atmospheric chemistry at ole john nielsen department of chemistry, university of copenhagen
TRANSCRIPT
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Atmospheric Chemistry at
Ole John NielsenDepartment of Chemistry, University of Copenhagen
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Outline1. Who am I?
2. What are the concerns on atmospheric emissions?
3. How do we study atmospheric chemistry?
4. Cases:
1. CFC alternatives
2. Trifluoroacetic acid (TFA) CF3COOH
3. Perfluoro organic acids (PFOAs)
4. Alternatives to the CFC alternatives
5. Conclusions
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5.5M people43000 km2
1009M people3287000 km2
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Why/How did I become interested inAtmospheric Environmental Chemistry?1954 Born1973 Began at UoC (chemistry and physics)1974 Important Atmospheric Year1978 M.Sc. and on to do a PhD at Risø Nat. Lab.1978-95 Risø National Laboratory1995-96 Ford Research Center Aachen, Germany1996-99 Risø National Laboratory1999-? Professor at UoC2007 Nobel Peace Prize together with Al Gore and 2500 scientists
Gas phase kinetics and reaction mechanisms - relevant to the atmosphere
IPCC – Intergovernmental Panel of Climate Change – India?
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Acknowledgements
• Mr. Jens Sehested• Mrs. Trine Møgelberg• Mrs. Merete Bilde• Mrs. Lene Christensen• Mr. Jesper Platz• Mrs. Anne Toft• Mr. Mads Andersen• Mrs. Meshkat Javadi
• Tim Wallington (Ford)• Mike Hurley (Ford)• Jim Ball (Ford)• John Owens (3M)• Rajiv Singh (Honeywell)• Bob Waterland (Dupont)• Scott Mabury (Toronto)• Brian Scott (CanEnv)
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What are the Concerns on Atmospheric Emissions ?
1. Radiation Forcing/Global Warming/Climate Change– (global)
2. Stratospheric Ozone Depletion (CFCs)– (global)
3. Tropospheric Oxidant Formation – (local-regional-global)
4. Harmful emissions and/or Harmful Degradation Products– (local-regional-global)– Example: 1984 Bhopal accident, methyl isocyante
• What do we need to know about a compound in order to quantify the environmental impacts ?
• "Guilty - until proven innocent"• We (the people of the Earth) have been extremely lucky (CFCs)
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NO
CF3
hh
aq
HF+C(O)F2
CF3C(O)O2NO2
CF3C(O)O
CF3COOH
NO2NO
Decomp/h
hh
O2
CF3C(O)O2
CF3C(O)
aqCF3COF
Atmospheric degradation of HFC-134a
HCOF
OH.
CF3CFH.
CF3OH
RRH
NO2NO
CF3O
CF3O2
O2
HO2
O2CF3CFHO
CF3CFHOOH CF3CFHOONO2CF3CFHO2
CF3CFH2
NO2NO
OH
NO2HO2
O2
H2O
FNOFOx
FCOx
FNO2
hNO
h
O3
We need to know theatmospheric chemistry
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And that is the research that we do:
• Atmospheric Science (Chemistry) Research
Investigations of chemical/physical processes
We use the lab and/or the field and/or modelling to provide a better understanding of atmospheric processes and composition.
• Will lead to better quantification of environmental impact• May not lead to a better environment
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NO
CF3
hh
aq
HF+C(O)F2
CF3C(O)O2NO2
CF3C(O)O
CF3COOH
NO2NO
Decomp/h
hh
O2
CF3C(O)O2
CF3C(O)
aqCF3COF
Atmospheric degradation of HFC-134a
HCOF
OH.
CF3CFH.
CF3OH
RRH
NO2NO
CF3O
CF3O2
O2
HO2
O2CF3CFHO
CF3CFHOOH CF3CFHOONO2CF3CFHO2
CF3CFH2
NO2NO
OH
NO2HO2
O2
H2O
FNOFOx
FCOx
FNO2
hNO
h
O3
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ContainerInitiation Detection
How ?
• Laser Photolysis• 1 liter stainless steel• UV/VIS-absorption
– pm or diode array– microsec. resolution
• Kinetics
• Continuous photolysis• 100 liter Quartz• FTIR spectroscopy
– 26 m and 0.25 cm-1– min. resolution
• Kinetics and Products
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How ?
