1
Non-paper*
Releases, Breakdown Products and Opportunities for Reduction of Releases of
Ozone-depleting Substances.
Background Information
EU
Preamble
1. At the thirty-fourth meeting of the Open-Ended Working Group the European Union had introduced a
draft decision on releases of ozone-depleting substances, breakdown products and opportunities to
reduce releases.
2. As recorded in Section E of the Report from the Twenty-Sixth Meeting of the Parties
(UNEP/OzL.Conv.10/7; UNEP/OzL.Pro.26/10), an outcome of the consultations at the MOP 26 was
that European Union would take into account the publication of the final assessment reports of the
Scientific Assessment Panel (SAP) and the Environmental Effects Assessment Panel (EEAP) in
2015 before reverting on the issues. This background incorporates information from the Panels’
quadrennial assessment to highlight some of the concerns expressed by the Parties.
Discrepancies in emissions
3. The production sector, in the context of the control measures of the Montreal Protocol, produces
annually about 1,136,807 tonnes of ODSs (carbon tetrachloride, CFCs, HCFC, methyl chloroform,
halons, methyl bromide) representing a total of 461,314 ODP tonnes (2012), most of which are
currently used as feedstock in production of other chemicals. TEAP (UNEP 2014) reports that the
above amount increased by 4 percent w.r.t. 2011. Generally, “production sector” feedstock uses are
exempted from phase-out measures of the Montreal Protocol under a notion that releases and
environmental impact from production are minimal.
4. TEAP (UNEP 2014) estimates emission levels ranging from 0.1% to 5% of the amount used as
feedstock. TEAP’s Chemicals TOC (CTOC) suggests that the average level of emission is 0.5% and
estimates total emission from the production sector to be about 5684 t/y of ozone depleting
substance (ODS). The release includes levels in the ultimate products and fugitive leaks in the
production, storage and/or transport stages.
5. J.C. Laube et al (March 2014) have reported a significant presence of CFC-113a, CFC-112, CFC112a and HCFC-133a in the atmosphere. CFC-113a and HCFC-133a are used as intermediates or
feedstocks to produce refrigerants HFC-134a and HFC-125. CTOC estimates emissions rates, on a
basis of worst case scenario associated with production of HFCs- 134a, 125 and 143a, to be about
1.6% (UNEP 2014). Laube et al estimate that ca 70,000 t/y (19,600 tonnes of CFC-112, 20,500
tonnes of CFC-113a, and 30,500 tonnes of HCFC-133a) have entered into the atmosphere.
6. The above estimates for emissions of ODS by TEAP/CTOC differ substantially from that reported by
the Scientific Assessment (SAP) assessment (UNEP 2010). For example SAP reported a Carbon
tetrachloride (CTC) production level, for feedstock uses, of 156 Gg (156,000 tonnes) for 2008 and a
global emission range of 40 and 80 Gg/y (40,000 and 80,000 tonnes/y) during 2005–2008. This
indicates emission rates of the order of 25-50%. The 2014 SAP assessment reports that the derived
emissions of carbon tetrachloride (CCl4), based on its estimated lifetime and its accurately
measured atmospheric abundances, have become much larger than those from reported production
and usage over the last decade. The estimate of the total global lifetime (26 years) combined with
the observed CCl4 trend in the atmosphere (−1.1 to −1.4 ppt yr-1 in 2011–2012) implies emissions
of 57,000 (40,000–74,000) tonnes per year , which cannot be reconciled with estimated emissions
*
The present document sets out background information submitted by the European Union. It is reproduced without
formal editing.
2
from net reported production. New evidence indicates that other poorly quantified sources, unrelated
to reported production, could contribute to the currently unaccounted emissions. Since the last
Assessment, the discrepancy between bottom-up and top-down CCl4 emission estimates has not
been resolved. Global emissions determined from AGAGE and NOAA atmospheric data, using a
total lifetime of 26 years, averaged 57 (40–74) Gg (57,000 tonnes) in 2012. After 2005 these topdown emission estimates are considerably higher than bottom-up emissions (derived from reported
production minus feedstock use and destruction) (Figure 1, below).
7. Emissions of HFC-23, a by-product of HCFC-22 production, have continued despite mitigation
efforts. Worldwide emissions of HFC-23, a potent greenhouse gas and by-product of HCFC-22
production, reached a maximum of ~15 Gg (15,000 tonnes) in 2006, decreased to ~9 Gg (9,000
tonnes) in 2009, and then increased again to reach ~13 Gg yr-1 (13,000 tonnes) in 2012. While
efforts in non-Article 5 Parties mitigated an increasing portion of HFC-23 emissions through 2004,
the temporary decrease in emissions after 2006 is consistent with destruction of HFC-23 in Article 5
Parties owing to the Clean Development Mechanism (CDM) of the Kyoto Protocol. The average
global mole fraction of HFC-23 reached 25 ppt in 2012, with an increase of nearly 1 ppt yr-1 in recent
years.
