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Agricultural Spray Adjuvant Technology

-Sorting Out the Adjuvant PuzzleSpray


Modifier
Adjuvants

Activator
Adjuvants

?
Utility
Modifier
Adjuvants

Utility
Products

Steve Barnhart Agriliance Regional Agronomist

Adjuvant Confusion!
Compendium of Herbicide Adjuvants
(Southern Illinois University 1/02)
Lists 36 different companies selling various types
of adjuvants. There are more!
Lists 440 different adjuvants. There are many
more!

What is an Adjuvant?
An adjuvant is any additive used in
conjunction with a pesticide to increase
biological activity and/or to modify various
physical properties of a spray solution.

Importance of Adjuvants
Spray applications are affected by many physical variables

Pesticide Stability
Solubility
Compatibility
Foaming
Suspension
Surface Tension

Droplet Size
Drift
Volatilization
Coverage
Adherence
Penetration

Adjuvants play a key role in controlling these variables

Adjuvants Are Classified Into


Four Categories
Activator Adjuvants
Enhance Pesticide Performance
Surfactants, Crop Oil Concentrates, Methylated Seed Oils, Fertilizer
Solutions, Penetrants

Spray Modifier Adjuvants


Affects Physical Properties Of Spray Solutions
Stickers, Deposition Aids, Drift Retardants, Evaporation Aids

Utility Modifier Adjuvants


Minimize Handling and Application Problems
Compatibility Agents, Buffering Agents, Defoamers, Anti-foams

Utility Products
Minimize Application Problems
Foam Markers, Tank Cleaners

Adjuvants Types
Surfactants (also called spreaders or wetting agents)
An adjuvant that reduces surface surface tension between
the spray solution droplets and the pest targets surface,
thus providing greater coverage.

Crop Oil Concentrates


A combination of oil (petroleum or vegetable) and
surfactants/emulsifiers. Crop oil concentrates act as
penetrants, stickers, spreaders (limited), humectants, etc.

Methylated or Ethylated Seed Oils


An emulsified methylated or ethylated seed oil. Act as
penetrants, spreaders (limited), humectants, etc.

Adjuvants Types - cont.


Penetrators
Enhance uptake of pesticides through target pests
surfaces.

Spreader/Stickers/Extenders
Combine spreading and adhesive qualities to improve
coverage and retention of pesticide.

Water Conditioning Agents


Reduce the antagonistic affects of impurities (Ca, Mg, Mn,
Fe, etc.) found in water carrier. Potentially greater
pesticide efficacy results.

Adjuvants Types - cont.


Humectants
Increase the drying time of spray solutions which provides
greater time for the pesticide to enter the targets surface.
Used during high temperature, low humidity and low
spray volume situations.

Deposition Aid
Reduces the amount of fine spray particles that carry
pesticide out of target areas. (polyacrylimides,
encapsulators, others)
Reduces evaporation of the spray droplet; Used during
high temperature, low humidity and low spray volume
situations.

Drift Control Agents


Reduces the amount of fine spray particles that carry
pesticide out of target areas. (polyacrylimides,
encapsulators, others)

Adjuvants Types - cont.


Compatibility Agents
Compounds that aid in stability and dispersion of various
pesticide formulations and spray carrier mixtures.

Buffer Agents/Acidifiers
Generally lower the pH of the spray solution and reduce
rapid changes in pH either higher or lower.
Reduces the degradation of pesticides by chemical hydrolysis.
Dimate, Malathion, Sevin, etc.

Some buffers are used to raise the solution pH for greater


herbicide solubility (Example: micro-rate herbicide
applications of Betamix + Upbeet + Stinger on sugar
beets)

Colorants
Used to alter the color of spray solutions.

Adjuvants Types - cont.


Suspension Agents
Extend the period of time a pesticide will remain in
suspension and if agitation is stopped for a time, upon
agitation they aid in re-suspension of the mixture

Defoaming Agents
Suppresses foam of various pesticide solutions, aids in
filling tanks

Foaming Agents
Used for marking swath width.

Who Regulates Adjuvants?


