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 anaflirmalivc-iJElion, equal-opportunily ins/itu/ion. p. 1



## MICHIGAN STATE
UNIVERSITY
March 25,2010

Joan Harrigan-Farrelly, Director, Antimicrobials Division Office ofPesticide 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 I . ") tan < 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 withglyphosate, 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 

### ormanufacture 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