Mar 25 10 04:51p

DEPARTMENT OF

CROP AND

SOIL SCIENCES

Michigan Stale Universi!y

Plant and Sail SCiencesBldg.

East Lansing, MI

48B24-1325

517/355-0271

FAX: 517/353-5174

'II'WW.css.msu.edu

MSU is an aflirmalivc-iJElion,

equal-opportunily ins/itu/ion.

p. 1

MICHIGAN STATE

UNIVERSITY

March 25,2010

Joan Harrigan-Farrelly, Director, Antimicrobials Division

Office of Pesticide Programs

U.S, Environmental Protection Agency

2777 South Crystal Dr., One Potomac Yard

Arlington, Virginia 22202

Dear Ms. Harrigan-Farrelly:

My name is Donald Penner, and I am a professor in the Department of Crop and Soil

Sciences at Michigan State University. A copy of my Curriculum Vitae is attached for your

review. It has come to my attention that Nalco has relied on my published work in its March

18, 2010 submission to EPA. That reliance is quite misplaced, and I am writing to correct

the record.

I was recently asked by Ashland, Inc., for whom I have been retained as a consulting

expert in this matter, to review a copy of Nalcos March 18.2010 submission. I have also

reviewed Nalcos February 16,2010 presentation and remarks to EPA, along with other,

prior Nalco submissions to EPA regarding its two unregistered products. Nalcon 60620

(ammonium sulfate) and Nalcon 60615 (urea). In apparent support of its March 18,2010

submission, Nalco enclosed a 18 I-page "Appendix 2" that included:

• a copy of my own presentation, "Adjuvants: Principles and Uses," in its entirety; and

• the first page of a 1995 Weed Science article, "The Basis for the Hard-Water

Antagonism of Glyphosate Activity," of which I am a co-author.

Nalco has referenced my work in support of its proposition that its unregistered ammonium

sulfate and urea products are adjuvants. Nalco is wrong.

Nalcu's products are not adjuvants and arc not comparable to adjuvants.

Nalco states that its products are "no different than the vast number of other

separately added adjuvants that are used with the majority of pesticide products used across

industries." Nalco March 18,2010 Comments, at 12. This is incorrect.

In order to generate monochloramine and chlorourea, Nalcos ammonium sulfate and

urea products form covalent bonds with sodium hypochlorite. This is a well-known

chemical fact. By contrast, adjuvants never form covalent bonds with pesticides to produce

new active compounds. As such. Nalcos products arc not adjuvants. The fact that

ammonium sulfate is commonly used as an agricultural crop adjuvant has no bearing on

Nalcos usc of ammonium sulfate or urea in reaction with sodium hypochlorite in the pulp

and paper mill context.

Second, Nalcos chemical reaction process is not analogous to an agricultural

pesticide to which adjuvants maybe added in a tank mix. When used as an adjuvant with

glyphosate, for example, ammonium sulfate is added directly to the spray tank, not premixed with glyphosate, In fact, tank mixing is the first element of the definition of an

adjuvant. See ASTM E-159 (defining "adjuvant" to mean "a material added to a

tan I< mIX_ .•. _ . ")

Mar 25 10 04: 51p

DEPARTMENT DF

CROP AND

SOIL SCIENCES

Michigan Stale University

Plant and Soil Sciences Bldg.

East Lansing, MI

48824.1315

517/355.027

FAX: 517/353.5174

VNiw.css.msu.edu

MSU is an aftitmatíve-ction,

tQuakipportunily inslniilÎon.

p. 1

MICHIGAN STATE UNIVERSITY

March 25, 2010

Joan Harrigan-Farrelly, Director, Antimicrobials Division

Offce of Pesticide Programs

U.S. Environmental Protection Agency

2777 South Crystal Dr., Onc Potomac Yard

Arlington, Virginia 22202

Dear Ms. Harrigan-Farrelly:

My name is Donald Pcnner, and I am a professor in the Department of Crop and Soil Sciences at Michigan State University. A copy of my Curriculum Vitae is attached for your

review. It has comc to my attention that NaIco has relied on my published work in its March

18, 20 I 0 submission to EPA. That reliance is quitc misplaccd, and I am writing to corrcct

the record.

I was recently asked by Ashland, Inc., for whom I have been retained as a consulting

expert in this matter, to rcview a copy ofNaIco's March 18,2010 submission. I have also

reviewed Nalco's February 16,2010 presentation and remarks to EPA, along with other,

prior NaIco submissions to EPA regarding its two unregistered products, NaIcon 60620

(ammonium sulfate) and Nalcon 60615 (urea). In apparent support of its March 18,2010

submission, Nalco enclosed a i 8 I -page "Appendix 2" that included:

· a copy of my own presentation, "Adjuvants: Principles and Uses," in its entirety; and

. the first page of a 1995 Weed S'cience article, 'The Basis for the Hard-Water

Antagonism of Glyphosate Activity," of which I am a co-author.

NaIco has referenced my work in support of its proposition that its unregistered ammonium

sulfàte and urea products are adjuvants. Nalco is wrong.

Nalco's products are not adjuvants and are not comparable to adjuvants.

Nalco states that its products are "no diITerent than the vast number of other

separately added adjuvants that are used with the majority of pesticide products uscd across

industries." NaIco March i 8, 2010 Comments, at 12. This is incon:ect.