To LeCroy and PC
Gas cell
Febetron
Xenon lamp
Monochromator
e-
Diode array
Photomultiplier
Shielding wall0 10 20 30 40
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.0
0.3
0.6
0.9
0.0
0.3
0.6
0.9
Wavenumber (cm-1)
800 1000 1200 1400 1600 1800 2000
0.0
0.2
0.4
Abs
orba
nce 10
A : Before UV irradiation
B : After UV irradiation
C : B - (0.49 x A)
laser
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What problems are we interested in?
• How and why are compounds degraded or transformed in the atmosphere in certain ways?
– CFC alternatives– Trifluoroacetic acid (TFA) CF3COOH– Perfluoro organic acids (PFOAs)– Alternatives to the CFC alternatives
– Biofuels for transportation– Greenhouse gases in general– Formation of cloud condensation nuclei
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What was the issue in 1974?
• Ask: “What happens with …..?” – and get the Nobel Prize (the real one)
• Rowland and Molina asked themselves
What happens to CFCs in the atmosphere?
CF2Cl2 does not react in the troposphere but is photolyzed in the stratosphere:
CF2Cl2 + hν → CF2Cl + Cl - and so what?
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CFC-11CFCl3
CFC-12CF2Cl2
What was the problem?1974?1985?
What did the chemists have to do to protect the ozone?
Cl + O3 → ClO + O2
ClO + O → Cl +O2
--------------------------O + O3 → O2 + O2
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• HCFC: Hydrochlorofluorocarbons: CHClF2
• HFC: Hydrofluorocarbons: CF3CFH2
• HFE:Hydrofluoroethers: CF3OCF2H
What did the chemists have to do to protect the ozone?
Make similar compounds with shorter lifetimes or make similar compounds with no Cl or both CHClF2 + OH → H2O + CClF2 → ……….
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NO
CF3
hh
aq
HF+C(O)F2
CF3C(O)O2NO2
CF3C(O)O
CF3COOH
NO2NO
Decomp/h
hh
O2
CF3C(O)O2
CF3C(O)
aqCF3COF
Atmospheric degradation of HFC-134a
HCOF
OH.
CF3CFH.
CF3OH
RRH
NO2NO
CF3O
CF3O2
O2
HO2
O2CF3CFHO
CF3CFHOOH CF3CFHOONO2CF3CFHO2
CF3CFH2
NO2NO
OH
NO2HO2
O2
H2O
FNOFOx
FCOx
FNO2
hNO
h
O3
Better in every way –But
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CFC alternatives - Conclusions• 25 papers with the title ”Atmospheric Chemistry
of……”• last one in 1998 – we thought !
• The new compounds did not destroy ozone• The new compounds did not produce ozone in
the troposphere• The new compounds were more acceptable as
green house gases – good enough?• Some of the new compounds produced TFA
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TFA (CF3COOH) IN THE ENVIRONMENTWhy are we interested ?
• pKa = 0.23
• Solubility > 10000 g/L
• Henry´s law constant 0.112 atm cm3/mole
• kOH = (1.7±0.5)x10-13 cm3molecule-1s-1 (68d)
• Other Sinks ? Bacteria ? No real sinks!
• Phytotoxic
• Atmospheric sources e.g.:– CF3CFH2, CF3CCl2H, CF3CFClH
• Analysis: Derivatization and GC-MS
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Objective 1
• Compare the levels of TFA calculated to arise from known sources with those observed in the environment.
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CF3COOH - KNOWN SOURCESCompound Name Molar yield Lifetime
years
Estimated
Flux (t/yr)
Estimated
Flux (t/yr)
CF3CHClBr Halothane 0.6 1.2 520
CF3CHClOCHF2 Isoflurane 0.6 5 280
CF3CHCl2 HCFC-123 0.6 1.5 < 760
CF3CHFCl HCFC-124 1.0 6.0 < 320
CF3CH2F HFC-134a 0.13 14.6 1200
Fluoropolymers 200
TFA (1000 t/y) Neg
Total 3080
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CF3COOH - CONCENTRATIONS
• TFA found in oceans, rivers, lakes, fog, snow, rainwater and air samples (U.S., Germany, Israel, Ireland, France, Switzerland, Austria, Russia, South Africa, and Finland)
• TFA in rainwater in Bayreuth 1995 was 100 ng/L– Jordan, A.; Frank, H., Environ. Sci. Tech., 1999, 33, 522.
