33, N, N22O ,,O ,,NoNoxx))
Great efforts to develop approaches, techniques Great efforts to develop approaches, techniques and Fertilizers to minimize damage and sustain and Fertilizers to minimize damage and sustain agriculture (soil, water, production potential)agriculture (soil, water, production potential)
Increasing awareness to fertilizer impact onIncreasing awareness to fertilizer impact onEnvironment
2
Pathways of Loss
Plant Uptake Plant Uptake --
NN--PP--K and MeK and Me
Microbial Reactions
SYNCRONISYNCRONIZAZATIONTION-- ..Plant Demand ..Plant Demand vs. Nutrients Supplyvs. Nutrients Supply
SUPPLY: Preferred & BioSUPPLY: Preferred & Bio--Available Available Nutrient CompositionsNutrient Compositions ammonium/nitrate; ammonium/nitrate;
NHNH44+ + /P/P
NHNH44+ + or K / Microelementsor K / Microelements
3
Improve Application MethodsImprove Application Methodsor or Modify FertilizersModify Fertilizers
•• Positioning: Banding, nesting,,, Super Granules (high NH4 conc. To reduce nitrification)
• Bio-Inhibitor Amendments (NI’s)
• Controlled Release Fertilizers•Targeted Delivery Fertigation, Precision Agriculture
CRF vs. SRFCRF vs. SRF
SRF SRF UF, MEU, SCU, PSCU?UF, MEU, SCU, PSCU?
CRFCRF Polymer coatedPolymer coatedOne single application,,, provides prolonged One single application,,, provides prolonged
supply of nutrientssupply of nutrients
Matches (better) plant demandMatches (better) plant demand……(level, proportions, timing)
The closer the synchrony
higher NUENUE and lower LOSSESLOSSES
4
CRF vs. SRFCRF vs. SRF Release Release less sensitive to:less sensitive to:Soil/medium type, moisture, pH, Soil/medium type, moisture, pH,
microbial activitymicrobial activity MinimizesMinimizes: : losses to environment, losses to environment, application cost, application cost, stress on plants,stress on plants, EnsuresEnsures: : --
better growth & yields, better growth & yields, high quality food/producthigh quality food/product
,,,,,,,,,,,,,,,,,,,,,,,,,YET ,,,,,,,,,,,,,,,,,,,,,,,,,YET -- CRF COST is A LIMITCRF COST is A LIMIT
Nutrient coreNutrient core
Polymer coatingPolymer coating
5
water vapordissolution
rupturerupture ((““failurefailure””))immediate releaseimmediate release
diffusion / convectiongradual release
swelling
PP
r
rrllPPSS
PPhh
Coatings: Coatings: Alkyd Type, Alkyd Type,
PolyPoly--Urethane like, Urethane like,
PolyPoly--Olefin (modified), Olefin (modified),
Poly Poly ––Sulfur Coated (??), Latex? Sulfur Coated (??), Latex?
Release Affected byRelease Affected by:
PermeabilityPermeability TT, Solubility ?!
RadiusRadius r,r,
Coating thickness – l,l,
Slightly affected bySlightly affected by water water content, pH, medium typecontent, pH, medium type
Rel
ease
Rel
ease
TimeTime
lagDiffusion
Failure
linearrelease
decay
Release from a Single Coated Urea Release from a Single Coated Urea Granule: Granule: Diffusion Diffusion vsvs FailureFailure
6
0
40
80
0 50 100 150 200
Time (days) %
R
elea
seP3�
hPlrt
*','C3),,( sat tttttlrPtlrg
s
s
laglag
linearlinear
*
3exp
C1),,(
s
sat ttlrP
tlrg s
decaydecay
Shaviv et al, 2003a,b, Envir. Sci & Tech, Model of Urea (or single fertilizer) ReleaseModel of Urea (or single fertilizer) Release
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 20 40 60 80 100 120 140
time [day]
rele
ase
exp. calculated
Modified Poly-Olefine
Exp vs Model for for Population of granulesPopulation of granules
7
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 20 40 60 80 100 120 140
time [day]
rele
ase
exp. calculated
Poly-Urethane Like
Exp vs Model –– for for Population of granulesPopulation of granules
R l in e a r ~ C s a t x P S = C s a t0 e x p ( -E A C /R T ) x P S
0 e x p ( -E A P s /R T )
R l in e a r ~ C s a t0 x P S
0 e x p [- (E A C + E A P s) / R T ]
L o g R l i n e a r v s 1 /R T E A = E A C + E A P s
Energy of Activation for Release helps Energy of Activation for Release helps in Modeling Temperature effectin Modeling Temperature effect
or,,,,,, the concept of the concept of Cumulative Rate of N releaseCumulative Rate of N release(Gandeza et al., 1991)
CRN = a + b (CT) + c (CT)2
8
Important Release FeaturesImportant Release Features
•• Pattern:Pattern:
•• FickianFickian (parabolic), linear, (parabolic), linear, sigmoidalsigmoidal, , bibi--modalmodal
•• Duration:Duration:
Time of releaseTime of release of content (of content (75%, 80%?)75%, 80%?)