Basically the industry is self-regulated
Formulations are considered trade secrets
not disclosed to the public

Quality Issues
Lack of consistent regulation
Confusion and Opportunity
Yes, there is a difference among adjuvants - All
adjuvants are NOT created equal.
(Dr. Richard K. Zollinger-NDSU)

Value of Spray Additives


What

value does the adjuvant bring?

Without adjuvants many herbicides would not perform!

Value of Spray Additives


(Accent, Pursuit, Spirit, etc.)

Activator Adjuvants

Activator Adjuvants are Specific


Why More Than One Activator Adjuvant?

Herbicide Specific
Work well with some herbicides, but not all!
Non-ionic surfactants work well with Roundup while
oil based surfactants inhibit Roundup performance.

Herbicides Differ
Water soluble versus oil soluble
Contact versus Systemic

Activator Adjuvants are Specific


Why More Than One Activator Adjuvant?

Weed Specific
Work well with some, but not all weeds!
Oil based surfactants are generally more effective for
annual grasses and lambsquarters which have waxy
cuticles.

Cuticle (wax type and thickness)


Leaf Surface (hairiness)
Leaf Angle (vertical or flat)

Activator Adjuvants are Specific


Why More Than One Activator Adjuvant?

Environmentally Specific
Soil moisture, temperature, humidity
Non-ionic surfactants provide better crop tolerance
during high humidity conditions than do oil based
adjuvants. Meanwhile, methylated seed oil based
adjuvants provide better control during very dry
conditions compared to non-ionic surfactants or
conventional crop oil concentrates.

Surfactants

Adjuvant vs. Surfactant


The terms Adjuvant and Surfactant are
often used interchangeably in our
daily spray discussions.
Surfactants are actually a specific
type of adjuvant.
All surfactants are adjuvants, but not
all adjuvants are surfactants.

Surfactants
Form a bridge between unlike chemicals
that dont readily mix
water and oil
water and the wax on a leaf surface

Lower the surface tension of spray droplets


Allow for more complete spray coverage
and sticking on plant surfaces
May contain fatty acids to further improve
herbicide retention and penetration

Surfactants

Without Surfactant

With Surfactant

Surfactants

Complex long chain polar molecules


Composed of alcohols and fatty acids
Lipophilic tail and hydrophilic head
Three general groups
Non-ionic, anionic, cationic

Surfactant Activity
Structure
Hydrophilic

Activity
Oil droplet

Lipophilic
Water

Charged Surfactants
(Anionic, Cationic and Amphoteric)
Anionic surfactants have a negative charge and
have limited compatibility with pesticides.
Cationic surfactants have a positive charge and
have limited compatibility with pesticides.
Amphoteric surfactants have both charges and
may vary their charge with changes in pH.
Charged adjuvants may be more effective with
salts (glyphosate, 2,4-D amine, etc.)

Uncharged Surfactants
(Non-Ionic)
Uncharged or non-ionic surfactants are
compatible with most pesticides
There is a wide variety of non-ionic chemistry
Some inert chemicals are considered to be
adjuvants as they reduce surface tension. These
chemicals (butanol, diethylene glycol, etc.) have
little or no biological activity.

Surfactants
Typical ingredients of surfactants

Surfactant active ingredient


Fatty acids
Alcohols
Water
Polyethylene glycols

Common Active Ingredients of


Nonionic Surfactants
Alcohol Ethoxylates - best biologically, very expensive
Nonyl Phenol Ethoxylates - good biologically, in 95% of
todays surfactants, being looked at by EPA as a endocrine
disrupter.
Alkyl Octylphenol Ethoxylates - good biologically, expensive
Alkyl Polysaccharides - good biologically, new chemistry,
corn starch base, mixes well with AMS
Urea Clathrates - good biologically, dry alcohol ethoxylate,
expensive
Fatty Acid Ethoxylates - good biologically, soybean base,
may replace phenol ethoxylates

Common Active Ingredients of


Nonionic Surfactants - cont.
Tallow Amine Ethoxyalates - good biologically, used in
Roundup Ultra, partially ties up free ions that can be
antagonistic to the glyphosate molecule.
Phosphate Esters - good biologically, also used in Roundup
Ultra, partially ties up free ions that can be antagonistic to
the glyphosate molecule.
Fatty Acids - usually tree oils, biologically active
EO/PO Block Copolymers (organosilicones) - expensive
Siloxanes (organosilicones) - expensive

