Sources, fate and transport of perfluorocarboxylates.
ABSTRACT This review describes the sources, fate, and transport of perfluorocarboxylates (PFCAs) in the environment, with a specific focus on perfluorooctanoate (PFO). The global historical industry-wide emissions of total PFCAs from direct (manufacture, use, consumer products) and indirect (PFCA impurities and/or precursors) sources were estimated to be 3200-7300 tonnes. It was estimated that the majority (approximately 80%) of PFCAs have been released to the environment from fluoropolymer manufacture and use. Although indirect sources were estimated to be much less importantthan direct sources, there were larger uncertainties associated with the calculations for indirect sources. The physical-chemical properties of PFO (negligible vapor pressure, high solubility in water, and moderate sorption to solids) suggested that PFO would accumulate in surface waters. Estimated mass inventories of PFO in various environmental compartments confirmed that surface waters, especially oceans, contain the majority of PFO. The only environmental sinks for PFO were identified to be sediment burial and transport to the deep oceans, implying a long environmental residence time. Transport pathways for PFCAs in the environment were reviewed, and it was concluded that, in addition to atmospheric transport/degradation of precursors, atmospheric and ocean water transport of the PFCAs themselves could significantly contribute to their long-range transport. It was estimated that 2-12 tonnes/ year of PFO are transported to the Artic by oceanic transport, which is greater than the amount estimated to result from atmospheric transport/degradation of precursors.
- SourceAvailable from: Marko Filipovic[Show abstract] [Hide abstract]
ABSTRACT: Perfluoroalkyl acids (PFAAs) are man-made chemicals. Their unique properties make them beneficial for a wide range of industrial and consumer applications, such as constituents in fire fighting foams, hydraulic oils and food packaging materials.PFAAs have shown to be highly persistent in the environment, and the toxicological potential of long chain PFAA homologues is of a concern. International regulation and voluntary actions by the industry have been implemented and led to reduced primary emissions of PFAAs to the environment. However, the concentrations of some PFAAs in e.g. birds from the Baltic Sea are still very high and of ecotoxicological concern. Measures to reduce the PFAA contamination require an understanding of the sources and how the PFAAs are being transported in the environment.In this licentiate thesis a mass balance was assembled for perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA) and perfluorooctane sulfonic acid (PFOS) in the Baltic Sea. A one-box model was used including the input pathways river inflow, atmospheric deposition, wastewater discharges and inflow from the North Sea via the Danish Straits, while the loss processes considered were sediment burial, transformation of the chemicals and outflow to the North Sea via the Danish Straits. Additionally, the inventories of the four target PFAAs in the Baltic Sea were estimated. Both chemical fluxes and inventories were estimated using recently published monitoring data (2005-2010).In order to obtain a detailed perspective on the current knowledge regarding PFAAs in the Baltic Sea, challenges and uncertainties in data selection were discussed for the most dominant input pathways. This included WWTP emissions and calculation of emission factors (EFs), atmospheric deposition and riverine inflow.River inflow and atmospheric deposition were the dominant inputs, while wastewater treatment plant (WWTP) effluents made a minor contribution. The input to the Baltic Sea exceeded the output for all 4 PFAAs, suggesting that inputs were higher during 2005-2010 than during the previous 20 years despite efforts to reduce emissions of PFAAs. Comparing the difference between PFAA input and output with the PFAA inventory, the doubling time for the concentration in the Baltic Sea was estimated to be 8-94 yr for PFHxA, 12-16 yr for PFOA, 3-5 yr for PFDA and 4 yr for PFOS. The surplus of the input can be an effect of retention and delayed release of PFAAs from