Since its inception in 1988, the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS) has provided the primary source of information on the potential environmental effects of the hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). More than U.S. $11 million has been expended to date. In 1991, the sponsors of AFEAS initiated a research program on the environmental fate and potential effects of trifluoroacetic acid (TFA), a likely degradation product of HFC-134a, HCFC-123, HCFC-124, and HFC-227ea. A total of U.S. $1 million has been spent on TFA research and assessment activities.  
        The research supported by AFEAS has been conducted by independent scientists at universities, private research organizations and government laboratories around the world. The results have been rapidly disseminated in accordance with the AFEAS policy of encouraging timely publication in the scientific literature. Most of the current knowledge about the formation of TFA and its properties and reactions is the result of AFEAS-supported research. The state of the science and research activities are described in this overview report.  
 
 
 
 

Program Overview

        The AFEAS program on TFA was planned in two phases: Phase I --- Preliminary Studies (1992), and Phase II --- Research and Assessment (1993-1997). After conducting initial studies to determine the basic characteristics of TFA (Phase I), AFEAS convened an advisory committee of leading international experts to review the state of scientific knowledge on TFA and its fate in the environment, and to define issues needing further research. Following their recommendations, AFEAS has directed its TFA research toward four broad areas. In Phase II, work has been conducted in parallel in the following program areas:  
 
Program Area A- Biodegradation and Biotransformation of TFA
Program Area B- Potential Environmental Sinks for TFA
Program Area C- Toxicity, Metabolism and Bioaccumulation of TFA
Program Area D- Effects of TFA on Key Biogeochemical Processes
 
        The results of the TFA program have been reviewed with academic experts at two scientific workshops and the proceedings have been published (AFEAS 1994a, 1994b). A final review and risk assessment is being conducted based on the results of the AFEAS program. Independent experts will again be involved in the review process. The results of the risk assessment will be published in the peer-reviewed literature.  
 
 
 
 

State of Knowledge

Atmospheric breakdown of HFC-134a, HCFC-123, HCFC-124, and HFC-227ea is likely to produce traces of trifluoroacetyl halides (CF3COCl or CF3COF) in the atmosphere.
Trifluoroacetyl halides will hydrolyze in cloud water droplets or in surface waters. Within a few weeks, the trifluoroacetate, chloride and fluoride salts formed in cloud water will be deposited with rain. In surface waters, trifluoroacetic acid will be present as trifluoroacetate ion (CF3COO-; TFA).
The process of TFA formation from alternative fluorocarbons will make a negligible contribution to acid rain. There will be no significant addition to the chloride and fluoride already present in the biosphere from natural sources.
Based on current knowledge, TFA derived from these alternative fluorocarbons is expected to occur in rain and snow in very low concentrations. At these concentrations, TFA is not likely to have an impact on any of the wide range of organisms studied to date, which includes humans, animals, plants and microorganisms.
TFA is expected to be generally resistant to microbial degradation based on studies with diverse natural or laboratory microbial cultures.
TFA does not inhibit the growth of bacteria and most of the algae tested, even at high concentrations. The growth of one species of alga was inhibited by TFA concentrations about 1,000 times above the levels expected in rain and snow from alternative fluorocarbons.
AFEAS-sponsored research has shown that plants take up TFA through the roots as well as through leaf surfaces. Trifluoroacetate has no known toxicity to plants at the concentrations at which it is expected to be deposited in rain and snow. In prolonged exposure, however, at concentrations several thousand times greater than these levels, TFA inhibits plant growth and development.
Because TFA has very low affinity for lipids (fatty materials), there is no potential for passive accumulation in fatty tissues, even after long exposure at low levels, thus precluding bioconcentration in the food chain.
TFA has been detected at low levels in surface water, rain and tropospheric air samples. The source of most of the TFA in today's environment is uncertain, but the breakdown of HCFCs and HFCs can explain only a tiny fraction of the observed levels because of the small quantities of these alternative fluorocarbons produced and released to date.
 
 
 
 

Research Activities

        The AFEAS research program focused on the key questions related to the ultimate physico-chemical and biological fate of TFA. A summary of the individual studies and available results follows.