Other Ingredients Found In


Surfactants
Water
Alcohols (IPA-isopropyl alcohol)
for storageability

Polyethylene Glycol
used mainly as a filler, no biological activity

Diethylene Glycol
used mainly as a filler, no biological activity

Diols

Adjuvant Labels Can Be Confusing

Nonyl phenol ethoxylate


Alkyl phenol ethoxylate
Poly ethoxylates
Alkyl aryl polyethoxylates
Alkyl polyoxyethylene
Polyethoxylated derivatives

These terms can all mean the same thing and may
refer to the same constituent.

Physical Properties Used To


Compare and Measure Surfactants

Surfactant Load
HLB - Hydrophilic:Lipophilic Balance
Contact Angle
Draves Wetting
Surface Tension

Surfactant Load
Is a measure of the exact content of true
non-ionic surfactants in a particular
product.
Expressed as percentage.
A product with a true surfactant load of
< 50% may not meet the requirement for
an adjuvant as specified by some
pesticide manufacturers.

Comparison Of Active Ingredients In Typical


Surfactants
- Performance Will Not Always Be The Same-

60% Alkyl Aryl


Ethoxylate
20% Fatty Acids
3% IPA
7% Polyethylene
Glycol
10% Water
90/10 Surfactant ?
(80/10)

50% Alkyl Aryl


Ethoxylate
20% Phosphate Ester
10% Diol
5% IPA
15% Water
80/20 Surfactant ?
(70/30)

Comparison Of Active Ingredients In Typical


Surfactants
- Performance Will Not Always Be The Same

82% Nonyl phenol


Ethoxylate
7.9% Fatty Acids
0.1% IPA

45% Nonyl phenol


Ethoxylate
10% Fatty acid esters
30% Glycols
5% IPA

10% Water
10% Water
90/10 Surfactant ?
(89.9/10.1)

90/10 Surfactant ?
(55/45)

HLB
(Hydrophilic:Lipophilic Balance)
HLB is the relationship between the nature
of the hydrophilic and lipophilic portions
of the surfactant molecule. The range of
HLB is 1-20. The higher the value the
more hydrophilic the surfactant. Most
effective surfactants have a value between
10-18. The HLB is not measured, it is
calculated. Research has shown that there
is significant herbicide/HLB/weed
interactions

HLB and Herbicide/Surfactant


Solubility
Herbicides
Accent, Assure II,
Atrazine,Beacon,
Classic, Fusilade DX,
Harmony GT, Poast, etc.
Oil Soluble
(Lipophilic)

10
Prime Oil
Destiny
Superb HC

Sterling/Banvel, Blazer,
Galaxy, Gramoxone,
Liberty, Pursuit, Reflex,
Cornerstone/Roundup/Touchdown,
etc.
Soluble
20 Water
(Hydrophilic)
Preference
Activate Plus
Silkin

Surfactants

Contact Angle
This is a profile measurement of a drop
of water in contact with a solid surface.
When a surfactant is added to water the
surface tension of the solution is reduced
and the spreads out over a greater area.
This flatter droplet has a lower contact
angle reading. A water droplet has a
contact angle of 93 degrees. A superior
wetter will have a contact angle of 45
degrees or less.

CONTACT ANGLE

Contact angle (CA) is a profile measurement of a drop of water in contact


with a solid surface. When a surfactant (wetting agent) is introduced into the
solution, the surface tension is reduced and the water droplet becomes flatter.
The lower the CA produced by the surfactant,
the greater the spreading and coverage properties
of that spray solution.
Water has a CA of 93 degrees. A typical
surfactant influences the contact angle
30-45 degrees, and a super wetter surfactant
can reduce contact angles to 15 degrees or less.

Contact Angle - cont.

Water
Water + Preference (NIS)
Water + Activate Plus (NIS)
Water + Silkin (silicone NIS)
Water + Prime Oil (COC)
Water + Destiny (MSO)

940
380
350
240
580
590

Crop Oil Concentrates and Methylated Seed Oils have


surfactants in their formulation, but do not as effectively
reduce contact angles like true surfactants.

