PFOA/PFSA overview and regulations
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Transcript PFOA/PFSA overview and regulations
PFOA/PFSA overview and
regulations
Jin Yang
6/17/2011
Outline
History of PFOA/PFSA
EPA regulations
Replacements of PFOA/PFSA
Conclusions
PFOA/PFSA
Chemistry
◦ PFOA
CF3(CF2)nCO2X
n=6
X=-H, NH4, etc.
◦ PFSA
CF3(CF2)nSO2X
n=7
X=F, OH, ONa, phosphate ester etc.
Applications and unique properties
Applications
◦ Surfactants
◦ Emulsifiers in fluoropolymers
(C7F15CO2NH4)
◦ Building block for introducing Rf chain.
Unique properties:
◦ Chemical inert and stable
◦ C8F17 is both hydrophobic and oleophobic.
History of PFOA/PFSA issues
3M announced phase-out of PFSA in May 2000
◦ Blood test results of 3M employees showed high level
of PFSA (ppm level in manufacturing workers, ~3020ppb level in blood bank)
◦ EPA also concerned the PFOA
EPA stepped in and other fluorine chemical
companies were pressed to do the similar thing.
Environment groups and state/local
administration stepped in.
EPA responses and actions
PFOA/PFSA 2010/2015 stewardship program
◦ Voluntary base program
◦ Arkema, Asahi, BASF Corporation (successor to
Ciba), Clariant, Daikin, 3M/Dyneon, DuPont, Solvay
Solexis
Participating companies:
◦ Submitted baseline year 2000 data on emissions and
product content.
◦ Report annual progress toward goals and report
progress in terms of both U.S. and global operations.
◦ Reduce 95% of PFOA/PFSA in 2010.
◦ Totally ban PFOA/PFSA in Dec. 2015.
The power of EPA-TSCA
TSCA (Toxic substances control act)
◦ It was established in 1976
◦ Scope of TSCA:
Manufacture in US (PMN-pre-manufacture notice)
Import
Blend/mixing
Export from US
◦ TSCA not only apply in new chemicals but
also apply in new applications of existing
chemicals.
PMN regulations
Exempts of PMN (pre-manufacture
notice):
◦ R&D only
◦ LV (Low Volume (<25,000lb/year))
◦ Export only
Fluorine-containing compounds are not
entitled to be LV exempt.
Anti-fluorine panic in US
Halogenated compounds (flame-retard
materials) had been strictly regulated by
various environment groups and green
movements such as cable manufactures,
green building movement and furnish
manufactures.
There is totally ban fluorine compounds
movement in US. Fluorine compounds are
under attacked by different groups.
What we can learn from US
Be pro-active.
◦ Involving the regulations decision in the
beginning.
Be open mind.
◦ Don’t deny and defend some fluorine
compounds are not health.
Be scientific mind.
◦ Using solid scientific data/evidences to
support the decisions. Do not be emotional.
International regulations
Organization for Economic Co-operation
and Development (OECD)
◦ 2000 - OECD developed a Hazard
Assessment of PFOS and Its Salts.
◦ 2006 - OECD released a Survey on the
Production and Use of PFOS, PFOA, PFAS,
PFCA, and related substances.
◦ 2006 - OECD held a workshop on PFCs and
precursors and published a Workshop Report
in 2007.
International regulations
United Nation's Economic Commission for Europe
(ECE)on Long-range Transboundary Air Pollution
(LRTAP)
◦ December 2005 - LRTAP parties agreed to consider PFOS as a
persistent organic pollutant (POPs).
◦ 2006 United Nations ECE published a report on existing
information on PFOSproduction, use, emissions and pathways to
the environment
United Nations Environment Program (UNEP)
◦ February 2009 - UNEP, in cooperation with U.S., hosted an
International Workshop on Managing PFCs and Transitioning to
Safer Alternatives
International regulations
Stockholm Convention on Persistent
Organic Pollutants (POPs)
◦ June 2005 - Sweden proposed the listing of
PFOS and its precursors in Annex A of POPs.
◦ May 2009 - The production and use of PFOS
and its salts, were restricted under Annex B.
Read more information on the chemicals
listed under Annex A and B.
International regulations
May 2009 - UN Strategic Approach to
International Chemicals Management
(SAICM)
◦ Agreed to consider stewardship programs
and regulatory approaches to reduce
emissions and product content of PFAC and
PFAS chemicals and to work toward their
elimination , where feasible
Expanding stewardship program
Reaching out to other countries,
especially to China
Chinese fluorine chemicals companies are
invited to join this stewardship program
Deadline for phase out PFOA/PFSA is
soon (Dec. 2015)
EPA regulations
The point view of EPA (PBT of
PFOA/PFSA)
◦ Persistent
◦ Bio-accumulative
◦ Toxic
◦ In Dec. 2015 phase out of PFOA/PFSA totally.
Regulations changed for F-polymers
Fluoro-polymers are treated as normal
polymers in term of EPA regulation
polymer exempt is gone.
Fluoro-polymer with CF3-CF2- chain
length of 2 or more need file TSCA and
PMN (pre-manufacture notice).
PMN is not only required for manufacture
in US but also for import from oversea.
Long-chain perfluorinated chemicals
Long-chain perfluorinated chemicals (LCPFC) are the
targets by EPA
EPA treats long chain perfluorinated chemicals as
PBT.
In Dec. 2009, EPA published actions plan on LCPFCs.
◦ Given the concerns with LCPFCs, it can reasonably be
anticipated that continued exposure could increase body
burdens to levels that would result in adverse outcomes
◦ TSCA section 6 provides EPA the authority to ban or
restrict the manufacture, processing, and use of these
chemicals
Some exempts for PFOA/PFSA
applications
Since the critical roles of PFOA/PFSA in
some industrials. So some industrials can
continue to use PFOA/PFSA
◦
◦
◦
◦
◦
Imaging/photography
Auto industrial
Aero-space industrial
Military applications
Semi-conductor industrial
Replacements of PFOA/PFSA
Currently EPA are reviewing over 120
chemicals for PFOA/PFSA replacements.
F(CF2)n- type compounds, n>=6 will be
considered PBT like PFOA/PFSA
C4F9- type compounds showed less toxic
and shorter half-life time in environment.
Approaches for PFOA/PFSA
replacement
Short perfluorinated chain:
◦ C4F9 or shorter than C4
Short perfluorinated chain with CH2 as
linkage:
◦ C4F9CH2C4F8CH2◦ -(CF2)n(CH2)m-, n<=3 and m>=1
Conclusion
PFOA/PFSA is Persistent, bio-accumulative
and toxic.
PFOA/PFSA will be totally phase out in Dec.
2015
Long-chain perfluorinated chemicals (n>4)
will be strictly monitored by EPA.
Short-chain perfluorinated chemicals will be
the focus for future development.