• Fog and rain 36 samples in 1994-1996 in California and Nevada contained 31-3779 ng/L TFA
– Wujcik, C. E.; Zehavi, D.; Seiber, J. N., Chemosphere, 1998, 36, 1233.
• TFA in ocean water (Pacific, Atlantic, Arctic) 20-250 ng/L– Wujcik, C. E.; Zehavi, D.; Seiber, J. N., Chemosphere, 1998, 36, 1233. – Scott, B. F. et al. at the Atmospheric Reactive Substances Symposium, April, 1999.
• No variation with depth down to 3000m (300years)– Scott, B. F. et al. at the Atmospheric Reactive Substances Symposium, April, 1999.
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Pol
ar M
ixed
Lay
er
Pac
ific
Hal
oclin
e~
10 y
ears
Atla
ntic
Lay
er ~
25 y
ears
Bot
tom
La
yer
~3
00 y
ears
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CF3COOH - BURDEN
• TFA in ocean water (Pacific, Atlantic, Arctic) 20-250 ng/L– Wujcik, C. E.; Zehavi, D.; Seiber, J. N., Chemosphere, 1998, 36, 1233.
– Scott, B. F. et al. at the Atmospheric Reactive Substances Symposium, April, 1999.
• The oceans: 1.4x1021 L• The oceans contain (0.3-3.5)x108 tonnes of TFA
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CF3COOH - DILEMMA
• The oceans contain (0.3-3.5)x108 tonnes• TFA flux of 3080 tonnes/yr• 10000-100000 years to give current TFA levels• But – we have only used these compounds for 50 years?• Possible conclusions:
– concentration measurements are all wrong ?– Under-estimated the sources ? Unknow sources ?– Or both ?
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Objective 2
• Have there been old/natural sources of TFA ?
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Old Groundwater
Sample 13-4 13-5 13-6TFA (ng/l) 22 7 3remark
Sample D9-3 D9-4 D9-5TFA (ng/l) 3 15 5remark
Sample D10-4 D10-5 79.992TFA (ng/l) N.D. 2 N.D.remark
3000 year old, CFC contaminated
2000 year old, NOT CFC contaminated
* Water Resour. Res., 28 (1992) 2257
3000 year old, CFC contaminated*
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Old Ice
Sample #1 #1 #2 #2TFA (ng/l) N.D. 0.5 N.D. N.D.remark 1250 meters = 3549 years old
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Conclusions
• TFA is not a natural component of the freshwater hydrosphere !
• TFA from underwater volcanic activity ?
• Sources of TFA in ocean water need to be determined !
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Long chain perfluorinated acids (PFCAs/PFAs) observed in fauna in urban and remote locations
PFOA (perfluorooctanoic acid) C7F15C(O)OH
PFNA (perfluorononanoic acid) C8F17C(O)OH
PFDA (perfluorodecanoic acid) C9F19C(O)OH
PFUA (perfluoroundecanoic acid) C10F21C(O)OH
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
CC
FF
FF
FF
FF
FF
FF
PFPeA
OHO
F
F
PERSISTENCE ! – ASK ME ABOUT IT
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Contamination Profile - Polar Bears (Sanikiluaq Isl.)
Box plots show the outliers, 10th, 25th, median, 75th and 90th centile.
n.d.<0.5
We’re0.0001% PFOS !
Martin et al. 2004
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C10F21C(O)OH
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No natural sources.
Water-soluble PFCA salts used in fluoropolymer processing.
Not released in significant quantities.
Presence of PFCAs in remote areas and in foxes suggests atmospheric source.
Where do long chain Perfluorocarboxylicacids
(PFCAs), CnF2n+1COOH come from?
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PolyfluoroAlcohols are highly volatile!!!
Observed in the atmosphere
5504503502501505050.01
.1
1
10
100
1000
10000
Molecular Mass
Log
P (
Pasc
als
)
Hydrocarbon Alcohols
Fluorotelomer Alcohols
HC data from Daubert & Danner; FTOH data from Lei et al, J Chem Eng Data and Stock et al, ES&T, both in press.