Phase I: Preliminary Studies (1992)

Physical / Chemical Properties

        In a study of the physical and chemical properties of TFA and sodium trifluoroacetate (NaTFA), Solvay's environmental research laboratory determined that TFA is completely miscible with water. With a pKa close to zero, TFA is entirely dissociated at all environmentally relevant pH levels. The extremely low octanol/water partition coefficient of TFA indicates that it has little or no potential for passive accumulation in fatty tissues and is likely to partition into aqueous compartments of the environment. Chemical degradation (i.e., decarboxylation, defluorination) was undetectable under environmental conditions and very slow under extreme conditions of heat and pH. The photolysis is unlikely because TFA does not absorb tropospheric radiation. TFA also demonstrated little or no potential for complexation and sequestration. No insoluble salts were formed in artificial seawater. In a screening test, no adsorption to three different standard soils was observed.

Preliminary Biodegradation Studies

        Biodegradation of TFA was not demonstrated under aerobic conditions using two standard OECD guideline tests: an extended closed bottle test, and a modified semi-continuous activated sludge (SCAS) test. In a study by Stroud Water Research Center, no evidence could be obtained for co- metabolic utilization of TFA by organisms growing on natural growth compounds. In a study of a TFA-containing industrial wastestream, there was no evidence for the presence of indigenous microorganisms adapted to growth on TFA as a sole carbon source.

Ecotoxicological Profile of TFA

        After the completion of these initial studies, a preliminary assessment of the available information on the environmental fate of TFA was conducted by Prof. Davide Calamari (University of Milan). He concluded that the compound is mobile and persistent with a mild herbicide potential and possible uptake by plants.

Phase II: Research and Assessment (1993-1997)

Program Area A --- Biodegradation and Biotransformation

Microbial Degradation

        Despite early results indicating anaerobic reductive dehalogenation (Visscher et al. 1994), the bulk of the results from several laboratories --- Michigan State University, U.S. Geological Survey, DuPont, Stroud Water Research, and Akzo --- suggests that TFA is generally recalcitrant to microbial degradation (Emptage et al. 1997). A broad range of microbial types have been investigated in these studies including aerobes, strict anaerobes, photosynthetics, and denitrifying bacteria. No reproducible evidence for TFA breakdown products has been obtained from studies of microbial activity inherent in any natural environmental sample. However, strong evidence was obtained for decarboxylation of TFA by particular bacterial strains under controlled laboratory conditions at Michigan State University. The conditions under which this transformation occurred are not likely to be reproduced in nature and therefore this mechanism would probably not represent a natural sink for TFA. The fate of the fluorine atoms in the Michigan State process is unknown.

Incorporation into Biomass

        A study conducted by Stroud Water Research Center focused on the incorporation of TFA into cellular components of aquatic microorganisms, aquatic invertebrates, and plants. Bacteria were shown to take up very low levels of TFA. Oligochete worms and one plant species contained low levels of radioactivity after exposure to 2-14C-TFA. No fluorinated biotransformation products were identified in the organisms studied.

Program Area B --- Potential Environmental Sinks for TFA

        AFEAS has sponsored work to examine potential environmental sinks for TFA. As indicated elsewhere in this review, no significant chemical or biological degradation or other loss processes have been identified so far. A summary of the studies on the environmental occurrence of TFA follows.

Environmental Occurrence of TFA

        The determination of background levels of TFA in the environment was conducted by two research groups. Prof. Hartmut Frank (University of Bayreuth, Germany) examined the presence of TFA in urban and remote areas. Prof. Anders Grimvall (Linköping University, Sweden) investigated the occurrence of TFA in precipitation at remote sites and in historic samples. 
        Air, rain and surface waters in Europe and Israel were extensively sampled and analyzed for trifluoroacetate by Prof. Frank during 1995 1996 and were reported in a letter to Nature (Frank et al. 1996). The results showed that trifluoroacetate is a ubiquitous contaminant of surface waters at the locations sampled, ranging in concentration from 6.4 µg/l in the Dead Sea to 0.25 µg/l in the North Atlantic and 0.04 µg/l in the Baltic Sea; concentrations in rivers ranged from 0.63 µg/l in the Rhine at Coblenz to 0.06 µg/l in the Roter Main near Bayreuth. TFA concentrations were near or below the detection limit of about 0.01 µg/l in centuries-old samples of ground water from Germany, and in samples of river water from remote areas of Siberia and South America. 
        TFA was also present consistently in air and rain samples at Bayreuth --- averaging 50 pg/m3 (0.01 parts per trillion by volume) in air and 0.1 µg/l in rain --- over the period March to December 1995. Since the current potential source of TFA from fluorochemicals in the atmosphere would provide about 0.0016 µg/l in rainwater in this region, a substantial additional --- but as yet unknown --- source of TFA must exist to account for the observations. 
        In the other study, Prof. Grimvall analyzed samples of rain and of glacier ice and snowpack collected at remote sites in the Northern and Southern hemispheres. Information about TFA concentrations in precipitation in both hemispheres will provide valuable input to global budget calculations which will help determine the nature of the other sources of TFA in the environment. 
        Work on TFA in the environment has also been conducted outside of the AFEAS-sponsored program under Dr. James Seiber (University of Nevada --- Reno). Rainwater collected in Nevada and California was found to contain 0.03 0.09 µg/l, while TFA levels in surface waters ranged up to 40 µg/l in surface samples taken from a land-locked lake in Nevada (Zehavi and Seiber, 1996). 