Draves Wetting
This is a test to measure the time in
seconds it takes to completely wet a
woven cotton skein. A superior wetter
will require less than 20 seconds for
wetting to occur. The lower the score in
this test the better wetting characteristics
the product has.

DRAVES WETTING TEST


Draves wetting correlates to how well a
pesticide solution will wet and spread on a
solid surface (i.e.: plant, weed, etc.). This
standard method test measures the time
(seconds) it take to wet a woven cotton
thread.

A superior wetting agent at a 0.25% v/v


concentration will require less than 20
seconds for wetting to occur. (Water
measures at >300 seconds.)

The lower the score on this test the better


wetting characteristics the product has.

Draves Wetting - cont.

Water
Water + Preference (NIS)
Water + Activate Plus (NIS)
Water + Silkin (silicone NIS)
Water + Prime Oil (COC)
Water + Destiny (MSO)

Seconds

>300
16
11
2
>300
>180

Crop Oil Concentrates and Methylated Seed Oils have


surfactants in their formulation, but do not have the
wetting characteristics of true surfactants.

Surface Tension
Surface tension is a condition that exists
at the free surface of a liquid. The
surface tension test measures the force
required to pull a floating ring off of the
surface of a liquid. This force is
measured in dynes/cm. Water has a
value of 74 while typical spreaders will
have a value of 30-50. Super wetters will
be 10-30.

SURFACE
TENSION
Surface tension is a condition that exists at the free surface of a solution.
The dynes per centimeter (dynes/cm) measurement in the test determines
the amount of force required to pull a floating ring off the surface of the
solution. The higher the dynes/cm, the more force is applied.
Since surfactants affect tension, the lower the
dynes/cm the better the coverage. Conversely,
the higher the dynes/cm of the solution, the
greater the impact on coverage.
The surface tension of water is approximately
74 dynes/cm. Typical wetting agents will reduce
surface tension to 30-50 dynes/cm, while
super wetters reduce this figure to 10-30
dynes/cm.

Surface Tension - cont.


Dynes/Cm

Water
Water + Preference (NIS)
Water + Activate Plus (NIS)
Water + Silkin (silicone NIS)
Water + Prime Oil (COC)
Water + Destiny (MSO)

73
35
32
27
36
52

Water Conditioning Agents

Water Conditioning Agents


Water Conditioning Agents
Reduce antagonism from hard water cations
(Ca++, Mg++, Fe++, K+, Na+, ZN++)
Free salts in water attach to sulfate ions

In some cases can help overcome antagonism


between certain herbicides
Can lower pH and buffer spray solution
Reduces breakdown of certain pesticides due a
process called Alkaline Hydrolysis.

Increase penetration of herbicide into plant cell


membranes through Ion-trapping

Common Active Ingredients Terms


in Water Conditioner Products

Alkylpolyglucoside (corn syrup)


Alkylpolyglycoside
Alkylpolyoxyethylene glycol
Ammonium Salts
Ammonium Sulfate
Ammonium Nitrate
Ammonium alkyl aryl
sulfanates
Ammonium polyacrylates
Citrophosphate

Glycerol acid
Hydroxy carboxylic acid
Phosphate esters
Phosphoric Acid
Plycarboxylic acid
Polyacrylic acid
Propionic acid
Sulphates
Urea
UAN

Nitrogen Fertilizers Role as a Water


Conditioner

Nitrogen Fertilizers (NH4)


Weeds which respond to the addition of UAN
solutions or AMS.
Foxtails, johnsongrass, quackgrass, woolly cupgrass,
velvetleaf, cocklebur, sunflower, P. smartweed, v. mallow,
devilsclaw, lambsquarters and w. mustard.

Herbicides which are enhanced by nitrogen

2,4-D Amine
MCPA Amine

Nitrogen Fertilizers (NH4)


Herbicides where antagonism from mineral salts in
the water can affect their performance:

Roundup, Cornerstone, etc. (glyphostate)


Liberty, Liberty ATZ (glufosinate)
Banvel, Clarity, Distinct, Sterling (dicamba)
2-4-D amine
MCPA amine

Herbicides where UAN does NOT overcome the


antagonism of mineral salts in the water; AMS
must be used:
Roundup, Cornerstone, etc. (glyphostate)
Liberty, Liberty ATZ (glufosinate)

Nitrogen Fertilizers (NH4)


Even in the absence of mineral salt
impurities in the water, weed
control of certain weeds is enhanced
by the addition of UAN solutions or
AMS.