FF
FFF
F
FFF
F
FF
F
C
FF
COH
F
F H
H
H
H
8:2 FTOH = 212 Pa
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FTOH based coatings heavily used in consumer products;
*TRP Presentation toUSEPA OPPT. Nov 25, 2002US Public Docket AR226-1141
5x106 kg/yr40% in North America80% are in polymers*
Carpet Treatment
Polymer
Potential Sources?
Degradation
N C
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
CH2
H2COH
F
F
F F
F F
F F
F F
F F
F F
F
FF
C
F FC
OHH H
H H
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
CH2
H2C
F
F
OO
OO
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
CH2
H2C
F
F
O
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
Urethane EtherEster
CH2
H2C
F
F
Residual
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Three necessary conditions:
(1) FTOH survive long enough for atmospheric transport
(2) FTOH degrade to give PFCAs
(3) Magnitude of PFCA formation must be significant
Use a FTIR Smog chamber
Research Question:
Does atmospheric oxidation of FTOHs contribute significantly to PFCA burden in remote locations?
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UV irradiation of
FTOH/reference/CH3ONO/NO/air mixtures
FTOH = 4:2 FTOH, 6:2 FTOH, or 8:2 FTOH
reference = C2H2 or C2H4
CH3ONO CH3O + NO
CH3O + O2 HCHO + HO2
HO2 + NO OH + NO2
OH + FTOH products (1)
OH + reference products (2)
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OH + FTOH products (1)
OH + reference products (2)
][reference[OH]k]reference[
]FTOH[]OH[k]FTOH[
ss2ss1
dt
d
dt
d
Integration gives:
t[OH]k]reference[
]reference[t[OH]k
]FTOH[
]FTOH[ss2ss1
t
toLn
t
toLn
FTOH and reference have equal exposure to OH radicals, hence:
t
to
2
1
t
to
][reference
][reference
k
k
[FTOH]
[FTOH]LnLn
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Ln ([Reference]to/[Reference]t)0.0 0.5 1.0 1.5
0.0
0.1
0.2
0.3
0.4
0.5
0.6L
n([
F(C
F2C
F2)
n(C
H2)
2OH
] to/[F
(CF
2CF
2)n(
CH
2)2O
H] t)
C2H2
C2H4
OH + CnF2n+1CH2CH2OH → products (10)
OH + C2H2 → products (11)
OH + C2H4 → products (12)
Linear fits give k10/k11 = 1.18±0.15 and k10/k12 = 0.131±0.018.
Using k11 = 8.5 x 10-13 and k12 = 8.66 x 10-12 gives
k10 = (1.00±0.13) x 10-12 and (1.13±0.16) x 10-12 cm3 molecule-1 s-1.
Final value, k10 = (1.07±0.22) x 10-12 cm3 molecule-1 s-1.
No discernable difference in reactivity of OH radicals towards 4:2, 6:2, and 8:2 FTOH
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Assuming:
atmospheric lifetime* for CH3CCl3 = 5.7 years
k(CH3CCl3 + OH) = 1.0 x 10-14 cm3 molecule-1 s-1
then
atmospheric lifetime* of CF3(CF2)nCH2CH2OH
(1.0x10-14)/(1.1x10-12) x 5.7 x 365 20 days.
* with respect to reaction with OH radicals
FTOH Lifetime Estimate
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Other loss mechanisms?
Photolysis – is negligible
Rainout – estimated to be negligible
Dry deposition – lifetime estimated to be 8 years
Homogeneous reactions other than with OH - unlikely
Atmospheric lifetime determined by reaction with OH and is approximately 20 days.
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Assuming 5m/s winds and a 20d lifetime, FTOHs could be transported over 8500 km
20 days… Long Enough for Long Range Transport?
Copenhagen to Detroit = 6500 km
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Three necessary conditions:
(1) Do FTOHs survive atmospheric transport?
YES
(2) Do FTOHs degrade to give PFCAs?
(3) Magnitude of PFCA formation must be significant
Does atmospheric oxidation of FTOHs contribute significantly to PFCA burden in remote locations?