Program Area C --- Toxicity, Metabolism and Bioaccumulation

        The results of the AFEAS-sponsored tests of toxicity, metabolism and bioaccumulation are discussed below. Table 1 contains a summary of the toxicity of sodium trifluoroacetic acid to the aquatic and terrestrial organisms studied, along with definitions of common terms (e.g., EC50, LOEC, NOEC).

Toxicity to Aquatic Organisms

        The effects of sodium trifluoroacetate (NaTFA) on the growth of duckweed (Lemna gibba) was studied by Brixham Environmental Laboratory (Zeneca, Ltd). The EC50 for frond increase was 1100 mg/l and for weight increase was 1200 mg/l. The tissues showed only a slight bioconcentration of the compound after 7 days. 
        The acute toxicity of NaTFA was evaluated in different aquatic organisms by Solvay's environmental research laboratory. The LC50 in fish and crustacea was greater than 1200 mg/l. The EC50 for a freshwater green alga, Selenastrum capricornutum (new name: Raphidocelis subcapitata), was 4.8 mg/l for biomass and 160 mg/l for growth rate; the NOEC was 0.12 mg/l. Elf Atochem's Laboratory of Ecotoxicology obtained similar results on the same species: EC50 was 1.5 mg/l for biomass and 7.7 mg/l for growth rate; EC10 was 0.15 and 1.2 mg/l, respectively, for biomass and growth rate. (Note: EC10 for biomass can be considered a surrogate for NOEC.) Brixham studied the effects of NaTFA on the growth of three other species of algae: a freshwater diatom (Navicula pelliculosa), a marine diatom (Skeletonema costatum), and a fresh-water blue-green alga (Anabaena flos-aquae). The EC50 value for biomass for all three species was calculated to be 1200 mg/l to >2400 mg/l, with a NOEC in the range of 600 2400 mg/l. All of the species studied are standard test organisms. 
        Following these experiments, Solvay compared the toxicity of sodium trifluoroacetate and its potential dehalogenation products --- difluoroacetic acid, sodium monofluoroacetate, and sodium fluoride --- with two different species of algae: Selenastrum capricornutum and Scenedesmus subspicatus. Sodium monofluoroacetate was the most toxic compound for both Selenastrum and Scenedesmus. Sodium fluoride showed a small inhibitory effect only on Selenastrum. Sodium trifluoroacetate and difluoroacetic acid showed an intermediate degree of toxicity to Selenastrum, while they were only slightly toxic to Scenedesmus
        Further research on the mechanism of the toxicity of TFA to the most sensitive species of alga studied, Selenastrum capricornutum, was inconclusive. The biotransformation of trifluoroacetate was less than 4% during the 3-day incubation period; the bioaccumulation factor was less than 10. 

Multi-Species Algal Study

        Further toxicity tests with sodium trifluoroacetate in algae were conducted by Solvay on the following species: Chlorella vulgaris, Chlamydomonas reinhardtii, Dunaliella tertiolecta, Euglena gracilis, Phaeodactylum tricornutum, and Microcystis aeruginosa. None of these species showed any effect when exposed to about 120 mg/l sodium trifluoroacetate. 
        Together with the species tested previously, a total of 11 different species of algae have now been evaluated. The species belong to four different classes: Chlorophyceae (4 freshwater and 1 marine species), Euglenophyceae (1 freshwater species), Cyanophyceae (2 freshwater species), and Bacillariophyceae (1 freshwater and 2 marine species). 
 
