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Improved continuous in situ

measurements of C1C3 PFCs, HFCs,
HCFCs, CFCs and SF6 in Europe and
Australia
a

B. R. Greally , P. G. Simmonds , S. O'Doherty , A. McCulloch

a

, B. R. Miller , P. K. Salameh , J. Mhle , T. Tanhua , C.

b

Harth , R. F. Weiss , P. J. Fraser , P. B. Krummel , B. L.

c

Dunse , L. W. Porter & R. G. Prinn

a

University of Bristol, School of Chemistry , Bristol, BS8 1TS, UK

Scripps Institution of Oceanography, University of California ,

San Diego, La Jolla, CA, USA
c

Commonwealth Scientific and Industrial Research Organisation,

Division of Marine and Atmospheric Research , Aspendale,
Victoria, Australia
d

Cape Grim Baseline Air Pollution Station, Bureau of

Meteorology , Tasmania, Australia
e

Department of Earth, Planetary and Atmospheric Sciences ,

Massachusetts Institute of Technology , Cambridge, MA, USA
Published online: 16 Feb 2007.

To cite this article: B. R. Greally , P. G. Simmonds , S. O'Doherty , A. McCulloch , B. R. Miller ,

P. K. Salameh , J. Mhle , T. Tanhua , C. Harth , R. F. Weiss , P. J. Fraser , P. B. Krummel , B. L.
Dunse , L. W. Porter & R. G. Prinn (2005) Improved continuous in situ measurements of C1C3 PFCs,
HFCs, HCFCs, CFCs and SF6 in Europe and Australia, Environmental Sciences, 2:2-3, 253-261, DOI:
10.1080/15693430500402614
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Environmental Sciences
June-September 2005; 2(2-3): 253 261

Improved continuous in situ measurements of C1 C3 PFCs,

HFCs, HCFCs, CFCs and SF6 in Europe and Australia

Downloaded by [Arif Setya] at 06:41 27 January 2015

B.
B.
R.
L.

R. GREALLY1, P. G. SIMMONDS1, S. ODOHERTY1, A. MCCULLOCH1,

HLE2, T. TANHUA2, C. HARTH2,
R. MILLER2, P. K. SALAMEH2, J. MU
2
3
F. WEISS , P. J. FRASER , P. B. KRUMMEL3, B. L. DUNSE3,
W. PORTER4, & R. G. PRINN5

University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK, 2Scripps Institution of Oceanography,
University of California, San Diego, La Jolla, CA, USA, 3Commonwealth Scientific and Industrial
Research Organisation, Division of Marine and Atmospheric Research, Aspendale, Victoria, Australia,
4
Cape Grim Baseline Air Pollution Station, Bureau of Meteorology, Tasmania, Australia, 5Department of
Earth, Planetary and Atmospheric Sciences, Massachusetts Institute of Technology, Cambridge, MA, USA

Abstract
Improved monitoring of non-CO2 greenhouse gases in air samples is presented, achieved using a new
analytical system based on preconcentration, gas-chromatography and mass spectrometry. In addition to
the major HFCs, HCFCs and CFCs, the new observations include the first in situ time series of the C1
C3 PFCs (CF4, C2F6 and C3F8) and the more volatile of the HFCs (CHF3, CH2F2, CH3CF3) alongside
SF6, all of which are now monitored routinely as part of the Advanced Global Atmospheric
Gases Experiment (AGAGE). Observed trends in newly monitored species are shown, obtained from
1 2 years continuous in situ air analyses at remote monitoring sites at Mace Head (Ireland) and Cape
Grim (Australia). Observed deviations in the air background for these gas species are linked to modelled
trajectories of air masses arriving at the monitoring stations to indicate potential source regions for
emissions in Europe and Australia. In addition, preliminary estimates of 2004 mixing ratio growth rates
of compounds are deduced from the observations, which highlight the importance of continuous
atmospheric monitoring for verification of consumption-based emission estimates of non-CO2
greenhouse gases.