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0.00
0.05
0.10
0.15
0.20
0.25
IR A
bso
rban
ce
0.00
0.05
0.10
0.15
0.20
0.25
0.00
0.02
0.04
0.06
0.08
Wavenumber (cm-1)
700 900 1100 1300 1500 1700 1900
0.00
0.05
0.10
0.15
(A) before irradiation
(B) 10 sec irradiation
(C) Product
(D) CF3(CF2)3CH2CHO
FTIR study of 4:2 FTOH oxidation
CF3(CF2)3CH2CHO
is the major primary
product from Cl
atom and OH
radical initiated
oxidation of 4:2 FTOH
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[CF3(CF2)3CH2CH2OH] / [CF3(CF2)3CH2CH2OH]0
0.0 0.2 0.4 0.6 0.8 1.0
[CF
3(C
F2) 3
CH
2C
HO
] /
[CF
3(C
F2) 3
CH
2C
H2O
H] 0
0.0
0.1
0.2
0.3
0.4
0.5
CnF2n+1CH2CHO is
reactive …Gives secondary
products …
CnF2n+1CH2CH2OH + OH CnF2n+1CH2C(•)HOH + H2O
CnF2n+1CH2C(•)HOH + O2 CnF2n+1CH2CHO + HO2
Secondary products:
C4F 9CHO,
C4F9CH2COOH
C4F9C(O)OOH
Secondary products are reactive …
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0.00
0.02
0.04
0.06
0.08
0.00
0.10
0.20
0.30
0.40
0.50
0.60
IR A
bso
rba
nc
e
0.00
0.20
0.40
0.60
0.80
Wavenumber (cm-1)
1400 1600 1800 3500
0.00
0.10
0.20
0.30
(A) before irradiation
(B) 8.5 minutes irradiation
(C) residual
(D) CF3(CF2)3COOH
Tertiary products include:
COF2, CF3OH
C4F9COOH
Conclusion of FTIR experiments:
simulated atmospheric
oxidation of 4:2 FTOH (in absence
of NOx) gives a small (few %) yield
of C4F9COOH
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FTIR data shows that in gas phase:
in absence of NOx
4:2 FTOH C4F9CHO C4F9COOH
Likely explanation, presence of HO2 radicals in absence of NOx because: HO2 + NO → OH + NO2 is a very fast reaction
Well established that CH3C(O)O2 + HO2 gives acetic acid and peracetic acid, ,
presumably CxF2x+1C(O)O2 + HO2 reaction gives CxF2x+1COOH and CxF2x+1COOOH.
Product study of CxF2x+1C(O)O2 + HO2 (x=1-4) to test this idea.
in presence of NOx
4:2 FTOH C4F9CHO C4F9COOH
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IR spectra obtained before (A) and after
(B) 55 s of irradiation of a mixture of 18.8 mTorr C2F5C(O)H,
218 mTorr Cl2 and
2.8 Torr H2 in 700
Torr of air. The consumption of
C2F5C(O)H was 63%.
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PFCAs are products of
CxF2x+1C(O)O2 + HO2 reaction
Offers reasonable
explanation of observed PFCA formation in 4:2
FTOH expts.
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CF2
CF3
O
OO HO2+
CF2
CF3
O
OO
OO
H
CF2
CF3
O
OO
O
OH
C2F5C(O)OH + O3
CF2
CF3
O
OO
OO
H
C2F5C(O)OOH + O 2
CF2
CF3
O
OO
OO
H
C2F5C(O)O + O2 + OH
a b c
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Three necessary conditions:
(1) Do FTOHs survive atmospheric transport?
YES
(2) Do FTOHs degrade to give PFCAs?
YES
(3) Magnitude of PFCA formation must be significant
Does atmospheric oxidation of FTOHs contribute significantly to PFCA burden in remote locations?
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Illinois Model and Michigan Model
Illinois – 2-D chemistry-transport model, zonal-averaged model of the chemistry and physics of the global atmosphere, 75 chemical species, 161 reactions, grid resolution 5 degrees of latitude and 1.5 km altitude, 8:2 FTOH emission assumed 500 tonnes per year, flux uniform in time and space over the
land area between 20 oN and 60oN
Michigan – “IMPACT” global 3-D, chemistry/transport model, 4 latitude by 5 longitude horizontal resolution, 46
vertical layers, 90 chemical species, 300 individual reactions, 8:2 FTOH emission assumed 1000 tons per year, with global
distribution assumed to be equal to that of propane.