Table 1. Summary of the Toxicity of Sodium Trifluoroacetate
Aquatic Organisms EC50 / LC50 LOEC NOEC
Selenastrum capricornutum
(freshwater green alga) (new name: Raphidocelis subcapitata)
4.8 mg/l
1.5 mg/l
0.36 mg/l0.12 mg/l
0.15 mg/l
Anabaena flos-aquae
(blue-green alga)
2400 mg/l1200 mg/l600 mg/l
Navicula pelliculosa
(freshwater diatom)
1200 mg/l1200 mg/l600 mg/l
Skeletonema costatum
(marine diatom)
>2400 mg/l---2400 mg/l
Chlorella vulgaris
(freshwater green alga)
>1200 mg/l---1200 mg/l
Scenedesmus subspicatus
(freshwater green alga)
>120 mg/l------
Chlamydomonas reinhardtii >120 mg/l >120 mg/l
Microcystis aeruginosa >117 mg/l >117 mg/l
Phaeodactylum tricornutum
(marine alga)
>117 mg/l >117 mg/l
Dunaliella tertiolecta >124 mg/l >124 mg/l
Euglena gracilis
(freshwater alga)
>112 mg/l >112 mg/l
Daphnia magna
(crustacea)
>1200 mg/l---1200 mg/l
Brachydanio rerio
(Zebra fish)
>1200 mg/l---1200 mg/l
Lemna gibba
(duckweed) --- vegetative growth
1100 mg/l600 mg/l300 mg/l
Terrestrial Plants
Multiple species
(monocotyledons and dicotyledons)
--- seed germination


>1000 mg/l


---


1000 mg/l
Mung Bean
--- soil application

5.7 mg/kg

10 mg/kg

1 mg/kg
Sunflower (Helianthus annuus)
--- soil application
--- foliar application

12 mg/kg
---

1 mg/kg
---

<1 mg/kg
100 mg/l
Wheat (Triticum aestivum)
--- soil application
--- root exposure
--- foliar application

12 mg/kg
---
---

10 mg/kg
5 mg/l
100 mg/l

1 mg/kg
1 mg/l
50 mg/l
Plantain (Plantago major)
--- root exposure
--- foliar application

---
---

100 mg/l
---

32 mg/l
100 mg/l
Soya
--- root exposure
--- foliar application

---
---

10 mg/l
100 mg/l

1 mg/l
10 mg/l
Maize, oilseed rape, rice
--- foliar application

---

---

100 mg/l

NOTE: For comparison, the anticipated environmental concentration is in the region of 0.00016 mg/l.
 
Units:
mg/l --- for tests with NaTFA in aqueous solution
mg/kg (dry weight of soil) --- for tests with NaTFA applied to soil
Terms:
EC50 = test concentration resulting in a 50% effect; the table lists EC50 for biomass
LC50 = concentration at which 50% of the organisms show an effect (mortality)
LOEC = lowest observed effect concentration
NOEC = no observed effect concentration

Mesocosm Study

        One semi-field stream study has been conducted by the Stroud Water Research Center with sodium trifluoroacetate to investigate the potential effects of trifluoroacetate on freshwater algal communities and primary productivity. The long-term exposure to a mean sodium trifluoroacetate concentration of ~30 µg/l had no effect on the algal primary production in the stream mesocosm. In addition, no severe effects or consistent trends were observed in the algal species composition.

