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November 27,2014

CONTAINS NO CONFIDENTIAL

BUSINESS INFORMATION

Bv Fedetal Exuress

-

OPPT Docurnent Control Office

U.S. Environmental Protection Agency

EPA East Building

Room 86428

12}l Constitution Ave., NW

Washington, DC 20004

Attn.: TSCA Section 4

Re: Significant Technical Issue Encounteted with Testing Conducted by Univar

USA undet the TSCA Section 4 Test Rule on the Testing of Certain lligh

Production Volume Chemicals: Second Grcup of Chemicals

D-erythto-Hex-2-enonic acid, .gamma.-lactone, monosodium salt

cAS RN 6381-77-7

(Sodium erythotbate)

Docket Identification No. EPA-HQ-OPPT-2007-0531.; 40 CFR 799.5087

Dear Sir/Madam:

On behalf of its client, Univar USA Inc. flJnivar or the Comp arry), Greenwich Chemical

Consulting, Inc. (Gteenwich Chemical Consulting) submits to the U.S. Environmental

Ptotection Agency EPA or the Agency) information on ^ significant technical issue

encountered during testing conducted on the chemical substaflce, D-erythto-hex-2-enonic

acid, .gamma.-lactone, monosodium salt [CAS RI{ 6381 -77-Tlwhich is curently subject to a
'"*T,1i','^l[3",i,T5f-ffi '#

U.S. Environmental Protection Agency

November 21,201"4

Page 2

Toxic Substances Conttol Act GSCA) Section 4 test ruIe.1 Specifically, as pafi of the

labotatory's method development urork ahead of the required ecotoxicity testing, it was

determined that the test material undergoes rapid hydrolysis when placed in water. The

material was found to be unstable in water and hydrolysis occurs in a matter of a few hours.

Through this lettet, Univat requests technical guidance from EPA on how to proceed with

this testing.

I. General Bachground

As a matter of background, this test rule addresses 1,9 hlgh production volume (HPU

chemicals that went unsponsored under the Agency's voluntary HPV Chemical Challenge

Ptogtam. One of the 19 chemicals identified in the rule is D-erythro-hex-2-enonic acid,

.gamma.-lactone, monosodium salt which is identified herein as sodium erythorbate. The rule

tequires manufacturers and importers of these HPV chemicals, including sodium erythorbate,

to conduct testing to obain screening level data for human health effects, environmental

effects, chemical fate, and physical/ chemical prop erties.

The Agency has issued this test rule under its TSCA Section +(a)(t)@) authority based on its

determination that HPV compounds, includrng sodium erythorbate, are "produced in

substantial quantities; there is or may be substantial human exposure to them; existing data are

insufficient to deterrnine or ptedict theit health and environmental effects; and testing is

necessary to develop such data."z The final rule identifi.es the following studies and test

ptotocols ofl sodium erythorbate:

n-Octanol/Watet Partition Coefficient [40 CFR 799.6755, ASTM E 11 47-92, or 40

cFR 799.67s61

Ready Biodegradation3

Aquatic Toxicity Tes tinga:

Acute toxicity to fi.sh [ASTM E 729-96]

Acute toxicity to Daphnza [ASTM E 729-96)

Toxicity to plants (rlgrE [ASTM 8 1,21,8-04'1]

Har1an Labotatories Ltd. (Hatlan Laboratories) was selected to conduct all of these tests. Also,

Greenwich Chemical Cons"lti"g is serving as the study monitor for this testing.

rlanuarv 7.2011:76 Fed. Res. 1067.

2 Id. at 1069.

3 The test rule identifies six ISO protocols and one ASTX,{ standard for biodegradation testing.

selection depends on the test substance's physical and chemical properties.

I Because the n-octanol/water partition coefficient is expected to be signif,rcantly less than 4.2

compound's high water solubility, Test Group 1 is expected to apply.

The protocol

based on the
CONTAINS NO CONFIDENTIAL

BUSINESS INFORMATION

U.S. Environmental Protection Agency

November 21,,201,4

Page 3

II. Significant Technical Issue during Method Development Work Ahead of Ecotoxicity

Testing

-

Harlan Laborator{es recendy advised Greenwich Chemical Consulting that in the method

development work pteceding ecotoxicity testing, it was determined that the sodium

erythorbate rapidly hydrolyzes in water. Specifically, the laboratory reports that a 100 mg/L

aqueous solution undergoes 600lo hydrolysis withrn three (3) hours. In addidon, a 10 mg/L

aqueous solution undergoes 100o/o hydrolysis within this same time period. See attached file

containing th. report from Harlan Laboratodes describing this technical issue. As discussed

in the report, the laboratory undettook addrtional efforts to stabilize the matedal in water.

However, nofle of these efforts were successfirl.