at given temperature, 21at given temperature, 2100C or 25C or 2500C (?)C (?)
•• Burst Burst (initial release < few %)(initial release < few %)
•• Tailing Tailing -- LockoffLockoff (non (non utilisedutilised nutrient)nutrient)
Cumulative Urea Release
0
40
80
0 50 100 150 200Time (days)
%
Rel
ease
Alkyd type PSCU Polyolefin Polyurethane
Burst
Lock-off / tailing
SigmoidalFickianFickian
9
CRU N - BALANACE
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100 120 140 160 180
TIME (DA YS)
N BA
LANC
E %
N R EC O VE R Y N U PTAKE INCUBATION
Release Prediction Important for Better Release Prediction Important for Better Synchronizing Plant Demand with Nutrient Synchronizing Plant Demand with Nutrient
SupplySupply
ReleaseRelease
Note Note –– SigmoidalSigmoidal PatternPattern
time , daystime , days
Cum
ula t
ive
Cu m
ula t
ive
Re l
eas e
Re l
eas e
Practically – release from large population => high variation – Ph, Ps, l, r, Statistics Statistics
50
10
long term release ,NO 3, 6C
020406080
100
0 50 100 150 200 250time ( days )
%
NO3
rele
ase
Osmocot Pluss 329
Osmocot Pluss 330
Osmocot Pluss 331
Plantacote Pluss 338
Nutricote 349
NPK 12-300
NPK 12-1998
long term release ,NO3, 21 C
02040
6080
100120
0 50 100 150 200 250time (days )%
N
O3
rele
ase
Osmocot Pluss 329
Osmocot Pluss 330Osmocot Pluss 331Plantacote Pluss 338
Nutricote 349
NPK 12-300NPK 12-1998
` balance
long term release ,NO 3 , 30 C
020406080
100120
0 50 100 150 200
time (days)
%
NO
3 re
leas
e
Osmocot Pluss 329
Osmocot Pluss 330
Osmocot Pluss 331
Plantacote Pluss 338
Nutricote 349
NPK 12-300
NPK 12-1998
Temperature Temperature EffectEffect
Various Various CRFsCRFs
~ 1.5 ~ 1.5 ––2.0 increase2.0 increase
for 10for 1000CC
0
10
20
30
40
50
60
70
80
90
0 50 100 150
% N
-NH
4re
leas
e
time (days)
8oC 21oC 30oC 40oC
~ 1.5 ~ 1.5 ––2.0 fold increase for each 102.0 fold increase for each 1000CC
~ ? ~ Q10 factor~ ? ~ Q10 factor
11
Effect of soil/medium properties Effect of soil/medium properties (or water status?)(or water status?)