atmospheric deposition in the soils and groundwater of the watershed.The licentiate thesis contributes to a holistic understanding of the major input and output pathways and inventories of PFAAs in the Baltic Sea. Furthermore, it points out current knowledge gaps in our understanding of sources and fate of PFAAs in the aquatic environment. http://su.diva-portal.org/smash/record.jsf?dswid=-8710&pid=diva2%3A613361&c=5&searchType=SIMPLE&language=sv&query=Marko&af=%5B%5D&aq=%5B%5B%5D%5D&aq2=%5B%5B%5D%5D&aqe=%5B%5D&noOfRows=50&sortOrder=author_sort_asc&onlyFullText=false&sf=all&jfwid=-871004/2013, Degree: Licentiate, Supervisor: Urs Berger, Michael McLachlan
- [Show abstract] [Hide abstract]
ABSTRACT: The sorption of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) onto five types of soils was investigated in this study. Effects of inorganic salts (CaCl2, NaCl, and Na2SO4) and humic acid (HA) in solution on the extent of sorption of PFOA and PFOS were evaluated. The results indicated that all types of soils had a higher affinity for PFOS than for PFOA. The extent of sorption for PFOA and PFOS increased with the fraction of organic carbon (foc) of soils. The partition coefficient (Kd) values of PFOA and PFOS increased with foc and ionic strengths of inorganic salts. On the contrary, the Kd values decreased with an increase in the concentrations of HA in the solution. The existence of organic matter is the parameter dominating the sorption behaviors of both PFOA and PFOS onto all types of soils studied. In addition, the presence of inorganic salts also affects PFAS’s sorption behaviors. The results in this study should verify profitable for PFOA and PFOS environmental fate modeling and risk assessment in wetland systems.Desalination and water treatment 12/2013; 51(40-42):7469-7475. · 0.99 Impact Factor
Dataset: Mudumbi caparthian
Sources, Fate and Transport of Perfluorocarboxylates
K O N S T A N T I N O S P R E V E D O U R O S ,†I A N T . C O U S I N S , *, †
R O B E R T C . B U C K ,‡A N D S T E P H E N H . K O R Z E N I O W S K I‡
Department of Applied Environmental Science (ITM), Stockholm University,
SE-10691 Stockholm, Sweden, and E. I. duPont de Nemours & Co., Inc.,
P.O. Box 80023, Wilmington, Delaware 19880-0023
This review describes the sources, fate, and transport of
perfluorocarboxylates (PFCAs) in the environment, with a
specific focus on perfluorooctanoate (PFO). The global
historical industry-wide emissions of total PFCAs from direct
(manufacture, use, consumer products) and indirect
to be 3200-7300 tonnes. It was estimated that the
majority (∼80%) of PFCAs have been released to the
environment from fluoropolymer manufacture and use.
Although indirect sources were estimated to be much less
associated with the calculations for indirect sources.
The physical-chemical properties of PFO (negligible vapor
pressure, high solubility in water, and moderate sorption
to solids) suggested that PFO would accumulate in surface
waters. Estimated mass inventories of PFO in various
especially oceans, contain the majority of PFO. The only
environmental sinks for PFO were identified to be sediment
burial and transport to the deep oceans, implying a long
in the environment were reviewed, and it was concluded
that, in addition to atmospheric transport/degradation
of precursors, atmospheric and ocean water transport of
the PFCAs themselves could significantly contribute to their
long-range transport. It was estimated that 2-12 tonnes/
which is greater than the amount estimated to result
from atmospheric transport/degradation of precursors.
Production of perfluoroalkyl carboxylates [F(CF2)nCO2, n g
process (1). Early uses documented in 1966 for this “new
class of compounds” were based upon their chemical
stability, surface tension lowering properties, and ability to
coating formulations, fire-fighting foams, polyurethane
textiles (2). Many of these uses were still in practice in the
PFCAs and their potential precursors are of increasing
scientific and regulatory (4) interest because they have been
found globally in wildlife and in humans (5-15). However,
the sources of PFCAs in the environment, their physical-
chemical properties, and fate and transport are not well
understood or described.