Toxicity to Terrestrial Plants

        The effects of sodium trifluoroacetate in soil on seed germination and early plant growth of wheat, sunflower and mung bean were studied by Brixham Environmental Laboratory. The EC50 values for wheat, sunflower and mung bean were calculated to be 12, 12 and 5.7 mg/kg dry soil, respectively. The NOEC's were determined to be 1 mg/kg dry soil for wheat and mung bean and < 1mg/kg dry soil for sunflower. In another study, the seeds of 10 species of plants (monocotyledons and dicotyledons) were exposed to a range of aqueous concentrations of NaTFA for 5 to 7 days. There was no significant inhibition of germination of any seeds up to a concentration of 1000 mg/l of NaTFA (maximum tested concentration). 
        Brixham Environmental Laboratory conducted a toxicity study with higher plants by aqueous exposure of the roots. Sodium trifluoroacetate showed toxicity to wheat and to Plantago major (plantain). In the preliminary study with wheat, a significant effect in both leaf and root weight was observed at all three concentrations (32, 100, 320 mg/l). In the definitive study, wheat seedlings were exposed to 1 and 10 mg/l concentrations of 14C radiolabelled NaTFA. The growth of plants exposed to 10 mg/l of NaTFA was significantly inhibited; there was no significant effect on growth at 1 mg/l exposure concentration and no other symptoms of toxicity were observed. Growth of Plantago major seedlings was inhibited at 100 mg/l of NaTFA. No effects on the seedlings were observed at or below 32 mg/l. 
        AFEAS also funded a study at the University of Missouri to investigate the effects of NaTFA-treated soils at concentrations of 1, 10 and 100 mg/kg soil on soybean germination and seedling growth. The results show no effect of 1 mg/kg NaTFA on germination or growth, or on acetylene reduction activity of the soybean nodules. Toxic effects on plant growth were observed at the 10 and 100 mg/kg levels. 
        Prof. Alan Davison at the University of Newcastle (U.K.) investigated the effects of foliar application of solutions of NaTFA. Seedlings of seven species of terrestrial plant --- sunflower, soya, wheat, maize, oilseed rape, rice and plantain --- were field-grown to ensure that the leaves were fully hardened, and exposed to sprayed solutions of NaTFA for 24 hours. The soil and plant roots were protected from the application. After three weeks, there was no effect of TFA on height, leaf number, stomatal conductance, final harvest weight, or chlorophyll and carotenoid concentrations of any of the species at the maximum concentration tested which was 100 mg NaTFA/l. There was a significant effect on specific leaf area for one species (wheat) at 100 mg/l, but no effect at 50 mg/l. 
        A subsequent study, at only 100 mg NaTFA/l, used a similar system but with laboratory-grown plants --- wheat, maize, sunflower and soya --- both with and without protection of the soil and roots from the spray. Only soya showed any symptoms of toxicity. These were apparent by both routes of exposure, suggesting that laboratory-grown plants were more sensitive to foliar application than those that had been field-hardened; however, the symptoms were more severe when the TFA solution was able to reach the roots. Soya seedlings, with soil and roots exposed to the foliar spraying, were treated with a range of concentrations of NaTFA to simulate 10 mm of rainfall. There was no effect at 1, 5 and 10 mg/l on dry weight, leaf size or stomatal conductance (transpiration). At 100 mg/l, symptoms of toxicity were apparent and leaf size --- but not dry weight --- was reduced, suggesting TFA affected leaf expansion. 
        Soya seedlings were exposed to 5 and 10 mg NaTFA/l for 6 weeks by root exposure using a hydroponic system. Symptoms of toxicity were observed after 20 days at 10 mg/l. Less severe and sporadic symptoms were observed at 5 mg/l by the end of the study. In a similar study with wheat (Hanno variety) no effects were seen at either concentration after 52 days, at which stage flowering was beginning. The absence of effects at 10 mg/l suggested that this variety of wheat might be less sensitive than the Katepwa variety used in Brixham's earlier study. Therefore, the experiment was repeated using seed from the same batch used by Brixham, testing at 1, 5, 10 and 100 mg NaTFA/l. At 100 mg/l, all the plants died and at 10 mg/l growth stopped. At 5 mg/l symptoms of toxicity were evident after 30 to 35 days. There was no significant effect on final harvest weight at 1 mg NaTFA/l after 43 days, which was in agreement with the Brixham study. Further hydroponic exposures with soya have also shown no effect on shoot weight at 1 mg NaTFA/l after 43 days. 