% r
elea
se
0
10
20
30
40
50
60
70
80
90
100
7 days 49 days 101 days
Sand
Peat pH 4.5
Limed peat
Water
Release at 30oC
Release only SLIGLTY affected by soil type and soil pH
Effect of dryingEffect of drying--wetting cycles (=irrigation)wetting cycles (=irrigation)
0
5
10
15
20
25
30
35
40
45
50
7 days 28 days 35 days 49 days
% r
elea
se
Dry&Wet
Control
• Important Important -Drying-wetting cycles do not damage the coating• TThe release is slowed down when the soil is dry he release is slowed down when the soil is dry ––(this prevents salt accumulation and root scorching)
12
Release from a compound CRF Release from a compound CRF
more complicatedmore complicated•Different Solubilities of NONO33 , NH, NH44 , P , K, P , K
•Limited amount of WATER for dissolution
•Moisture content Changes:
Free Water,
Saturated Soil
Unsaturated Soil
•Temperature Changes
Rrelease, NO3, 30C
0
20
40
60
80
100
120
0 50 100 150 200time (days)
%
NO
3 re
leas
e Osmocot Pluss 327
Plantacote Pluss 335
Nutricote 347
AGROBE len 351
NPK 8-300
NPK 8-31
Release , P, 30C
0
20
40
60
80
100
0 50 100 150 200time (days)
%
P re
leas
e
Osmocot Pluss 327
Plantacote Pluss 335
Nutricote 347
AGROBE len 351
NPK 8-300
NPK 8-31
DifferentDifferent
Release Release Patterns/Patterns/
RateRate
Typical Typical
For All For All single single FertsFerts. . basis basis CRFsCRFs
13
Release F1 - free water (20 C)
0
20
40
60
80
0 20 40 60 80
day
Rel
ease
(%)
K
NO3
NH4
P
Release F1 - free water (40C)
0
50
100
0 20 40 60 80
Day
Rel
ease
e (%
)
KNO3NH4P
NONO3 3 ~ NH~ NH4 4 > K > P> K > P
Characteristic Coated CRF – limitedlimited water amount in granulegranule
•• Characterization,,,,,,,,,,,,Characterization,,,,,,,,,,,,
•• Testing,,,,,,,,,,,,Testing,,,,,,,,,,,,
•• Performance EvaluationPerformance Evaluation
14
15
Experiments in Different Planting Systems
• Pots, low volume
• Containers (detached media), 30 Liter
• Lysimeters , 130 liter (to mimic field conditions ,,,ACAP)
• Real soil experiments, complicated/difficult when Mass Balance & Environmnetal Impact needed
16
Ryegrass Experiment – to test the effect of
Urea ReleaseUrea Release Pattern on Growth and Leaching
4 cuttings (each 4-5 weeks)
Leaching before each cutting
CRFs –
Three N levels 0.8, 1.2, 1.6 gN/pot
Special CRU 932; CRU 948; CRU 1049 with different SIGMOIDAL N release patterns and Durations
PSCU – Polymer sulphur Coated Urea - with “burst” and “lockoff”
Compared to urea application : 1/3 at start (solid) 1/3 after 1st harvest (liquid); 1/3 after 2nd harvest,
PSCU
932
948
PSCU
35d80d
17
CRF vs. SRF CRF vs. SRF Ryegrass in pots, 4 cuttings & Ryegrass in pots, 4 cuttings & leachingsleachings
CRU N - BALANACE
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100 120 140 160 180
TIME ( DAYS )
N B
ALA
NC
E
N RECOVERY N UPTAKE INCUBATION
PSCU N - BALANCE
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100 120 140 160 180
TIME ( DAYS )
N BA
LANA
CE
N RECOVERY N UPTAKE INCUBATION
ShavivShaviv, 1966, 1966
Synchronizing Urea Supply with plant demand resulted in Synchronizing Urea Supply with plant demand resulted in maximal DM yield and Minimal N losses, No Damage to maximal DM yield and Minimal N losses, No Damage to
PlantsPlants
CRU CRU 80 d80 d
CRU CRU 35 d35 d
18
Container Experiments:Container Experiments:Volcanic Tuff Volcanic Tuff -- 1999, 1999, PerlitePerlite -- 20002000
Red Volcanic Tuff, 0Red Volcanic Tuff, 0--8 mm (porous)8 mm (porous)CEC 15 CEC 15 meqmeq/100g, /100g, Qsat Qsat 50%50%(Amorphous Clay, Volcanic Glass, Primary Min., Iron (Amorphous Clay, Volcanic Glass, Primary Min., Iron Min.)Min.)PerlitePerlite, 2, 2--3mm (porous)3mm (porous)low CEC, low CEC, QsatQsat 65%65%
Basil Basil -- 4 4 Harvestes Harvestes (30 days)(30 days)33--5 5 fertigationsfertigations/days/dayscontinuoscontinuos leaching + collectionleaching + collectionmonitoringmonitoring : : fertigationfertigation, , leachateleachate, , assayassay: plants => nutrient uptake: plants => nutrient uptake
Experimental setup, Tuff, 1999.