This paper provides the first detailed accounting of the
direct and indirect sources of PFCAs released into the
historical global emissions from production and use as well
as PFCA emissions from potential degradation of poly- and
2004. Recent industry actions to reduce PFCA global emis-
sions are described. The paper additionally reviews the
which there is the most available information as representa-
tive of PFCAs in general. PFO mass inventories in different
environmental compartments are estimated to provide an
indication of environmental distribution. Finally, key PFO
Sources of PFCAs
PFCAs. The historical period of use or production and an
estimation of the global industry-wide emissions for each
estimations are provided as ranges based on available data
to account for the uncertainty in production, use, and
emissions values over time. Computational details for the
acronyms, and chemical structures are provided in the
namely: electrochemical fluorination (ECF), fluorotelomer
iodide oxidation, fluorotelomer olefin oxidation, and fluo-
rotelomer iodide carboxylation. Historically, commercial
carbon PFCAs as their major component. Depending upon
the synthesis route and raw material, the PFCA products
also contained homologues ranging from four to thirteen
carbons with as much as 30 wt % branched PFCAs present
(16, 17). An overview of the chain length composition,
predominance of even (E) or odd (O) and straight (S) or
branched (B) character from PFCA manufacture is shown in
Figure 2. Direct PFCA sources are highlighted in the upper
part of Figure 2. The chemical synthesis routes and com-
position of some representative commercial PFCA products
are provided in the Supporting Information.
From 1947 through 2002, the ECF process (16) was used
worldwide to manufacture the majority (80-90% in 2000) of
* Corresponding author phone: (+46)(0) 8 16 4012; fax: (+46)(0)
8 674 7638; e-mail: email@example.com.
‡E. I. duPont de Nemours & Co., Inc.
329ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 200610.1021/es0512475 CCC: $33.50
2006 American Chemical Society
Published on Web 12/01/2005
ammonium perfluorooctanoate (APFO). The largest produc-
tion sites were in the United States and Belgium, the next
largest were in Italy, and small scale producers were located
from about 1975 to present by direct oxidation of perfluo-
rooctyl iodide (18) at one site in Germany and at least one
FC-118) has been used in recent years because solid APFO
readily sublimes and proved difficult to handle. Additional
production, use, and disposal of limited research quantities
of PFCAs has taken place in numerous academic and
industrial locations worldwide over the past 50 years as
indicated by patents and papers in the scientific literature.
In 1999, global annual APFO production was approximately
260 tonnes (t) (20). PFO emissions from the largest ECF
FIGURE 1. Potential sources of perfluorocarboxylates (PFCAs) F(CF2)nCOO-: APFO ) ammonium perfluorooctanoate; APFN ) ammonium
perfluorononanoate; AFFF ) aqueous fire-fighting foam; POSF ) perfluorooctylsulfonyl fluoride.
TABLE 1. Global Historical PFCA Production and Emissions Summarya
environmental input source
estimated total global
historical PFCA emissions
Direct PFCA Sources
Industrial and Consumer Uses
fluoropolymer manufacture (APFO)
fluoropolymer dispersion processing (APFO)
fluoropolymer manufacture (APFN)
fluoropolymer processing (APFN)
aqueous fire fighting foams (AFFF)
consumer and industrial products
Indirect PFCA Sources
PFCA residual impurities
POSF-based precursor degradation
PFCA residual impurities
fluorotelomer-based precursor degradation
total source emissions (direct + indirect)
aLow and high estimated values as well as the period of use/production for each source are based upon publicly available information cited
in the text. See the Supporting Information for additional details.
VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY933
in 2000, roughly 5% discharged to air and 95% to water (21).
The estimated historical (1951-2004) industry-wide global
emissions from APFO manufacture are between 400 and
By 2002, the principal worldwide APFO manufacturer by
the ECF process discontinued external sales and ceased
production leaving only a number of relatively small pro-
ducers in Europe and in Asia (22). New APFO production
capacity based on >99% pure perfluorooctyl iodide com-
releases of approximately 50 kg per year to air (23). With the
termination of U.S. ECF-based manufacture, current and
future U.S. releases from APFO manufacture have been
dramatically reduced from many t per year to kg per year.