8. Inference of emissions of other CFC, HCFC, HFC on the basis of atmospheric measurements need
to consider amounts emitted from banked substances. A study by Velders et al (2014) indicates that
emissions from banks to be about 36% per year for CFCs (1988), 18% per year for HCFC (2014)
and expected to range 13-20% per year for HFC by 2020.
9. In light of the above, there is a pressing necessity to obtain further clarity on releases and best
available techniques and practices associated with reducing release of ozone-depleting substances
to the environment, including releases from co- or by-production in the production of other
substances.
3
New Substances
10. TEAP (2014) also reports on new substances that are expected to replace ODS including HCFCs in
a number of applications. The main groups of new substances are unsaturated HFCs and
unsaturated HCFCs such as HFC-1234yf, HFC-1234ze, HFC 1233zd and HFC 1336mzz. In
addition, a production of HCFC-1233zd (CF3-CH=CH-Cl, trans isomer) is reported and mention is
made of a submission to USEPA for approval to commercialise 3,3,3-trifluoro-2-bromopropene (2BTP). Information on the amounts, emissions and risks associated with the use is not generally
available.
11. Following the above, further information is required on the amounts of new substances produced,
their feedstock(s), emissions, degradation products to enable further assessment of their
environmental impact or effect.
Effects of Release from the Production Sector
12. In general, HCFC and HFC (saturated and unsaturated) break-down products include trifluoroacetic
acid ((TFA; CF3C (O) OH).and chlorodifluoroacetic acid (CDFA). Under certain conditions
breakdown product may also result in formation of toxic carbonyl fluoride, see below. The sector also
releases poly- and perfluorinated alkylated substances (PFAS) in the form of products or
degradation products. A number of these substances, below termed poly- and perfluorinated organic
compounds (PFCs), have also been observed to be ubiquitous in the Arctic environment (C.M. Butt
et al, 2010) and are increasing rapidly. Recent findings of drinking water supplies in Sweden show
high levels of PFAS. PFCs are being released into the eco-system since many decades. While PFCs
– as products, co-products, and degradation products-- are removed from the atmosphere via
deposition and washout processes, they are accumulating in oceans, lakes, and other reservoirs,
including living beings.
13. Current estimates indicate an ODS production of about 1.14 million tonnes per year. HFCs
production is estimated to be about 800 000 t/y (World Bank, 2010). Production of other poly- and
perfluorinated alkylated substances in the form of products or degradation products are in addition.
The issue of fluorinated substances co- and degradation products in the context of the technosphere is complex and there is inadequate knowledge of its extent, impact and danger posed by
breakdown products.
14. The Environmental Effects Assessment Panel (EEAP) reported (UNEP 1998) that trifluoroacetic acid
(TFA) precursors are relatively long lived and widely distributed on a global scale. Based on an
annual global rainfall of 4.9 x 10^17 litres the global average TFA concentration in rainwater was
expected to be less than 5 ng/l and a global average TFA concentration in rainwater for 2010 was
estimated to reach a range of 100-160 ng/l. Samples of rain and surface waters (oceans, rivers,
lakes, and springs) obtained from geographical widespread areas (USA, Canada, Australia, South
Africa, Germany, Israel, Ireland, France, Switzerland, Finland), however, show that TFA is a
ubiquitous contaminant of the hydrosphere with values up to 40 900 ng/l (EEAP, 1998). The
observed TFA concentrations are orders of magnitude larger than those of background levels or
predicted to result from the atmospheric degradation of HCFCs and HFCs. High concentrations of
observed TFA in contemporary water and air samples, suggest existence large unknown sources.
15. EEAP reported (UNEP 2002) that TFA is persistent but it is water soluble and chemically
nonreactive. Because of their properties, the breakdown products ultimately collect in the
environment. EEAP informed that breakdown products have a low toxicity to aquatic organisms and
are unlikely to adversely affect human health or the environment. Risks from the effects on humans
and the environment of TFA and chlorodifluoroacetic acid (CDFA) produced by atmospheric
degradation of HCFCs and HFCs were judged to be minimal. EEAP (2014) reports that TFA is very
resistant to breakdown, and amounts deposited in flowing surface water will ultimately accumulate in
the oceans. Based on estimates of current and future use of HFCs and HCFCs, additional inputs to
the ocean will add only fractionally (less than 0.1%) to amounts already present from natural sources
such as undersea vents and volcanic activity.
