Regulatory Issues Associated with the Development and Use ...411.fit.edu/icmcf/documents/Thomas...

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Regulatory Issues Associated with the Development and Use of Biocide-(DCOIT)- Containing Rubber Thomas S. Ramotowski NUWC Division Newport, Newport, RI, 02841, USA 19th International Congress on Marine Corrosion and Fouling June 26, 2018 Melbourne, Florida, USA UNCLASSIFIED Distribution Statement A Approved for Public Release; Distribution is Unlimited

Transcript of Regulatory Issues Associated with the Development and Use ...411.fit.edu/icmcf/documents/Thomas...

Page 1: Regulatory Issues Associated with the Development and Use ...411.fit.edu/icmcf/documents/Thomas Ramotowski.pdf · Regulatory Issues Associated with the Development and Use of Biocide-(DCOIT)-Containing

Regulatory Issues Associated with the

Development and Use of Biocide-(DCOIT)-

Containing Rubber

Thomas S. Ramotowski

NUWC Division Newport, Newport, RI, 02841, USA

19th International Congress on Marine Corrosion and Fouling

June 26, 2018 Melbourne, Florida, USA

UNCLASSIFIED – Distribution Statement A – Approved for Public Release; Distribution is Unlimited

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Topics

• Background

> DCOIT Biocide in Rubber

• FIFRA

> Legal Definitions and Requirements

• The Regulatory Approval Process

> Modify Existing Label or Register a “Treated

Article”

> DCOIT “Blooming” from the Rubber

> ASTM D-6903

• Final Approval from US-EPA

• Summary and Acknowledgements

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Protecting Elastomers from Marine

Biofouling: Problems & Opportunities

The options: paint/coat or include a biocide

Paints/coatings

typically do not work

well on rubbery

substrates.

Differences in modulus

lead to cracking and

peeling.

There are adhesion

and abrasion issues.

Biocide-based paints

and coatings only work

for short periods of

time due to limited

biocide storage

capacity (thickness

based reservoir effect).

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Starting in 2013, NUWC Newport had been working to determine whether

DCOIT, a heavy metal free, isothiazolinone-based biocide that breaks down

rapidly once released into the marine environment, could be used to protect

critical elastomer-based parts from marine biofouling.

Rohm & Haas (now part of Dow Chemical) was awarded a

Green Chemistry Prize by the US-EPA in 1996 for the development of DCOIT.

4,5-dichloro-2-n-octyl-4-isothiazolin-3-one,

a.k.a. Vinyzene-Max, Kathon-287T and

DCOIT, a heavy-metal free marine biocide

made by the Dow Chemical Company

DCOIT: An Environmentally Friendly Marine Biocide

Half-life in seawater/sediment:

DCOIT = one hour/one day

TBTO = nine days/six-nine months

Bioaccumulation factors:

DCOIT = essentially none

TBTO = 10,000x

Max. Allowable Env. Conc.

DCOIT = 0.63 ppb

TBTO = 0.002 ppb

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1% 6% 3% 0%

Neoprene test panels after 14 months exposure, FIT, Melbourne, Florida

EPDM Rubber test panels after 24 months exposure, FIT, Melbourne, Florida

EPDM Rubber test panel after

44 months of exposure

Narragansett Bay, Rhode Island

6%

Static Testing of Rubber Panels Containing DCOIT

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12 months, TMSI, Singapore

0% 3% 6%

14 months, FIT, Melbourne, Florida, USA

0% 3% 6%

12 months, Pearl Harbor, Hawaii, USA

0% 3% 6%

Conathane EN-7 Polyurethane Test Panels

Containing DCOIT

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VM Release Rate versus Time Plot

Red curve = fixed D; blue curve = 4x fixed DRubber thickness = 0.25”.

• Smaller (slower) D showsmore severe changes in VM release rate to thewater – a “D” of thatmagnitude cannot replenish the rubber/waterinterface fast enough to balance VM loss to the water.

• Dow suggests a level of3.0 μg/cm2-day is the minimum release rate needed to protect a surface from biofouling. That valuecould be used to estimateuseful service life for a VMprotected article.

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FIFRA

Even though the intended targets of marine biocides are not insects,

fungi or rodents, such materials are regulated in the USA under the

Federal Insecticide, Fungicide and Rodenticide Act (FIFRA)

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FIFRA Background

● FIFRA dates back to the Federal Insecticide Act of 1910.

● Originally enacted in 1947, codified under 7 USC chapter 6 § 136 et cet.