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Concentration of PFOA (in molecule cm-3) at 50 m.
altitude in the University of Michigan model (IMPACT) for (a) January and (b) July. The color scale extends from (a) 0 to 1.2x103 and (b) 0 to 3x103
molecule cm-3.
January
July
Results from Michigan
Integrating over the latitude range 65-90oN provides an estimate of 0.4
tonnes yr-1 for the PFOA
deposition flux to the Arctic.
Results from Illinois are
the same within uncertainties
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PFCA - Conclusions1. Smog chamber experiments can be used to explain
why polar bears contain PFOA.
2. The results show that atmospheric oxidation of FTOHs makes a significant contribution to the PFCA burden in remote locations.
3. Front page of Environmental Science & Technology 2007
4. Future: Ice-core study on FTOHs and PFCAs (contamination from “teflon” ?)
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Conclusions – if I am out of time
– CFC alternatives• New ozone friendly alternatives were found – However….
– Trifluoroacetic acid (TFA) CF3COOH• The TFA dilemma still needs to be solved
– Perfluoro organic acids (PFOAs)• PFOAs are formed from FTOH• The mechanism can explain observations
– Alternatives to the CFC alternatives• The is a continued effort finding more global warming
friendly compounds
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Atm. residence time+ IR Absorbance
EnvironmentalFate
Alternatives to the alternatives (HCFCs and HFCs)
Cl or Br + O3
Ozone Depletion Greenhouse Gas
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2005 Global Greenhouse Gas Emissions
% Contribution on CO2 Basis
Change since 1990
CO2 +1.6%
CH4 -18%
N2O -20%
FCs +19%
HFCs +154%PFCs -45%SF6 -62%
UNFCCC data for Annex I countries
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Effect of Ether Oxygen on Atmospheric Lifetime
Atm. GWPCompound Lifetime (yrs) (100 Yr ITH) CH3CF3 (HFC-143a) 52 4,470 alkaneCH3OCF3 (HFE-143a) 4.3 756 ether
CF3CFHCF3 (HFC-227ea) 34.2 3,220CF3CFHOCF3 (HFE-227ea) 11 1,500
CF3CH2CF3 (HFC-236fa) 240 9,810CF3CH2OCF3 (HFE-236fa) 3.7 470
CF3CH2CHF2 (HFC-245fa) 7.6 1,030CF3CH2OCHF2 (HFE-245fa2) 4.9 659
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Rf - O - Rh k(OH) (cm3molecules-1s-1)
(years)
n-C4F9 - OCH3 1.20 x 10-14 4.7
i-C4F9 - OCH3 1.54 x 10-14 3.7
n-C4F9 - OC2H5 6.4 x 10-14 0.9
i-C4F9 - OC2H5 7.7 x 10-14 0.7
C4F9-O-(CH2)3-O-C4F9 1.44 x 10-13 0.4
5.93 x 10-14 1.0
Atmospheric Lifetimes of Segregated HFEs
O CF
O
CF
F
F FFF
CH2CH3
CF3
CF3CF3CF3
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Design of New Chemical Technology
Environmentalnon-ozone depletingshort atmospheric lifetimelow global warming potential
Performancestabilitycompatibilityboiling/freezing point
Safety low toxicitynonflammable
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Potential Reductions in Greenhouse Gas Emissions
(on a CO2 basis)
C4F9OC2H5 HFE-569sfc2 (GWP=59)
HFC-43-10mee (GWP=1640)
C4F9OCH3 HFE-449sc1 (GWP=297)
PFC-5-1-14 (GWP=9300)
82% reduction 97% reduction
96% reduction 99% reduction
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Conclusions
– CFC alternatives• New ozone friendly alternatives were found – However….
– Trifluoroacetic acid (TFA) CF3COOH• The TFA dilemma still needs to be solved
– Perfluoro organic acids (PFOAs)• PFOAs are formed from FTOH• The mechanism can explain observations
– Alternatives to the CFC alternatives• The is a continued effort finding more global warming
friendly compounds
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Atmospheric Chemistry at
The End