Keywords: Perfluorocarbons, hydrofluorocarbons, air analysis, GC-MS, AGAGE, C1-C3 PFC, SF6,
HFC-23, HFC-32, HFC-143a

1. Introduction and methodology

The environmental impact of the release of radiatively important gases from anthropogenic
and biogenic activities will depend on factors such as infra-red absorption, the amount of gas
emitted, the geographic location of the emission and the chemical processes that remove such
gases from the atmosphere. For example, while high emissions of shorter lived greenhouse

Correspondence: B. R. Greally, University of Bristol, School of Chemistry, Bristol, BS8 1TS, UK. E-mail: brian.greally@bristol.ac.uk
ISSN 1569-3430 print/ISSN 1744-4225 online 2005 Taylor & Francis
DOI: 10.1080/15693430500402614

Downloaded by [Arif Setya] at 06:41 27 January 2015

254

B. R. Greally et al.

gases (GHGs) can have an important influence on the overall radiative forcing in the
atmosphere, relatively modest emissions of strongly infra-red adsorbing gases with
long atmospheric lifetimes can also significantly influence the overall radiative forcing of
the atmosphere (Abrahamson 1992).
An important factor when discussing impacts of GHG emissions is the evolution of the
mixing ratios in the atmosphere with respect to time. Numerous approaches to air analysis
for halogenated gases are employed at various geographic locations worldwide. Short-term
in situ atmospheric monitoring can reveal possible source regions of GHG emissions, and
in the case of chemically reactive species, is useful in the determination of regional
chemistry. However, such short-term monitoring campaigns cannot determine the growth
rate of a compound with time. Long-term flask sampling of air from remote locations
(with subsequent central laboratory analysis) allows accurate growth rate deduction of
GHG mixing ratios, but does not allow for the accurate determination of the source (or
strength) of the emission region. On the other hand, flask sampling has the benefit of
allowing increased spatial coverage, and hence more representative deduction of global
distribution of GHGs.
In situ monitoring of radiatively important non-CO2 greenhouse gases (NCGGs) in
the atmosphere has been performed since 1978 by the ALE/GAGE/AGAGE
(Atmospheric Lifetime Experiment/Global Atmospheric Gases Experiment/Advanced
GAGE, henceforth referred to as AGAGE) network at 5 locations worldwide. The
network has monitored the principle NCGGs (CH4, N2O, CFC-11 (CFCl3), CFC-12
(CF2Cl2), CFC-113 (CF2ClCFCl2)) alongside important halogenated species such as
CH3CCl3, CHCl3 and CCl4, using gas chromatography in combination with multiple
detectors (GC-MD) at a frequency of up to 36 fully calibrated measurements each 24
hours. Such high temporal coverage allows for the determination of both the long term
growth rate of these compounds (the baseline, in both northern and southern
hemispheres), and the determination of regional emissions (which manifest as a mixing
ratio above the baseline). In addition, the network has stations in both hemispheres
which enable the measurement of the average baseline mixing ratio growth rates (Prinn
et al. 2000).
The GC-MD instruments analyze gases of sufficient concentrations in the atmosphere
by whole air analysis using conventional GC detectors such as Flame Ionization Detector
(FID for CH4 analysis) and Electron Capture Detector (ECD, all other listed species).
The GC-MD instrument detectors are not sufficiently sensitive or selective to measure the
CFC replacement compounds (HCFCs and HFCs) nor lightly halogenated compounds
(e.g. CH3Cl, CH3Br and CH2Cl2). The in situ air analysis of such compounds requires
significant preconcentration with enrichment devices such as carbon adsorbents operating
at sub-ambient temperature, higher resolution chromatographic columns, and a more
selective and sensitive detector. An adsorption desorption system (ADS) coupled to a
commercial gas chromatograph-mass spectrometer (GC-MS) has been developed and
operated at the AGAGE stations at Mace Head (MH), Ireland (538N, 98W) from 1994 to
2005 and Cape Grim (CG), Tasmania (408S, 1448E) from 1998 to 2005 (Simmonds et al.
1995). The ADS-GC-MS instrument enriches HFCs, HCFCs and other halocarbons from
2 litres of ambient air onto a microtrap filled with 10 mg Carboxen adsorbent operating at
7508C. Thermoelectric coolers are used, as non-expendable cryogenics are a key
requirement for operating at remote locations. Separation of the sampled gases
(approximately 28 individual compounds) and detection using unique mass spectral ions
is performed automatically with a frequency of 6 calibrated air samples each 24 hours.