4
16. SAP (UNEP 2010) reported that TFA is a widespread in the environment, but uncertainties remain
regarding its natural and anthropogenic sources, long-term fate, and abundances. The molar yield of
TFA from oxidation of unsaturated HFC range from <10% (for trans-HFC-1234ze, transCF3CH=CHF) to 100% (for HFC-1234yf, CF3CF=CH2). HFC 1234ze is considered as an alternative
in the foam sector and R1234yf is being considered as a refrigerant e.g. in air conditioning systems
in cars. Recent studies report that in the event of a fire, there is also release of highly poisonous
carbonyl fluoride from R1234yf, and calls for a reassessment of safety (A. Kornath; Zeitschrift für
Naturforschung 2014).
17. SAP 2014 Assessment (UNEP 2014) reports that alternative low-GWP compounds (such as
hydrofluoro-olefins (HFOs)), one of which (HFO-1234yf), yields the persistent degradation product
trifluoroacetic acid (TFA) upon atmospheric oxidation. While the environmental effects of TFA are
considered to be negligible over the next few decades, potential longer-term impacts could require
future evaluations due to the environmental persistence of TFA and uncertainty in future uses of
HFOs.
18. The European Food Safety Authority (EFSA, 2012: EFSA Journal 2012;10(2):2596) observes that
TFA is a common metabolite to a wide range of pesticides and urges further information regarding
the toxicological profile of TFA to exclude a potential consumer health risk.
19. In conclusion, the amount of releases of fluorinated substances, formation of their degradation
products and their overall impact on heath and the eco-system is associated with much uncertainty.
20. Figure 2 below summarises the SAP 2014 options to advance the return of the ozone layer to the
1980 level (analyses based on mid-altitude EESC). The cumulative effect of elimination of emissions
from banks and production sector (e.g. CTC, CCl4) advances this return by 11 years. It is therefore
important to consider how the information could be used to to accelerate recovery of the ozone layer.
References:
i)
UNEP TEAP, 2014 Technology and Economic Assessment Panel (TEAP); UNEP Report of the
Technology and Economic Assessment Panel; May 2014; Volume 1; Progress Report; pp 3-47.
ii)
UNEP SAP, 2010; Science Assessment Panel (SAP); World Meteorological Organization;
Global Ozone Research and Monitoring Project—Report No. 52 Scientific Assessment of Ozone
Depletion: 2010; Pursuant to Article 6 of the Montreal Protocol on Substances that Deplete the
Ozone Layer; National Oceanic and Atmospheric Administration; National Aeronautics and
Space Administration; United Nations Environment Programme; World Meteorological
Organization; European Commission; Ozone -Depleting Substances (ODSs) and Related
Chemicals; Stephen A. Montzka and Stefan Reimann; pp I.7 - I.108.
5
iii)
UNEP, Environment Effects Assessment Panel (EEAP, 1998) Environmental Effects of Ozone
Depletion: 1998 Assessment, United Nations Environment Programme, 205pp, November 1998;
J.C. van der Leun, X. Tang and M. Tevini; ISBN 92-807-1724-3; Atmospheric Production and
Fate of Trifluoroacetic Acid; pp 147-159.
iv)
UNEP EEAP 2002; The Environmental Effects Assessment Panel Report for 2002;
Environmental Effects of Ozone Depletion and its Interactions with Climate Change: 2002; Jan
van der Leun, Xiaoyan Tang, and Manfred Tevin ISBN 92-807-2312-X.; pp 169.
v)
UNEP EEAP 2014; Environmental Effects of Ozone Depletion and its Interactions with Climate
Change: 2014 assessment.
vi)
J.C. Laube et al (2014); Newly detected ozone-depleting substances in the atmosphere; Nature
Geoscience Letters; 7,266–269(2014)doi:10.1038/ngeo2109; Published online 09 March 2014;
http://www.nature.com/ngeo/journal/v7/n4/full/ngeo2109.html
vii)
World Bank; UNEP and FECO (2010); Seminar on Current and Future Technology Options for
Meeting Montreal Protocol Accelerated HCFC Phase-out Obligations; Beijing October 27-28,
2010.
viii)
Swedish Ministry of the Environment (2014); Council (ENV) 12 June 2014 – Swedish AOB point:
Need for an EU Action plan for highly fluorinated substances (PFAS) Information from the
Swedish delegation; Monica Törnlund, 2014-06-23.
ix)
Kornath, A; Refreshingly Cool, Potentially Toxic; http://www.en.unimuenchen.de/news/newsarchiv/2014/kornath_refrigerant.html; Feller, MA; et al (2014); Z.