As a result, global APFO manufacturing emissions have
decreased from about 45 t in 1999 to about 15 t in 2004 and
to an expected 7 t in 2006 (20).
primarily in Japan by oxidation of a mixture of linear
fluorotelomer olefins (FTOs) to the corresponding odd-
numbered PFCAs (24, 25). The principal raw material is 8-2
fluorotelomer olefin (8-2 FTO). Surflon S-111, a commercial
product (CAS 72968-3-88), is described as “Fatty acids,
C7-13, perfluoro, ammonium salts” a mixture of PFCAs
between seven and thirteen carbons in length (26). Patent
a process for APFN production (27). The starting fluorote-
lomer olefin or iodide dictates the resulting PFCA composi-
tion. APFN production is believed to have started in about
1975 (24) and continues today. APFN is primarily used as a
processing aid in fluoropolymer manufacture, most notably
polyvinylidene fluoride (PVDF). We estimate annual APFN
production in 2004 to be between 15 and 75 t. We further
estimate emissions to air and water from APFN production
to be 10% of the amount produced. Based upon APFN
production from 1975 to 2004, estimated historical global
emissions from APFN manufacture are between 70 and 200
t. No information was found describing efforts to reduce
emissions from APFN manufacture.
Fluoropolymer Manufacture and Processing. PFCAs have
been used for over fifty years as processing aids in the
manufacture of fluoropolymers such as polytetrafluoroet-
hylene (PTFE) and polyvinylidene fluoride (PVDF) (28).
Fluoropolymer manufacture is the single largest direct use
of the ammonium salts of perfluorooctanoic and perfluo-
rononanoic acid (PFOA and PFNA). They act to solubilize
fluoromonomers to facilitate their aqueous polymerization.
worldwide located in North America (eight), Japan (seven),
manufacture was 61% emitted, 14% reprocessed, 7% de-
stroyed, and 16% remaining in fluoropolymer dispersion
products (20, 31). In 2000, it is estimated that 230-375 t of
PFCAs were produced and used globally as processing aids
for fluoropolymer manufacture: 85% APFO and 15% APFN.
PFCA point source emissions from fluoropolymer manu-
total PFCAs used corresponding to 110 and 250 t per year
with 23%, 65%, and 12% distributed to air, water, and land,
respectively (20, 31). Reported annual APFO emissions from
were 30 and 4 t, respectively (30). Historical APFO use,
for a U.S. fluoropolymer manufacturing site have been
recently tabulated (31). Based upon annual industry-wide
fluoropolymer production data from 1951 to 2003 (29, 31),
estimated historical global PFCA emissions (as APFO and
in the range of 2400-5400 t. Historical use of PFCAs in
fluoropolymer manufacturing facilities is the single largest
known source of PFCA emissions.
Fluoropolymer manufacturers have recently installed
additional capability to capture and recycle APFO (20).
Aqueous APFO solutions have been processed for reuse in
all regions. Dramatic (>90%) reductions in overall APFO
environmental releases over the past few years have been
reported (23, 30). The recent historical trend in APFO
Fluoropolymer producers who use APFN have forecasted a
67% reduction in emissions by 2006 (26).
Fluoropolymer Dispersions. PTFE-based fluoropolymers
heat histories that dictate APFO disposition (32, 33). Most
fluoropolymers are sold as solid granules or pellets with the
majority (>99%) of APFO removed (33). Approximately 16%
FIGURE 2. Commercial PFCAs composition and chain length distribution: S ) contains straight, linear carbon chains; B ) contains
branched carbon chains; E ) even carbon chain(s) predominates; O ) odd carbon chain(s) predominate; the black shaded areas highlight
the major carbon chain length isomer(s). Shaded areas are the minor carbon chain length isomers. Where noted “possible,” it is not clear
from information available to what extent these chain lengths have been manufactured. Future producer and monitoring information may
349ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 2006
are sold as aqueous dispersions, which still contain APFO.
ppm or less APFO but may contain up to 7000 ppm (34).
treatment up to and including temperatures which decom-
pose all APFO present (33). Recently, the fluoropolymer
manufacturers have completed a study to determine the
that on-average 62% was thermally destroyed and 38% was
emitted to the environment (34).