Treatment DescriptionB Control A D A- Fertigation: First 1/3 irrigation only, 2/3 with
100% of referenceD C B Total applied- 65% of reference
A C D B- 20% fertigation and 45% as banded CRF.
Control C B A Total applied - 65% of reference
D C B C- Fertigation with 65% of reference level, no leaching period
B A Control D Total applied- 65% of reference
C D A D- Fertigation according to commercial recommendations, Reference treat
A Control B
C Total applied - 100% (reference)
Reference Treatment: 70 ppm N after planting, raising to 120 after 2 weeks
1. Fertilizer used for fertigation: 6-3-6 +6ME (Deshen Gat), ammonium/nitrate – 60:40
2. Applied controlled release fertilizer (CRF) “Multicote” (Haifa Chemicals), with a “tailor made”
composition of : 16.5-8.5-16.5
19
37
45
25
41
4944
63
29
0
10
20
30
40
50
60
70
A B C D
N Use Efficiency(Shoots) & N Leaching Fraction - Basil grown on Tuff
% of N( Output/Input) % of N (Plant/Input)
22
46
11
42
22
55
24
48
0
10
20
30
40
50
60
A B C D
N Use efficiency (Shoots)& N Leaching Percentage -Basil grown on Perlite
% of N( Output/Input) % of N (Plant/Input)
TuffTuff
PerlitePerlite
20
Lysimeters (substitute experiment in “real” soil)
21
Tensiometer
Wicks Sampler
2lit/hr emitters Rhizon soil moisture sampler
41
17
40
68
83
cm
cm
cmcm
cmcmcm
55
5-7
Drainage layercm
37
thermometer
5
Sandy LoamSandy Loam
Cumulative yield in lysimeter- grown basil plants
50
7450
78
57.67
102
127
66.67
109
135
20.67
18.670
20
40
6080
100
120
140
160
3.5 8 12Time from planting (weeks)
Yield (dry weight
g / lysimeter)
Treatment-A(100reference ) Treatment-B(80referenceTreatment-C(Ncoat 80) Treatment-D(Multigrow-80)
22
Cumulative leaching of nitrogen in drainage of basil lysimeters
0.002.004.006.008.00
10.00
2 3 4 6 7 10 11 13 17 20 23 31 38 44 50 59 66 80
Time from planting (days)
Nitrogen leached
(g / lysimeter)
Treatment A(100 reference)Treatment B(80 reference)Treatment C(Ncoat-80)Treatment D(Multigrow-80)
Cumulative - P uptake g / lysimeterBASIL in lyzimeters
0.25
0.25
0.440.37
0.10
0.36
0.10
0.39
0.56
0.25
0.66
0.53
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
3.5 8 12Time (weeks)
P g
Treatment-A(100reference) Treatment-B(80referenceTreatment-C(Ncoat 80) Treatment-D(Multigrow-80)
23
Important Features Summary
• Release Pattern, (shape, lag, lock off)
• Release Duration
• Differential Release N-P-K
• Temperature effect on Release
• Medium/Env. Cond. effect on Release
Additional points for consideration Additional points for consideration …………•• Microelements release (??)Microelements release (??)
•• Ammonium/Nitrate RatioAmmonium/Nitrate Ratio
•• Urea in the CRF (?)Urea in the CRF (?)
•• DegrabilityDegrability ((erodibilityerodibility)/Bio)/Bio--degrabilitydegrability of coatingof coating
24
When are “real” advantages of the CRF vs. “More Conventional” alternative expected?
Depends on factors such :
• Culturing Conditions: field (row, whole bulk, orchard), greenhouse (soil or detached media), potting media (small, large)
• Medium or soil type: Light? Heavy? CEC? OM?