Naturforsch. 2014, 69b, pp 379 – 387.
x)
Butt, CM et al (2010); Levels and Trends of Poly- and Perfluorinated Compounds in the Arctic
Environment; Science of the Total Environment; 408 (2010) pp 2936–2965.
xi)
European Food Safety Authority (EFSA); (2012); Setting of new MRLs for saflufenacil in a wide
range of food commodities. EFSA Journal 2012; 10(2):2596. P.3 [62 pp.];
doi:10.2903/j.efsa.2012.2596. Available online: www.efsa.europa.eu/efsajournal.
xii)
Velders G. J. M.; Solomon, S; and Daniel, J. S. (2014) Growth of Climate Change Commitments
from HFC Banks and Emissions; Atmos. Chem. Phys., 14, 4563–4572, 2014; www.atmos-chemphys.net/14/4563/2014/doi:10.5194/acp-14-4563-2014.
xiii)
UNEP SAP 2014: Assessment for Decision-Makers: Scientific Assessment of Ozone Depletion:
2014, World Meteorological Organization, Global Ozone Research and Monitoring Project—
Report No. 56, Geneva, Switzerland, 2014.
xiv)
UNEP SAP 2014: Scientific Assessment Of Ozone Depletion: 2014 (WMO Report 55))
6
ANNEX
Figure 1- Trends and emissions CFC-113a and HCFC-133a. The range from Northern Hemispheric trend
reconstructions (originating from firn air collected in Greenland in summer 2008; Supplementary Information)
is shown as black dashed lines. Diamonds represent averages of measurements of individual samples
(collected at Cape Grim between 1978 and 2012) with 1standard deviations as error bars. The black solid
line is the model fit through this Southern Hemispheric time series that was used to infer the emissions (red
line, right-hand axis) and their 1uncertainties (red dashed lines). (Ref: Johannes C. Laube; 2014)
Fig 2: Atmospheric (“top-down”) global CCl4 emissions (Gg/yr) derived from observations (blue, red, and
orange lines some of which are shown in Figure 1-3) compared to “potential emissions” derived from UNEP
production data (green lines). The lower “potential emissions” green line is derived from the difference
between total CCl4 production (solid black line labelled “P”) reported to UNEP and the sum of feedstock and
amounts destroyed (dashed line labelled “F&D”) (production magnitudes to feedstock alone are indicated
with the dotted line labelled “F”). The upper “potential emission” green line was derived similarly as the lower
line but was augmented by additional amounts to fill apparent gaps in UNEP reporting, plus an allotment for
fugitive emissions of 2% of reported CCl4 feedstock use, plus an efficiency of only 75% for reported
destruction. Top down emission estimates are derived from a 1-box model of NOAA atmospheric data (red
line labelled N1) and a 12-box analysis of the AGAGE data (orange line labelled A12) with a lifetime of 26
years (see Box 1-1). The influence of lifetimes between 23 and 33 years on emissions derived with the 1-box
model from AGAGE data are also indicated (blue lines labelled A1, tau=23 and A1, tau=33). The TEAP
“bottom-up” emission estimate for 1996 is shown as a brown diamond (UNEP/TEAP, 1998) (Ref: SAP 2010)
7
Fig. 3-- “Top-down” and “bottom-up” global emission estimates for ozone-depleting substances (in Gg/yr).
“Top-down” emissions are derived with NOAA (red lines) and AGAGE (blue lines) global data and a 1-box
model. These emissions are also derived with a 12-box model and AGAGE data (grey lines with
uncertainties indicated) (see Box 1-1). Halon and HCFC emissions derived with the 12-box model in years
before 2004 are based on an analysis of the Cape Grim Air Archive only (Fraser et al., 1999). A1 scenario
emissions from the 2006 Assessment are black lines (Daniel and Velders et al., 2007). “Bottom-up”
emissions from banks (refrigeration, air conditioning, foams, and fire protection uses) are given as black plus
symbols (IPCC/TEAP, 2005; UNEP, 2007a), and total, “bottom-up” emissions (green lines) including fastrelease applications are shown for comparison (UNEP/TEAP, 2006). A previous bottom-up emission
estimate for CCl4 is shown as a brown point for 1996 (UNEP/TEAP, 1998). The influence of a range of
lifetimes for CCl4 (23–33 years) and a lifetime of 64 years for CFC-11 are given as light blue lines. (Ref SAP
2010)
8
Table 1. Emissions and banks of CFCs, HCFCs, and HFCs, and emissions of CO2. (Velders et al 2014)