On the basis of total APFO use in fluoropolymer manu-
facture from 1951 to 2004, estimated total historical global
APFO emissions from fluoropolymer dispersion processing
Group (FMG) recently announced they would reduce the
concentration of APFO in fluoropolymer dispersions by at
least 90% and thereby dramatically reduce the future
emissions from dispersion processing (34). This action will
reduce APFO emissions of 20 t in 1999 by 90% in 2006.
PVDF polymers produced using APFN are not generally
sold as aqueous dispersions. PVDF polymers are sold as a
solid with an estimated residual content of 100-200 ppm
of PVDF containing these levels of APFN is estimated to be
between 10 and 20 t.
by the ECF process were used as a component in aqueous
fire-fighting foam (AFFF) from approximately 1965 to 1975
(2, 35, 36). In this time period, ECF-based PFCA surfactants
utilizing AFFF formulations containing PFCAs were con-
ducted with direct release to soil and water resulting in
widespread input to the environment from a host of point
Alaska pipeline after 1977, Northern Region Arctic Military
Bases) as well as to the oceans from shipboard and oil rig
training exercises (37-41). Annual use of PFCA-based AFFF
products is estimated to have been between 5 and 10 t per
emissions to soil and water from the use of AFFF products
based on PFCAs is between 50 and 100 t.
Consumer and Industrial Products. Widespread use of
baths, self-shine floor polishes, cement, fire-fighting for-
mulations, varnishes, emulsion polymerization, lubricants,
gasoline, and paper, leather, and textile treatments (2).
Additional PFCA industrial uses indicated by recent patents
and technical bulletins include copier, toner, magnetic
(42-44). The typical concentrations of PFCAs used in
industrial formulations range between 100 and 5000 ppm.
PFCAs are indicated in patents as components in con-
sumer products including floor polishes, cleaning formula-
paper, air fresheners, and textile treatments (19, 45-54).
Confirmation of these uses, PFCA amounts, and time frame
of use have not been determined. It is not known to what
extent these patents were actually practiced. It is estimated
that annual PFCA use in consumer and industrial products
was between 1 and 6 t per year from 1960 to 2000 yielding
to air and water. These industrial and consumer uses
represent direct human exposure routes not normally
(POSF) products made by the ECF process contained PFCA
impurities (55-58). Further, fluorotelomer-based products
may contain trace levels of PFCAs (<1-100 ppm) as
unintended reaction byproducts (59). Investigations to
determine the environmental fate through the life cycle
(manufacture, use, and disposal) of these two different
material classes have revealed that there are potential
each class may degrade to form PFCAs in the environment
POSF-Based Products. POSF-based products have been
manufactured at several sites in the United States as well as
in the 1960s and increased until the principal (estimated
in 2002 (58). Global production by the major manufacturer
of POSF as a raw material in 2000 was approximately 3700
t (58). The global use, distribution, and release of POSF-
trial applications and consumer products (i.e., food-contact
POSF-based products contained between 200 and 1600
ppm of PFO (56). Although principally composed of eight-
carbon fluorinated chains, the PFCA impurities in POSF-
based product were a mixture of linear and branched (up to
30 wt %) chain isomers from four to nine carbons in length
(17). A recent analysis of a series of consumer spray
ranging in concentration from 5 to 100 ppm (67). Perfluo-
not been determined. However, if these sulfonates originate
from ECF processes, PFCAs, both linear and branched, of
in the environment. The PFCAs present in POSF-based
products were emitted to the environment (principally air
and water) from point sources as well as dispersive use and
disposal (i.e., landfill and incineration) of industrial and
consumer products (i.e., textile fabrics, carpet, and paper).
On the basis of the reported data for global production of
POSF-based products (58) and a use period from 1960 to
2002, the global historical emissions of PFCAs from POSF
products are estimated to be between 20 and 130 t.
and became the products of choice for fire protection
companies and suppliers from the 1970s forward. These
products contained between 0.1 and 1.0 wt % of PFCAs
with PFO as the largest component (37-39). Although no
longer manufactured, POSF-based AFFF products are still
in use today from inventories previously in place (70, 71).