A conference call between the labotatory and Greenwich Chernical Consulting was

subsequently held to discuss this issue. During the call the laboratory indeed confrmed that it

was not possible to suffi.ciently stabilize the test item in water to enable the quantitative analysis

to be petfotmed dudng the planned ecotoxicity testing. Moreover, Flarlan Laboratory had no

suggestiofls oll how to stabilize the material in water despite its sigruficant experience in

conducting ecotoxicity testing.

Thetefote, through this lettet, we are requestrng technical guidance from the Agency on how

to ptoceed on this mattet. In the absence of EPA being able to provide such technical

Euidance, Univar teguests that EPA give ever,v consideration to eliminating the three (3)

ecotoxiciW studies ftom the tests reouired under the TSCA Section 4 test rule. This is because

there is no practical reason or scientific justification for measuring the ecotoxicity of a

substance that immediately hydrolyzes in water.

III. Likelv Extension Reouest

Based on the significant technical issue described above and in the case where this issue can

be resolved and the three (3) ecotoxicity tests petformed, it is highly likely that an extension

request beyond the Febru^ry 11,,2015 deadhne will be needed. Under this scenaflo, Greenwich

Chemical Consulting will subrnit such an extension request to EPA on behalf of Univar.
CONTAINS NO CONFIDENTIAL

BUSINESS INFORMATION

U.S. Environmental Protecdon Agency

November 2'1.,201,4

Page 4

Univar thanks the Agency fot its considerarion in this matter. For all questions, comments,

and determinatiofls coflcerning this matter, please use the contact information given below.

Mr. John V. Massingale

Greenwich Chemical Consulting, Inc.

3300 PGA Boulevard, Suite 635

Palm Beach Gardens, F'L 33410

Telephone: (561) 578-81 10

Facsirnile: (561) 578-81 20

E-mail: i oh n(r},urc.ci. com

Sincerely,

John V. Massingale

Principal

Ms. I{. Gilje - Univar

Ms. S. Lilley - Univar

Mt.J. Schaeffer - EPA
Study Numbert 414fr1176

Summary of method development for d-erythro-hex-2-enoic acid, gamma lactone, monosodium

salt.

Figure l: Chemical structure of the test item

It was suspected that given the sffucture of the test item that it was likely to undergo rapid hydrolysis

when exposed to aqueous media.

The test item was initial dissolved in RO water and injected on a Cl8 column looking at245 nm. It

was run isocratic at 50/50 0.1% formic acid in RO&IeCN. The peak was not retained, a gradient

starting at 95% aqueous to 100% organic and the peak was still not retained. Other columns were

tested however no retention was possible.

The test item solution was scanned in positive mode on a mass spectrometer and a response at 199

m/z was seen, this correlates to the sodium adduct of the test item. After 24 hours another scan was

carried out of the test item solution and the 199 ion was not seen, a fresh standard was prepared and

the 199 ion could be seen. No other ions were seen in the old standard that were not present in blank

spectrum.

A UV scan between 200 to 400 nm was carried out on both the fresh and the old standard. A large

response was seen at?45 nm for the fresh standard however the response had significant decreased in

the old standard.

This data correlates with the idea that the test item is rapidly hydrolysing and the standard solution is

not stable.

The test item was found to be soluble in Methanol, standards were prepare in at 100 and l0 mElL.

These were then analysed by LC-UV and after - 3 hours the response for the 100 mg/L standard was

approximately 40Yo of the original response, after the same period of time the 10 milL standard was

undetectable.

This implies that the test item is not stable in MeOH. Other solvents were tested to see if it was

possible to obtain a solution which was stable. It was seen that the test item was insoluble in

Acetonitrile, THF, Hexane, MTBE and DCM.

As it was insoluble in other solvents, an attempt was made to stabilise the test item in a water solution

by acidiffing to the solution with 57o acetic acid, the UV response dropped by approximately I 1%

over 2.75 hours. This is still not acceptable for a reproducible analysis. A further attempt was made by

the addition of phosphoric acid (3%). A 100 milL standard was prepared in this phosphoric acid

solution, this was then analysed by LC-UV, the response dropped by ll% over 90 minutes and was

approximately 52Vo of the original response after 4 hours. Therefore the test item is not stable in an

acidic solution.

Due to the fact that no way of stabilising the test item in solution could be found and that no response

either by mass specfometry or UV detection could be identified for a degradation product it is not

possible to analyse for the presence of this test item in the ecotoxicology analysis samples.

+

Na
FedEx Ship Manager API Label Page

From: (561) 578-8110

JOHN V. MASSINGALE

Odgin lD: PBIA

GREENWCH CHEMICAL CONSULTING, INC.

33OO PGA BLVD

SUrIE 635

PALM BEACH GARDENS, FL 33410

SHIP TO: {202} 564-8330

OPPT Document Control Office

U.S. Environmental Protection Agenc

Room E6428; EPA East Bldg.

1201 Constitution Ave., NW

Washington, DC 20004

Page 1 of I

Ship Date: 21NOV14

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