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Improved monitoring of PFCs

255

With the ADS-GC-MS, near-decadal air mixing ratio growth rates have been determined
for the major CFC replacement compounds (principally CHF2Cl, CH3CFCl2, CH3CF2Cl
(HCFC 22, 141b, 142b) and CH2FCF3 (HFC-134a)) in all four semi-hemispheres
(Simmonds et al. 1998, ODoherty et al. 2004), alongside other important biogenic/
anthropogenic gases (e.g. CH3Cl, CH3Br, (Simmonds et al. 2004)). Extension of the ADS
technology to other European locations through the SOGE programme (System of
Observation of halogenated Greenhouse gases in Europe) has allowed increased regional
coverage of detection of above-baseline mixing ratios and determination of more accurate
European greenhouse gas emissions and northern hemispheric growth rates (Greally et al.
2002, Reimann et al. 2004, 2005).
The range of analytes which can be detected with the ADS-GC-MS is restricted by the
temperature to which the adsorbent filled microtraps can be cooled (7508C). This
temperature is not sufficiently cold to quantitatively adsorb perfluorocarbons, SF6 and some
low boiling point HFCs. In addition, the methodology requires 2 hours for the enrichment,
separation and detection stages, permitting only six calibrated air measurements each day.
Consequently, a short-term elevation above the baseline (where air is arriving at the sampling
site after crossing over an emission region) may not be well defined as air sampling occurs
only each 4 hours.
A new advanced GC-MS instrument (denoted Medusa GC-MS) has been jointly developed
by Scripps Institution of Oceanography (USA) and University of Bristol (UK). The Medusa
GC-MS instrument uses advanced cryo-cooling (to 71808C), faster chromatography and
greatly improved customized Mass Spectrometry to allow the determination of C1 C3 PFCs,
SF6 and highly volatile HFCs in air samples at double the sampling frequency achieving 12
fully calibrated analyses per 24 hours. Full details of the instrumental method will be submitted
for publication shortly (Miller et al., manuscript in preparation, 2005). Results for the 2
Medusa GC-MS instruments operated at the Mace Head and Cape Grim monitoring stations
from 2003 2004 are presented in this manuscript. A one year overlap period of simultaneous
operation of the older ADS-GC-MS and the new Medusa GC-MS at Mace Head and Cape
Grim ensured satisfactory agreement between instruments in order to continue the time series
of the key HFC, HCFC and halocarbon species at both monitoring stations (ODoherty et al.
2004, Simmonds et al., 2004). We present the first recorded continuous in situ measurements
of new gases measured by Medusa GC-MS of differing atmospheric lifetime (IPCC 2001),
namely PFC-14 (CF4, lifetime 450,000 yrs), PFC-116 (C2F6, 10,000 yrs), PFC-218 (C3F8,
2,600 yrs), SF6 (3,200 yrs), HFC-23 (CHF3, 260 yrs), HFC-32 (CH2F2, 5 yrs) and HFC-143a
(CH3CF3, 52 yrs) in Europe and Australia.
It must be noted that the data from the Medusa GC-MS are presented on a preliminary
calibration scale derived from a dilution of a commercially prepared gravimetric standard,
with a bootstrap to a GC-MD derived CFC-12 mixing ratio value (see Prinn et al. 2000
for details of the technique) so hence may change slightly in future publications. The
Medusa GC-MS calibrations will improve when the latest calibration scale being
developed at SIO becomes available and are applied to both the Mace Head and Cape
Grim records. Mixing ratios are reported in ppt (10712 mol/mol). Of important note, the
CF4 data from Cape Grim is reported on a calibration scale developed at the Max-PlanckInstitute for Aeronomy laboratories (R. Borchers (MPAE) and D. Etheridge (CSIRO),
personal communication, 2004), so it is not yet possible to directly compare the CF4
mixing ratio observed at Mace Head with those observed at Cape Grim. The other new
gases observed using Medusa GC-MS are not presently calibrated for Cape Grim; an issue
to be rectified shortly.