• Leaching: (irrigation system, rain-fed,),
• Nutrient loss mechanisms
• Balanced/Imbalanced nutrient supply (availability problems)
• Environmnetal aspects
• pH, Ec, Eh constrains
• Special needs: e.g. ionic species combinations of
ammonium-nitrate,, ammonium-P,
Future Needs,,,,,,, or ImprovementsFuture Needs,,,,,,, or Improvements• Improved utilization of advanced technologies , development of new concepts for preparing more cost-effective CRFs
• Better Quantification of the agronomic and economic advantages
• Better assessment of expected benefits to the environment
• Development/Standardization of teststests for characterizing the release performance of SRF/CRFs to improve
-- useruser’’s decisions decision--making process, making process,
-- industrial quality control, industrial quality control,
-- assist legislation efforts.assist legislation efforts.
•• Utilization of mechanisticUtilization of mechanistic--mathematical mathematical models models for for predictingpredictingrelease of nutrients under laboratory and field conditions, and release of nutrients under laboratory and field conditions, and as a as a design tool for technologistsdesign tool for technologists
25
• Knowledge Integration to result inKnowledge Integration to result in: :
-- Better Use Instructions, Better Use Instructions,
-- Proper definitions of products Proper definitions of products
-- Improved/Relevant Performance InformationImproved/Relevant Performance Information
•• Users should be exposedUsers should be exposed to this knowledge to help them choose to this knowledge to help them choose SRF/SRF/CRFsCRFs professionally and on quantitative basisprofessionally and on quantitative basis
•• Agronomists, EnvironmentalistsAgronomists, Environmentalists should be should be exposedexposed to this to this knowledge to help them in better advising from both Agronomic knowledge to help them in better advising from both Agronomic (&economic) and Environmnetal points of view (&economic) and Environmnetal points of view
Thanks
26
Specific Points in Case of Questions
Urea hydrolysis increases soil pH Urea hydrolysis increases soil pH and losses of and losses of AmmoniaAmmonia
Nitrification Nitrification -- FIRST STEP FIRST STEP -- inhibited by:inhibited by:specific inhibitorsspecific inhibitors,
2NH+4 + 3 O2 => 2NO2NO--
22 + 2H+ 2H22O + 4 HO + 4 H++
((NitrosomonasNitrosomonas, , NitrosospiraNitrosospira))
2NO2NO--22 + O+ O2 2 => 2NO=> 2NO--
33 ((NitrobacterNitrobacter) () (high pH, NHhigh pH, NH33))
(NH2)2CO + HH++ + 2H2O => 2NH+4 + HCO-
3
(NH4)2CO3 NHNH33 + H2CO3
2NO2NO--22
High pH and AmmoniaHigh pH and Ammonia reduce activity of Nitrobacter and hence cause accumulation of “toxic” Nitrite during nitrification
27
Application of local high urea concentrations (e.g., basal placement) may cause:
1. Increased pH (due to formation of ammonium carbonate)
2. Increased ammonia levels due to the decomposition of the ammonium carbonate and high pH. In calcareous soils the effect is dramatically enhanced!!
3. In containers, with restricted volume – the local concentration of applied urea may be high (if not carefully applied) and may stimulate processes like in 1 and 2.
4. High pH and ammonia may damage roots and also affect the fast oxidation of nitrite into nitrate and cause accumulation of Toxic levels of Nitrite
Any system providing metered supply or controlled supply of urea has a great potential to reduce the above effects.
Too high (local) levels of applied urea may turn soon into Ammonium after urea the hydrolysis (~half a day).
Exposing plants to high loads of ammonium and particularly in containers (detached media) with restricted volume and neutral to slightly acidic pH, may induce further acidification due to nitrification or ammonium uptake by plants.
Metered or Controlled Supply of the ammoniacal source (including urea) is not expected to cause dramatic acidification, particularly when a balanced supply of urea/ammonium and nitrate is given.
28
Potting media
LEVEL 1 Fe in drainage (Melisa exp)
0.0
0.5
1.0
1.5
20 40 60 80 100 120 140 160days
Acc
umul
Fe
DSN 482 MEIO DSN 496 W/0 ME OSMOCOTLEVEL 2 Zn indr ainage
01234567
20 70 120 170days
Acu
umul
Zn
D SN 482 MEIO D SN 496 W/0 ME OSMOCOT
AccumulatiAccumulatingng FeFe with with leaching timeleaching time
Accumulatingccumulating ZnZn with with leaching timeleaching time
29