Bioaccumulation via Plant Root

        Brixham Environmental Laboratory conducted experiments on the potential for bioaccumulation of TFA via plant roots. Sunflower seedlings were exposed to a single concentration of radiolabelled TFA of 2 µg/l (0.002 mg/l) in the aqueous medium surrounding the roots. The bioconcentration factor (BCF) in the leaves was calculated to be 22 after 12 days; the BCF for the whole plant was ~10. The accumulation rate was somewhat less than would be expected from passive influx in the transpiration stream without efflux. A significant quantity of radiolabel was lost to the medium surrounding the roots. It was concluded that the plants showed some excretion via the roots. Further studies would be required to quantify the depuration rate. 
        At the end of the sunflower study, more than 80% of the 14C-residues in the leaves were found to be extractable in water after tissue maceration. Fractionation of the extract using ion chromatography showed the residues co-eluted with a trifluoroacetate standard spiked into leaf extract, suggesting that no significant metabolism of TFA had occurred. 
        The accumulation of 14C-residues of trifluoroacetate was also monitored as part of Zeneca's hydroponic toxicity study with wheat (described previously). At 1 mg/l, the bioconcentration factor, based on fresh weight, increased continuously over the exposure period to a final value of 27. The concentrations in the tips of the leaves were approximately 4 times greater than in the remaining leaf tissues. At 10 mg/l, a similar BCF was observed and tissue necrosis in the tips of the leaves appeared to occur as tissue residues reached approximately 1000 mg/kg (fresh weight). 
        Accumulation of trifluoroacetate by soya and wheat was investigated by the University of Newcastle, by determination of fluoride ion, after fusion of the tissue with sodium carbonate to cleave CF bonds. For soya exposed to 5 mg/l, the tissue concentration in the oldest leaves reached a plateau after about 20 days. Each successive set of leaves, if fully developed, attained higher tissue concentrations. First symptoms of toxicity were associated with average leaf tissue levels of approximately 150 mg/kg (dry weight). For wheat exposed to 1 mg/l, tissue concentrations also reached a plateau after approximately 25 days. At 5 mg/l, the average leaf tissue concentration was approximately 200 mg/kg (dry weight) when growth inhibition was first evident. 

Program Area D --- Effects of TFA on Key Biogeochemical Processes

Effects on Carbon Cycling

        The effects of a range of concentrations of TFA on carbon cycling was determined in freshwater environments by Stroud Water Research Center. No evidence of acute toxicity of TFA to the freshwater incubated communities was observed, as described previously. Overall, the data showed evidence of a very weak competitive interaction between TFA and acetate when TFA concentrations were at several hundred fold higher concentrations than those anticipated in the environment. There was no evidence of a TFA effect on photosynthetic carbon dioxide fixation at or even near the concentration which could be anticipated in the environment.

Soil Adsorption Studies

        Preliminary studies in Phase I indicated that TFA did not adsorb to three different soils. However, in a much more extensive investigation of 54 soils by researchers at Syracuse University, TFA adsorption was found to correlate with the content of oxidizable organic matter. Soils from wetlands, peat bogs and a boreal forest showed the highest TFA retention. Soils low in organics were found to be non-interactive with TFA. TFA retention was influenced by pH and other anions. The indications are that some soils could act to retard the transmission of TFA with water and that the TFA could accumulate to some degree in these soils.

Effects on Nitrogen Fixation

        DuPont's environmental biotechnology group initiated laboratory experiments to determine whether there was any impact of TFA on the ability of pure cultures of certain eubacterial strains to grow by nitrogen fixation. Two parameters were measured as a function of TFA concentration: nitrogen-dependent growth and nitrogenase activity. 
        The effect of TFA has been investigated in free-living nitrogen-fixing bacteria as well as nitrogen-fixing bacteria which live in symbiosis with leguminous plants. Three species of free-living nitrogen-fixing bacteria have been investigated: an aerobic organism (Azotobacter vinelandii), a photosynthetic bacterium (Rhodobacter capsulatus), and an anaerobe (Clostridium pasteurianum). These species were tested for their ability to grow by nitrogen fixation. Tests for any direct effects of TFA on nitrogen fixation were also performed. The investigators found no effects of TFA on growth in these species at concentrations up to 100 mg/kg. 
        Studies conducted at the University of Missouri have shown that TFA at concentrations of 1 mg/kg of soil had no effect on the germination or growth of soybean seedlings; 1 mg/kg TFA also had no discernible effect on the nitrogen-fixing capacity of these soybean plants as determined by plant nodule development as well as acetylene reduction activity of the nodules. Toxic effects were observed at the level of 10 100 mg/kg TFA. 