As noted earlier, AFFF use resulted in widespread input to
water and soil from sources in urban, rural, and remote
regions, including the Arctic, as well as to the oceans from
emission of PFCAs from 1970 to 2004, total global emissions
of PFCAs are estimated to be between 3 and 30 t from this
Degradation of POSF-based residual raw materials and
products is also a potential indirect source of PFCAs in the
environment. However, there is little information regarding
their degradation pathways and more studies are needed. It
has been reported that 0.6% of raw material sulfonamide
alcohol N-EtFOSE, F(CF2)8SO2N(Et)CH2CH2OH, was trans-
of perfluoroalkylsulfonamido raw materials to PFCAs has
VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY935
from 1960 to 2002 from degradation of POSF-based raw
materials are between 1 and 30 t.
To date, there is no scientific evidence that POSF-based
polymeric or surfactant products degrade to form PFCAs
under environmentally relevant conditions. These products
have been released into the environment (e.g., landfills,
of PFCAs if they degrade in these situations. A recent
incineration study showed that only one- and two-carbon
based substances (75).
Numerous POSF derivatives, most notably PFOS, have
been found widely in people and the environment (5-15).
If the PFCAs present in POSF-based products followed the
same exposure and environmental release pathways, they
would be expected to be present in people and the environ-
ment as well. A “signature” of PFCAs originating from ECF
manufacture would be the presence of branched PFCA
isomers. Additional research is needed to fully determine
the significance of these potential exposure and release
Fluorotelomer-Based Products. Fluorotelomer-based prod-
in many of the same industrial and consumer product
applications as POSF-based products (17, 76). Telomer A is
that other smaller manufacturing and processing facilities
between 2000 and 2002 was between 5000 and 6000 t per
and acrylate monomer.
Two methods are used to manufacture fluorotelomer
alcohol (FTOH) from fluorotelomer iodide: sulfation/hy-
drolysis and solvolysis (76). In both, 2% or less residual
unreacted fluorotelomer iodide remains. Additionally, 2-5
wt % byproduct fluorotelomer olefin (FTO) is formed in the
solvolysis process. Similarly, fluorotelomer alcohol or fluo-
rotelomer iodide is used to make acrylate monomer, a
fundamental building block for the polymeric products
representing >80% of the fluorotelomer-based products
manufactured and used worldwide. The reaction of fluo-
rotelomer alcohol to make fluorotelomer acrylate or meth-
Alternatively, reaction of fluorotelomer iodide and acrylic
acid salt to form acrylate monomer results in 3-8 wt % FTO
byproduct (78). The FTOHs and FTOs are present in the
ultimate sales products unless removed. Using the 5000-
6000 t of Telomer A production in 2002, it is estimated that
2 wt %, or approximately 100 t, each of FTOHs and FTOs
were present annually in fluorotelomer-based products.
of PFCAs, including PFO, may be present in some fluoro-
telomer-based products as unintended manufacturing
byproducts (<1-100 ppm) (59). Environmental release of
PFO to air and water from a fluorotelomer-based products
manufacturing facility as a point source was reported to be
less than 1 kg to air and less than 100 kg to water per year
(79). Recent study results show that trace levels of PFO or
fluorotelomer alcohols (FTOHs) present in fluorotelomer-
based products are likely to be released to the air during
industrial application of fluorotelomer-based products to
to 2004 of PFCAs to air and/or water from fluorotelomer-
are between 0.3 and 30 t.
present in fluorotelomer-based products is a potential
indirect source of PFCAs. It is estimated that from 2000 to
2002, fluorotelomer-based products contained a sum total
and FTO as a reaction byproduct. FTOHs and FTOs have
sufficient vapor pressure to be present in air (81). FTOHs
with 6, 8, and 10 fluorinated carbons have been identified
in air samples (82, 83). The 100 t of FTOHs residual in the
to 2002 is at the low end of the computed 100-1000 t/year
global input necessary to maintain reported atmospheric
of FTOHs present in air in the gas phase may transform to
NOxis absent. No PFCAs are predicted to form when NOxis
present in concentrations common in urban and boreal
in the atmosphere by the same transformation pathway as
FTOHs (85). An additional atmospheric pathway which may
be important for FTOs is reaction with ozone. Ozonolysis of
FTOs directly produces odd-numbered PFCAs. Substantial
data gaps must be explored to elucidate the atmospheric
fate of these substances.