256

B. R. Greally et al.

2. Results and discussion

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2.1. Instrumental overlap

The ADS-GC-MS and Medusa GC-MS instruments were operated under similar conditions
at both the Mace Head and Cape Grim monitoring stations. The samples were taken at a
similar height from the air sampling towers, with a common calibration routine to quantify
the air measurements. Air samples which coincided within +2 hours were examined for the
percentage differences in their response between the ADS and the Medusa systems, the
results for key species are presented in Table I. Positive percentage difference infers a higher
value from the air analysis on the Medusa GC-MS than the value from the matched air
analysis on the ADS-GC-MS.
It is clear that the agreement has been excellent with the exception of an offset between the
two instruments for CH3Br. This issue is being currently addressed in order to continue
the longer term records from the ADS-GC-MS with the more recent and future records of
the Medusa GC-MS. The difference may be due to non-concurrent sampling of air by the two
instruments, and is also complicated by CH3Br having natural as well as anthropogenic
sources, particularly at Mace Head (Dimmer et al. 2001, Simmonds et al. 2004).
2.2. Measurements of new Medusa GC-MS species from Mace Head and Cape Grim
Perfluorocarbons and SF6. The in situ measurements of perfluorocarbons reveal some
interesting features. The atmospheric background of CF4 at Mace Head averages 81.3 ppt
in 2004, with a growth rate of approximately 0.7%/yr (0.6 ppt/yr). Incidences of abovebaseline elevations (i.e. regional emissions of the PFCs) show that for the European site, the
emissions of C2F6 and C3F8 are much higher in percentage terms than for CF4. A relatively
low frequency of events above the baseline are seen at Mace Head for CF4, about nine
significant events of high magnitude are recorded between Nov 2003 to May 2005, the largest
event (March 2004) being 2.5% above the baseline (see Figure 1). The major emission
source for CF4 is aluminium electrolysis, specifically when an intermittent process condition
occurs in the electrolysis procedure (a condition known as an Anode Effect) (Weston Jr.
1996). The Mace Head site (on the West coast of Ireland) receives air masses from Europe
approximately 30% of the time. Observations of above-baseline elevations in CF4 in the Mace
Head are associated with air masses passing over a CF4 release processes from Europe, such
as releases from Aluminium electrolysis or semiconductor manufacturing.
There is a striking difference in the record for C2F6 at Mace Head. Above-baseline
elevations are observed regularly. These baseline deviations are occasionally correlated with

Table I. Instrumental agreement as percentage difference of ADS-GC-MS versus Medusa GC-MS for air
measurements at Mace Head (Ireland), Jan to Dec 2004 and Cape Grim (Tasmania), May 2004 to Feb 2005.
Mace Head
Compound

% difference

HFC-134a
HCFC-22
HCFC-142b
HCFC-141b
CH3Cl
CH3Br

0.3
0.0
0.5
70.1
0.2
11.1

Cape Grim

% Std. Dev, n
1.2,
1.0,
1.0,
1.0,
2.0,
4.7,

1221
1218
1220
1218
1186
1192

% difference
70.9
70.4
0.0
70.6
70.5
73.4

% Std. Dev, n
1.0,
0.5,
0.7,
0.8,
2.6,
4.1,

861
851
855
847
849
845

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Improved monitoring of PFCs

257

Figure 1. Observed CF4 and C2F6 time series at Mace Head, Ireland using Medusa GC-MS.

deviations for CF4 but are of much higher magnitude (being up to 25% above the baseline),
also shown in Figure 1. Often, significant above-baseline events in C2F6 are not well
correlated with CF4 events. This finding is surprising given that one source of C2F6 is also
from an anode effect during aluminium smelting; CF4 and C2F6 should be emitted in an
average reported ratio of 10:1. At Mace Head, the emissions observed from Europe for C2F6
are far stronger and indicate a greater source for European C2F6 emissions (in percentage
terms). As the semiconductor industry uses C2F6 in applications such as silicon etching and
CVD chamber cleaning, our conclusion is that the above-baseline C2F6 (and C3F8) recorded
at Mace Head are much more likely to be from a semiconductor source than an aluminium
smelting source. The baseline growth rate for C2F6 in 2004 was approximately 0.05 ppt/yr
(1.4%/yr). The average mixing ratio for C2F6 was 3.5 ppt in 2004 at Mace Head. The 2004
growth rate for CF4 and C2F6 observed at Mace Head are lower than those values previously
reported by Khalil et al. (2003) and Harnisch et al. (1996, 1999) (see Table II), which is
consistent with a decrease in global emissions in both compounds from the late 1990s.
The baseline mixing ratios of CF4 were measured historically from the Cape Grim air
archive (from 1981). The overall trend in the growth rate has slowed significantly from the
1980/1990s value of 1.1 ppt/yr to the current observation of 0.8 ppt/yr for 2004, which could
indicate a significant reduction in emissions of CF4 from the aluminium industry. The 2004
average CF4 mixing ratio measured by Medusa GC-MS at Cape Grim is 79.6 ppt (on the
MPAE scale). Above-baseline CF4 mixing ratios at Cape Grim have been linked to a source of
aluminium electrolysis on mainland Australia, with a case study on 23 July 2004 indicating a
3.7 ppt (4.6 %) enhancement above the baseline. Air trajectories indicated that the air mass
had passed over an aluminium electrolysis plant in Point Henry (SW of Melbourne) and took
8 hours to transport to Cape Grim (on NW Tasmania). There is less baseline deviation in the
C2F6 record, which indicates no close sources of emissions near Cape Grim.
Observed C3F8 at Mace Head indicates strong emissions also from Europe, with deviations
above the baseline of up to 30%. Such strong European emissions may be resulting from