Concerns with
AMS/Polyglycolether Products
Ammoniated Salt Adjuvants
Advertised as AMS substitutes
Do not meet label recommendations for NIS or AMS
Generally NOT approved

Value of Spray Additives

SPRAY GRADE
AMMONIUM
SULFATE.
AMMONIUM
SULFATE
SOLUTION
PREMIXES

AMS AFFECT ON ROUNDUP


ULTRA
University of Minnesota- Waseca
100
95
90
85
80
75
70
65
60
55
50

HARD WATER
WATER pH 8.2
DEIONIZED
WATER
WATER 800
PPM CA

RRPW

COLQ

VELE

800 PPM CA +
AMS

Roundup/Adjuvant/AMS Trial
% Barnyardgrass Control (17 DAT)
100
90
80
70

W/AMS
WO/AMS

60
50
40
30
Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. No
1
2
3
4
5
6
7
8
9
10
11 Adj.

Adjuvant
Roundup Original Rate = 16 oz/a; LSD (.10) = 2; Adjuvants rates varied by product

Roundup/Adjuvant/AMS Trial
% Waterhemp Control (17 DAT)
100
90
80
70

W AMS
W/O AMS

60
50
40
30
Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. No
1
2
3
4
5
6
7
8
9
10
11 Adj.

Adjuvant
Roundup Original Rate = 16 oz/a; LSD (.10) = 13.8; Adjuvants rates varied by product

Roundup/Adjuvant/AMS Trial
% Velvetleaf Control (17 DAT)
100
90
80

W AMS
W/O AMS

70
60
50
Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. No
1
2
3
4
5
6
7
8
9
10
11 Adj.

Adjuvant
Roundup Original Rate = 16 oz/a; LSD (.10) = 11; Adjuvants rates varied by product

Roundup/Adjuvant/AMS Trial
% Foxtail Control (17 DAT)
100
90
80
70

W/AMS
WO/AMS

60
50
40
30
Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. Adj. No
1
2
3
4
5
6
7
8
9
10
11 Adj.

Adjuvant
Roundup Original Rate = 16 oz/a; LSD (.10) = 2; Adjuvants rates varied by product

2003 Dumont Answer Plot

Crop Oil Concentrates


Non-phytotoxic oils + emulsifiers (surfactants)
Generally 80-95% oil and 5-20% emulsifier
Petroleum based or vegetable in origin

Surfactant portion aids in spreading/wetting


Increase spray retention/prolong drying time
Increase penetration through the leaf cuticle
More effective than NIS adjuvants in low
humidity, and on drought stressed or larger
weeds

Accent/Beacon Adjuvant Trial


Kansas State University
% Shattercane Control (87 DAT)
100
90
80
70
60
50
40
30
20
10
0
Accent+Prime Oil
(1% v/v)

Accent

Beacon + Prime Oil


(1 v/v)

Beacon

Accent Rate = 0.168oz/a; Beacon Rate = 0.19 oz/a; LSD (.05) = 14

Methylated Seed Oil (MSO)


-Typical Ingredients Oils

85-92%

Seed Oil + methanol

Emulsifier/Surfactants 8-15%

Akyl Aryl Ethoxylates


Castor Oil Ethoxylates
Polyethylene glycol esters
etc.

Beacon/Accent Adjuvant Trial


% Velvetleaf Control (19 DAT)
100
90
80
70
60
50
Activate Plus
+ UAN

Prime
Oil+UAN

Destiny+UAN

Only UAN

Beacon/Accent Rate = 0.38 oz/a + 0.33 oz/a;


Activate Plus = 0.25% v/v; Prime Oil and Destiny = 2 pt/a; UAN = 2 qt/a

No Additives
LSD (.10) = 5

Minimizing Spray Drift

Best Spray Management Practices To


Minimize Spray Drift Issues
Use good judgement
Consider wind speed and direction
Consider climatic conditions

Select the proper equipment


Manage spray droplet size
Nozzle type, size & pressure

Keep boom height low

Use a drift control/deposition agent


Maximize spray deposition
Reduce spray drift
It is necessary to consider all of the above in order to do the best
you can to reduce drift and maximize herbicide performance.