Studies to determine the biodegradation in sludge of
PFO (60-62). Assuming 1.0-2.0 wt % FTOH and/or FTO
to PFCAs, the global historical contribution from 1974 to
2004 of PFCAs due to degradation of FTOHs and FTOs is
estimated to be between 6 and 130 t. One telomer manu-
facturer recently announced their intent to implement
process technology that will significantly reduce residual
fluorotelomer raw materials and PFCAs in products (23).
Finally, degradation of fluorotelomer-based polymeric
degradation during use (e.g., sewage treatment plant sludge
from laundering textiles) or disposal (e.g., landfill or incin-
eration). Recent studies showed that no PFO was formed
under simulated typical municipal incineration conditions
of fabrics treated with fluorotelomer-based polymers (86).
Twenty-eight day degradation studies in sludge and soil did
not indicate polymer degradation to PFO (87, 88). Long-
term (up to one year) abiotic and biotic degradation studies
of fluorotelomer-based polymeric products in soils, sedi-
ments, and anaerobic sludge are underway (89). To date,
there is no scientific evidence that fluorotelomer-based
polymers degrade to form PFCAs under environmentally
relevant and representative conditions.
until May 2000 were POSF-based surfactant products (40,
70, 71). Fluorotelomer-based AFFF surfactant products
became available in the 1970s. Because the POSF-based
products were well established and specified in long-term
government contracts, fluorotelomer-based AFFF products
had a market share of less than 50% for most of the 30 years
both were in use until POSF-based products manufacture
C6F13-chains with small amounts of longer perfluorocarbon
369ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 2006
training exercises and actual use originated from the POSF-
based products and not from fluorotelomer-based products
based AFFF agents was reported to be the 6-2 fluorotelomer
Summary. PFCA Sources. Total industry-wide global
mainly of 8-, 9-, and 11-carbon PFCAs. Figure 3 shows the
global historical emissions for each potential PFCA source
length. A figure showing the sum of direct and indirect PFO
sources from 1999 to 2006 (projected) is included in the
has occurred between 1999 and 2004. The reduction is
projected to be >75% by 2006. These emission data provide
a basis for exploring the global fate and transport of PFO,
which is the focus of the remainder of the paper.
This section summarizes the physical-chemical properties
of PFO and PFOA and uses them to provide an indication of
their environmental behavior.
The low reported pKa values of PFOA of 2-3 (17, 90)
indicate that both PFO and PFOA are present in the en-
properties and environmental partitioning behavior. At pH
7, only 3-6 in 100 000 molecules are PFOA, with the
remaining being PFO. At pH 4, about 6% will be PFOA
The vapor pressure (VP) for PFO has not been measured
but is expected to be negligible. Vapor pressures of PFOA
and perfluorononanoic, -decanoic, -undecanoic, and -dode-
canoic acids have been measured at the temperature range
Antoine equation to 25 °C for PFOA results in an estimated
VPof 4.2 Pa. In the same study, solid APFO was shown to
readily sublime to gaseous PFOA at room temperatures.
The solubility of PFO in water is reported to be 4.1 g/L
at 22 °C (92) and 9.5 g/L at 25 °C (93). The sharp increase
the reported Krafft point of PFO of 20 °C and critical micelle
concentration (CMC) of 3.7 g/L (94). The Krafft temperature
and begin to form micelles. Above the Krafft point, the
solubility increases abruptly on account of the formation of
micelles. The solubility of PFOA in water has not been
published, although it is expected to be less soluble than
PFO. The aqueous solubility of PFOA could be determined
in a concentrated acid solution.
water making determination of the octanol-water partition
coefficient (KOW) extremely difficult (90). KOWmay anyway
be an irrelevant measurement for estimating the environ-
mental partitioning of perfluorinated compounds (95, 96).