● Originally enforced by the Department of Agiculture, but in 1972 the

enforcing agency was changed to the Environmental Protection Agency

(EPA) with a change in emphasis to protect the environment and public

health.

● Under FIFRA, the US-EPA has the authority to regulate the marketing

of economic poisons in the USA. It can enter into cooperative agreements

with States to cooperate in the enforcement of FIFRA.

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FIFRA: Legal Requirements

● FIFRA: Established the registration requirement for all pesticides

only after a period of data collection to determine:

> effectiveness (for intended use)

> appropriate dosage

> hazards

● Pesticide label holds users responsible for proper usage. If

restrictions are ignored, users are liable for any regulatory

consequences.

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FIFRA: What Is a “Pest”?

● FIFRA: A “pest” is any insect, rodent, nematode, fungus, weed or any

other form of terrestrial or aquatic plant or animal life or virus,

bacterium or other micro-organism.

> Does not apply to the last three examples when present in/on

living people or animals.

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FIFRA: What Is a “Pesticide”?

● FIFRA: A “pesticide” is any substance or mixture of substances

intended for preventing, destroying, expelling or mitigating any

pest.

> To obtain regulatory approval, applicant needs to prove

the active ingredient(s) will not cause unreasonable

adverse effects on human health and/or the environment.

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FIFRA: The Difference between

R&D and Production

● FIFRA: No individual may sell, use, or distribute a pesticide not

registered with the US-EPA.

● One major exception: Experimental Use/Testing.

● If the pesticide is not registered, then it must be provided gratis

for experimental use/testing.

● Once the use changes from R&D to production, the pesticide may

be sold, but formal registration is required.

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The EPA Options

By late 2014, testing had shown

that DCOIT could protect

rubbery substrates from marine

biofouling for significant lengths

of time. The Navy use switched

from R&D to production. That

meant we would have to get

regulatory approval from the

US-EPA.

EPA Options

● Modify an existing label (there were several because of Rohm & Haas/Dow

merger – e.g., “Vinyzene Max”; “Kathon 287T”; “Sea-Nine”)

> No existing label had > 0.2% DCOIT content; we needed up to 6%

> Easiest/fastest way to get approved because existing data from

Dow could be used.

> Requires cooperation/help from Dow Chemical

● View the DCOIT-containing rubber as a “treated article”

> Onus is on the Navy to provide required data

> Takes more time/could require additional testing

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The EPA’s Concern About DCOIT

“Blooming” from the Rubber

Both US-EPA and Dow Chemical were

concerned about reports of the DCOIT

biocide “blooming” from the rubber

substrate the Navy was using.

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DCOIT “Blooming” (Continued)

Sampling rubber boots for DCOIT FT-IR spectrum of DCOIT biocide

● FT-IR sampling of several old, large panels indicated the white material

on their surfaces was DCOIT biocide.

● Extensive sampling of Navy sensor rubber boots containing 6% DCOIT by

weight revealed no detectable trace of DCOIT biocide on their surfaces.

● Large panels were the first ones ever made with DCOIT – 12% by weight.

> exceeded solubility limit, hence blooming behavior

> 6% by weight or less of DCOIT is below solubility limit = no bloom

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Rotating Cylinder Release Rate Data

(ASTM D-6903) for Biocides in Rubber

ASTM D-6903 method (developed for AF paints) had to be modified for our

rubber samples. Thin sheets of treated rubber were cut and glued to the

rotating cylinder.

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US-EPA Registration Approval

On June 26, 2017, the US-EPA approved the Dow/Navy requested

label change for Vinyzene Max.

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US-EPA Registration Approval (Continued)

This covers Federal requirements…now we need to satisfy State requirements!

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Summary and Acknowledgements

● Marine biocides are regulated under FIFRA – the Federal Insecticide,

Fungicide and Rodenticide Act – by the US-EPA

> It does not matter if –

- the federal Government paid for the R&D

- the R&D was carried out by U.S. Government

scientists and engineers at a U.S. Government

facility for a U.S. Government need.

● An appropriate label must be developed for the biocide

> an existing label can be changed/updated

> approval as a “treated article”

> needed once biocide transitions from R&D to production

● Need to show effectiveness, dosage, and document hazards

● US Navy now has proper US-EPA registration for use of DCOIT biocide

in polymers up to 6% by weight; working on State specific approvals.

Special thanks to:

Elizabeth Haslbeck (NSWC Carderock)

David Laganella and Joanne Ryder (Dow Chemical Co.)

David Mercier, esquire (NUWC-NPT)

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Questions?