Drift Control Agents


Encapsulators
Suspends small capsules(150-180 Micron size) of
pesticide in the spray solution significantly reducing the
amount of pesticide contained in drift susceptible fines.
Placement & Placement Pro Pak
Do not affect spray droplet size

Thickeners or Viscosity Modifiers


Increases the viscosity of spray solutions which in turn
increases droplet size and reduces the amount of drift
susceptible fines.
Corral Poly, Corral AMS Dry, Arrow four, AG1040
Do enlarge spray droplet size

Neither a Thickener or an Encapsulator


InterLock

Can Drift Control / Deposition Aids


Improve Pesticide Efficacy?

Yes !

Can Drift Control / Deposition Aids Improve Pesticide Efficacy?


Yes !
European Corn Borer Damage as Influenced by Adjuvants
Treatment

Rate

% Visual Damage

% Damaged Stalks

----

73

67

4 oz/a

37

33

Pounce +
Preference

4 oz/a
2 pt/100 g

30

23

Pounce +
Placement

4 oz/a
4 oz/a

27

23

Pounce +
Placement +
Preference

4 oz/a
4 oz/a
2 pt/100 g

23

17

Pounce +
Rivet

4 oz/a
2 qt/100 g

30

23

7.6

9.5

None
Pounce

LSD P=(0.05)

Source: Plant Research Service Bethel, Missouri

Cotton Defoliation: 8/30/02


Dropp .2 + Finish 16 0z/Ac + Class Act Next
Gen. 2.5 Gal/200 + 4 0z/Ac Placement

PLACEMENT!

NO PLACEMENT!

While the previous pictures show


defoliation of cotton. Could this same
canopy penetration enhancement carryover to better control of such soybean
insects as soybean aphids or spider mites
which tend to colonize under leaves and
down in the crop canopy? How about
improved soybean rust control?
Probably!

InterLock 2004 Canopy Penetration Trial


(Desert Air Ag Mud Lake, Idaho)
Treatment Average:

Droplets/cm2

Untreated

12.8

InterLock + Preference (4 oz/a +1 pt/100 g)

20.8

Canopy Location Average:

Droplets/cm2

Upper Untreated

16.6

Upper - InterLock + Preference (4 oz/a +1 pt/100 g)

22.5

Middle Untreated

12.0

Middle - InterLock + Preference (4 oz/a +1 pt/100 g)

22.3

Lower - Untreated

9.7

Lower InterLock + Preference (4 oz/a +1 pt/100 g)

17.6

Amistar (4 oz/a) fungicide


Airtractor 502 airplane, CP flat fan nozzles, 5 g/a at 120-140 mph.
Water sensitive paper used to evaluate and collect spray.

% Improvement
63%
% Improvement
36%

86%

81%

InterLock + Preference (4oz/a + 1 pt/100 g)

Upper Canopy 22.5 droplets/cm2

Middle Canopy 27.2 droplets/cm2

Lower Canopy 14.0 droplets/cm2


Untreated
Upper Canopy 12.25 droplets/cm2
Middle Canopy 10.75 droplets/cm2
8.25 droplets/cm2
Lower Canopy
InterLock 2004 Canopy Penetration Trial

InterLock for Soybean Rust

2004 I Brink ,South Africa


InterLock = deposition aid at 4 oz/a
Activate Plus = non-ionic surfactant at 1 pt/100 g.

Interactions Which Affect


Postemergence Performance
Adjuvants

Plants

Herbicide

Environment

Selecting the Best Adjuvant or


Adjuvant Combinations

Adverse

Spray
Conditions

Good

Oils and Fertilizers


Methylated Seed Oils
Crop Oil Concentrates
Surfactants and Fertilizers
Nitrogen Fertilizers
Silicone Surfactants
Non-Ionic Surfactants

High
Weed
Control
and/or
Crop
Injury
Low

Thank You!
Steve Barnhart