In order to generate monoehloramine and chlorourea, Nalco's ammonium sulfate and

urea products form covalent bonds with sodium hypochlorite. This is a well-known

chemical fàct. By contrast, adjuvants never form covalent bonds with pesticidcs to produce

new active compounds. As such, Nalco's products arc not adjuvants. The fact that

ammonium sulfate is commonly used as an agricultural crop adjuvant has no bearing on

Nalco's use of ammonium sulfàte or urea in reaction with sodium hypochlorite in the pulp

and paper mill context.

Second, Nalco's chemical reaction process is not analogous to an agricultural

pesticide to which adjuvants may be added in a tank mix. Whcn used as an adjuvant with

glyphosate, for example, ammonium sulfate is added directly to the spray tank, not premixed with glyphosatc. In fact, tank mixing is the first clemcnt of the dctìnition of an

adjuvant. See ASTM E- I 59 (defining "adjuvant" to mean "a matcrial addcd to a

tank mix. . .").
Mar 25 10 04:51p p.2

By contrast, Nalco's unregistered products are first chemically reacted with sodium

hypochlorite in a reaction vessel. This pre-reacted new chemical formulation is then

delivered to Nalco's customers' process waters. February 16,2010 Meeting Transcript, at

64. Chemically reacting two products is fundamentally different than tank mixing and this

fact alone independently precludes characterization ofNalcos products as adjuvants.

Nalcos attempted analogy is not only wrong but misleading.

* *

In all of Nalco's submissions that I have read, Na1co has erroneously referred to

ammonium sulfate and urea as adjuvants when used in Nalcos system to synthesize or

manufacture chloramines and chlorourea. As described above, Na1co is wrong on two

accounts.

·First, when used as an adjuvant with a pesticide, ammonium sulfate may form a

readily reversible salt link with the pesticide. However, as used by Nalco, ammonium

sulfate and urea become chemical substrates for the synthesis or manufacture of chlorarnines

and chlorourea. These are not reversible reactions but rather exothermic or heat (energy)

producing reactions that form covalent bonds. Adjuvants by definition do not undergo such

reactions.

Nalco is also wrong on a second account. The definition of an adjuvant is very clear:

adjuvants must be added into a tank mix (i.e., added to the applicator's spray tank for direct

application to the soil or plants in the field). Nalco does not add its ammonium sulfate or

urea products to a tank mix. Instead, Nalco adds its amrnoni um sulfate and urea products

into a reaction tank.

I appreciate this opportunity to address Nalcos entirely misplaced reliance on my

published work. Nalcos submission includes numerous technical errors that I am not

addressing here, but understand will be separately addressed by Ashland in subsequent

correspondence to EPA.

I hope that the Agency finds this information helpful, Please let me know if you

have questions about any aspect of this letter.

Sincerel s. <~.-'."-~»"~'.-'..~~

(

~ ./ I ) ". .//

~~eY ~.~ e-5--(

Donald Penner, Ph.D.

Professor, Dept. of Crop and Soil Sciences

Michigan State University

DPldcm

Mar 25 10 04:51p p.2

By contrast, Naleo's unregistcred products are first chemically reacted with sodium

hypochlorite in a reaction vesseL This pre-reactcd new chemical formulation is then

delivered to Naleo's customers' process watcrs. Fcbruary 16,2010 Meeting Transcript, at

64. Chemically reacting two products is fundamcntally different than tank mixing and this

fact alone independently precludes characterization ofNalco's products as adjuvants.

Nalco's attemptcd analogy is not only wrong but mislcading.

* * *

In all ofNaleo's submissions that I have read, Nalco has erroneously referred to

ammonium sulfate and urea as adjuvants whcn used in Naleo's system to synthcsize or

manufacture chloramines and chlorourea. As describcd abovc, Na1co is wrong on two

accounts,

'First, when used as an adjuvant with a pesticide, ammonium sulfate may lorm a

readily reversible salt link with the pesticide. However, as used by Naleo, ammonium

sultàtc and urea bccome chemical substrates for thc synthesis or manufacturc of chloramines

and chlorourea. These are not reversiblc rcactions but rather exothermic or heat (cnergy)

producing reactions that form covalcnt bonds. Adjuvants by definition do not undergo such

reactions.

Na1co is also wrong on a second account. The definition of an adjuvant is very clear:

adjuvants must be added into a tank mix (i.e., added to the applicator's spray tank for direct

application to the soil or plants in the field). Naleo does not add its ammonium sulfate or

urca products to a tank mix. Instead, Nalco adds its ammoni um sulJàte and urea products

into a reaction tanc

1 appreciatc this opportunity to address Naleo's entirely misplaced reliance on my

publishcd work. Naleo' s submission includes numerous technical errors that i am not

addressing here, but understand wil be scparately addrcssed by Ashland in subsequent

correspondcnce to EPA.

I hope that the Agency finds this infonnation helpfuL Please let mc know if you

have questions about any aspect of this letter.

Sincerely, .;_.__........""

~.-e/ ~~~'-( ) )"',.../ ("" ./

Donald Penner, Ph.D,

Professor, Dept. of Crop and Soil Sciences

Michigan State University

DPldcm