Projected Distribution of TFA

        Using the U.S. Environmental Protection Agency's precursor emission scenario, Atmospheric and Environmental Research, Inc. (AER) calculated the global average concentration of TFA in precipitation for the year 2010 to be about 0.16 µg/l (0.00016 mg/l). The results were discussed at the AFEAS workshop on the environmental fate of trifluoroacetic acid in 1994 and by Kotamarthi et al. (1997). 
        A review of the literature was conducted by Dr. Steven E. Schwarzbach and co-workers (U.S. Fish and Wildlife Service) to assess the extent to which relatively stable solutes deposited with rain and snow may become more concentrated through evaporative processes. The measurements reported in the literature, limited to surface water samples, have indicated seasonal evaporative concentrations factors ranging from 1.2 to 6.5 and from 1.5 to 50 for vernal pools and playa lakes, respectively. 
        In a second study, AER conducted a sensitivity analysis addressing possible future concentrations of TFA in surface waters and soils under a range of various environmental conditions, using the U.S. EPA precursor emission scenario. The possible outcomes cover a broad range of concentrations. At the low end, there will be considerable dilution of TFA-containing precipitation in the oceans and other bodies of water with a long residence time. At the other extreme, TFA concentrations may conceivably be enhanced in seasonal wetlands and other surface waters undergoing rapid seasonal evaporation. Depending on meteorological conditions, further enhancement might occur due to transport of precursors originating in urban areas. A paper on this study was published by Nature (Tromp et al. 1995). 
        In the sensitivity study, AER considered several factors that may increase the concentration of TFA in precipitation in urban areas above the expected global averaged values. These factors include enhanced concentrations of precursor gases due to local emission sources, trapping and buildup of precursor gases in a stagnant air mass in a basin during an air inversion, and elevated concentrations of the OH radical (the principal oxidant initiating atmospheric degradation of precursors) occurring during air pollution episodes coupled with rainout. Using observed values of ozone, NOx and hydrocarbons at one location in the Los Angeles basin (Riverside) during June 1990, calculations indicated that maximum OH concentrations would be less than a factor of two greater than the monthly averaged value. AER also concluded that OH concentrations in typical urban pollution events will not be significantly elevated over clean air background levels because OH is suppressed by high concentrations of NOx and hydrocarbons. The study did not include detailed assessments of the other factors influencing TFA deposition.
 
 
 
 

Final Review and Risk Assessment

        The AFEAS-sponsored research activities were completed in 1997. An environmental risk assessment has been conducted based on the results of the TFA studies. Leading international experts were involved in the review and assessment process. The risk assessment and several review articles have been published in the peer-reviewed literature (Boutonnet et al., 1998; Berends et al., 1998).
 
 
 
 

Bibliography

AFEAS. Proceedings of a Workshop on the Decomposition of TFA in the Environment. (February 1994; Washington D.C.), publ. by Alternative Fluorocarbons Environmental Acceptability Study, Washington D.C., 1994a.
AFEAS. Proceedings of a Workshop on the Environmental Fate of Trifluoroacetic Acid. (March 1994; Miami Beach, Florida), publ. by Alternative Fluorocarbons Environmental Acceptability Study, Washington D.C., 1994b..
Berends, A.G., J.C. Boutonnet, C.G. de Rooij, and R.S. Thompson. "The Toxicity of Trifluoroacetate to Aquatic Organisms," Environmental Toxicology and Chemistry, in press, 1998.
Boutonnet, J.C., et al. "Environmental Risk Assessment of Trifluoroacetic Acid," Human and Ecological Risk Assessment, in press, Feb. 1999.
Emptage, M.N.J., J. Tabinowski, and J.M. Odom. "The effects of fluoroacetates on methanogenesis in samples from selected methanogenic environments," Environmental Science & Technology, 31, 2, 1997.
Frank, H., A. Klein, and D. Renschen. "Environmental trifluoroacetate," Nature, 382, 34, 1996.
Kotamarthi, V.R., J.M. Rodriguez, M.K.W. Ko, T.K. Tromp, and N.D. Sze. "Trifluoroacetic acid from the degradation of HCFCs and HFCs: A three-dimensional modeling study," J. Geophys. Research, 1997.
Tromp, T.K., M.K.W. Ko, J.M. Rodriguez, and N.D. Sze. "Potential accumulation of a CFC-replacement degradation product in seasonal wetlands," Nature, 376, 327, 1995.
Visscher, P.T., C.W. Culbertson, and R.S. Oremland. "Degradation of trifluoroacetate in oxic and anoxic sediments," Nature, 369, 729, 1994.
Zehavi, D., and J.N. Seiber. "An analytical method for trifluoroacetic acid in water and air samples using headspace gas chromatographic determination of the methyl ester," Analytical Chemistry, 68, 3450-9, 1996.
 
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