258

B. R. Greally et al.

Table II. Observed trends in fluorinated gases at Mace Head, Ireland by Medusa GC-MS during 2004, comparing
growth rates with previously reported values.
2004 Medusa GC-MS
observations at Mace Head

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Gas

Mixing Ratio

CF4

81.3 ppt

C2F6

3.5 ppt

C3F8

0.47 ppt

SF6

5.5 ppt

CH2F2

0.7 ppt

CHF3

22.6 ppt

CH3CF3

5.5 ppt

Growth Rate

Recent Literature reported growth rate (trend, period, reference)

0.7%
0.6 ppt
1.4%
0.05 ppt
8.7%
0.04 ppt
4.7%
0.25 ppt
60 70%
0.4 0.5 ppt
7.3%
1.6 ppt
16%
0.9 ppt

0.85 ppt/yr, 1986 1997 (Khalil et al. 2003)

0.72 ppt/yr, 1992 1998 (Harnisch et al. 1999)
0.09 ppt/yr, 1987 1997 (Khalil et al. 2003)
0.087 ppt/yr, 1987 1995 (Harnisch et al. 1996)
0.01 ppt/yr, 1986 1997 (Culbertson et al. 2004)
6.8 7.5%/yr, 1994 1996 (after Maiss and Brenninkmeijer 1998)
Not reported
0.69 ppt/yr (5.0%/yr), 1986 1997 (Culbertson et al. 2004)
0.55 ppt/yr (5.0%/yr), 1990 1995 (Oram et al. 1998, SH)
80%/yr, 1996 1997 (Culbertson et al. 2004)

the use of C3F8 by the semiconductor industry in etching applications given that supply
problems exist in the use of an alternative etching gas NF3. Nevertheless, the growth rate of
the C3F8 baseline in 2004 was approximately 0.04 ppt/yr (8.7%/yr) so global emission of
PFC-218 remain low. The average mixing ratio for C3F8 was 0.47 ppt in 2004 at Mace Head.
The increase in the growth rate from that reported by Culbertson et al. (2004) confirms an
increased global emission rate of C3F8 since 1997. The record of SF6 observed at Mace Head
shows some baseline elevations, and the baseline average in 2004 was 5.5 ppt. The observed
growth rate was 0.25 ppt/yr (4.7%/yr) which is a lower rate than observed by Maiss and
Brenninkmeijer (1998) (6.86%/yr in 1996). The lower observed growth rate in the 2004
Medusa GC-MS dataset may be due to decreased global emissions and is consistent with
better containment of SF6 in equipment for the power distribution and semiconductor
industries (the major users).
Hydrofluorocarbons. The HFC-23 (CHF3) and HCFC-22 (CHF2Cl) records at Mace Head
are illustrated in Figure 2. The reported major source for HFC-23 emissions is a byproduct from the production of HCFC-22 (via overfluorination of CHCl3). Despite this,
the observed record shows little deviation of HFC-23 when air reaches Mace Head from
Europe and is rarely correlated with above-baseline deviation in the HCFC-22 record. This
suggests that European emissions of HFC-23 are low and also indicates that emissions of
HCFC-22 from Europe are more likely due to use of HCFC-22 rather than from
production losses of HCFC-22. The average baseline mixing ratio for HFC-23 recorded at
Mace Head in 2004 was 22.6 ppt, with a growth rate of 1.6 ppt/yr (7.3%/yr). This
growth rate is larger than the 5%/yr recorded by both Culbertson et al. (2004) and Oram
et al. (1998) and may indicate increased emissions since the late 1990s. However, the
estimated analysis scatter in the Culbertson paper is order of 12% RSD, compared to the
Mace Head Medusa GC-MS scatter of 52.0% RSD (standard-standard ratio), this could
indicate that the truer estimate of CHF3 growth rate will be generated from the Medusa
GC-MS in situ record over an observation period greater than 1 year. Additionally, a

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Improved monitoring of PFCs

259

Figure 2. Observed HFC-23 and HCFC-22 time series at Mace Head.

reconstruction of the CHF3 growth rate from Medusa GC-MS analysis of the Cape Grim
archive is ongoing which will allow a direct comparison with the results from Oram et al.
(1998) for the same air archive.
The record for HFC-32 (CH2F2) at Mace Head shows two distinct baseline growth periods
during 2004. The baseline appears to grow at 43%/yr for the first 6 months, and then
accelerates to 86%/yr in the latter half of the year. Overall growth rate was approximately
60 70%/yr in 2004. The increase in the baseline growth rate during 2004 is difficult to
explain. It may be indicative of an instrumental problem, or may be a reflection of what is
being released to the atmosphere globally. The major use of HFC-32 is in refrigerant blends,
typically leading to slow long-term release, so while there may be increased production of
HFC-32 for use, the rapid change in the baseline growth rate was unexpected given that it
would have been caused by significant short-term emissions. HFC-125 (CHF2CF3) is used as
a significant fraction (25% and upwards) in most blends containing HFC-32, yet the Mace
Head baseline for HFC-125 does not show the same rapid increase as is observed for the
HFC-32 baseline. On the other hand, a strong uptake in refrigerant blends could be
responsible and would be consistent with European regulations to reduce the use of HCFCs
in refrigeration. The baseline mixing ratio of HFC-32 is low (*0.7 ppt), so such a rapid
acceleration should be treated with caution until a longer time series can be established.
HFC-32 is observed at Cape Grim, and further work on the calibration for HFC-32 is
ongoing but as yet incomplete.
Mixing ratios for HFC-143a (CH3CF3) from Mace Head show that the baseline has
increased by 0.9 ppt/yr (16%/yr) in 2004. The baseline average mixing ratio was 5.5 ppt.
Above-baseline deviations were significant in the MH record in 2004, some events being from
2 6 times the baseline value. The major use of HFC-143a is in refrigerant blends with other
HFCs, and future work will aim to show a correlation of HFC-143a above-baseline emissions

260

B. R. Greally et al.

with other known components of the refrigerant blends. It is difficult to match our reported
growth rate for CH3CF3 (16%/yr) with the 80%/yr reported in Culbertson et al. (2004)
except to note that the Culbertson value for 1996 1997 indicated an exceptional acceleration
in the emission rate. Our 2004 growth rate may now indicate a lower percentage emission
rate. Our ongoing work in analyzing the Cape Grim air archive (1978 to date) will aim to
confirm the accelerated growth rate in CH3CF3 atmospheric mixing ratio, and we will address
this issue in future publications.

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3. Conclusions
New improved and continuous measurements of the C1-C3 perfluorocarbons, SF6 and new
HFC species (HFC-23, HFC-32 and HFC-143a) are reported from northern and southern
hemisphere observation stations. Baseline growth rates for 2004 are reported, along with
observations of above-baseline elevations, which are indicators of regional emissions of these
species. In Europe, there are much stronger relative increases in above-baseline events for
C2F6 and C3F8 versus CF4 (in percentage terms) which indicates different sources. For CF4
the predominant source is aluminium smelting, while for C2F6 the most likely source is
semiconductor manufacturing. At Tasmania, observations of above-baseline CF4 are highly
correlated with air passing over known point sources (aluminium electrolysis plants). There is
a low correlation of observed HFC-23 and HCFC-22 at the northern hemisphere station,
indicating that HCFC-22 emissions are from use, rather than production leakage. Rapid
growth rate in the baseline is observed for HFC-32 (60 70%/yr) and HFC-143a (16%/yr)
in the European station in 2004.
Acknowledgements
Funding for this work has come from many sources. We acknowledge support for both
instrument design/manufacture and field operation from NASA (USA), DEFRA (UK),
NERC (UK), FP-5 (EU), the Commonwealth Scientific and Industrial Research Organization (CSIRO Australia) and the Bureau of Meteorology (Australia). We also thank the field
station operators at Mace Head (Gerry Spain, Duncan Brown) and Cape Grim (Stuart Baly,
Chris Rickard) for their steadfast efforts in maintaining continuous operations of the
measurements. In addition, we thank Alistair Manning at the UK Meteorological Office for
preliminary baseline filtering results.

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