No measurements of the Henry’s law constant (H) have
been made for PFO or PFOA. H is usually given by the ratio
of vapor pressure and water solubility (97). Care should be
taken in calculating H for PFOA and PFO. It is critical that
water solubility and vapor pressure measurements are for
the same species. H for PFO is expected to be very low and
H for PFOA is expected to be relatively high so that any
volatilization that occurs is likely to be of PFOA. However,
the volatilization of PFOA from water will depend on the
15 000-30 000 times lower than PFO at pH 7 making
pH 4), 6% would be PFOA, thus a larger fraction would be
available to volatilize.
The sorption mechanism of PFO to solids is not well
in six soil types of 2-40% organic carbon (OC) content have
been determined (98). Soil-water partition coefficient (Kd)
values of PFCAs exhibited linear relationships with soil OC
content and KOCincreased with chain length of the acid. A
KOCof 52 L/kg was reported for PFO. A recent industry study
tested for four different soil types (0.8-5.8% OC) confirmed
these results. Kds for the soils were again linearly correlated
Sorption isotherms were linear over a wide concentration
range. A strong inverse relationship between OC content
and desorption was also shown. Finally, a separate study
reported a lower KOCfor PFO in soil of 17 L/kg (100). It is
FIGURE 3. Percent of total historical global PFCA emissions by source.
FIGURE 4. Estimated 2000 global PFCA emissions by carbon chain
VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY937
likely that sediment-water partitioning exhibits behavior
similar to soil-water partitioning.
Bioconcentration factor (BCF) measurements with rain-
bow trout for a suite of PFCAs (8-12 carbons) yielded BCFs
with carbon chain length (a factor of 8 for each additional
carbon). It is noteworthy that there was a strong correlation
measured BCFs (101) and KOCs (98). Bioconcentration and
sorption models based on CMC (102) that have been
previously developed for other surfactants may also be
applicable to the PFCAs.
If present in the atmosphere, PFO is expected to be
associated with particles since its vapor pressure is thought
to be negligible. PFO could either bind to the organic phase
in aerosols and/or dissolve in water present in the aerosols.
of PFOA/PFO in the gas and aerosol phases in air is
In summary, PFOA is expected to dissociate in the
pressure, a high solubility in water, and moderate sorption
waters is expected. Limited environmentally relevant physi-
cal-chemical properties and partitioning data prohibit the
application of classical fate models based on partitioning in
the air/water/octanol system (97).
Environmental Inventories and Sinks
Environmental Inventories. In this section, environmental
monitoring data are reviewed and used to estimate mass
inventories in different environmental compartments, and
it is necessary to estimate the regional background concen-
to avoid positive bias in the inventory estimations. A major
limitation in the inventory estimates is the lack of literature
studies reporting environmental levels. To account for the
environment because monitoring data for the southern
hemisphere are absent. Inventories in the southern hemi-
production or use of PFCAs is known to have occurred there
and atmospheric and aquatic mass exchange between the
two hemispheres is generally limited (103).
densely populated or industrialized countries/regions (e.g.,
SE Asia and North Sea) (104-109) and in the Faroe Islands
(110). Major riverine and sewage treatment input would be
significant for most of these sites. Reported PFO levels in
coastal waters generally vary between 0.2 and 20 ng/L, but
were as high as 450 ng/L in SE Asia samples.
and as deep as 4400 m, have been reported for a number of
seas and oceans (106-109). PFO levels were orders of
magnitude lower than in coastal areas with concentrations
in surface open ocean waters varying from 0.015 (Central to
Eastern Pacific Ocean) (107) to 0.5 ng/L (open North Sea)
4400 m) has been reported (107). Surface levels in the same
area were 107 pg/L. Since PFO has been manufactured for
time of several hundred years) (111), these deep ocean
concentrations are difficult to explain and need to be
For the ocean inventory calculations, a northern hemi-
a global model (112) and the sea surface mixed layer was
assumed to vary between 50 and 150 m. PFO was assumed
water concentrations used for calculations were taken from
the Eastern Pacific (0.015-0.142 ng/L) and North Atlantic
(0.100-0.439 ng/L) (107), as these two oceans comprise the
greatest surface area in the northern hemisphere. The range
of open ocean concentrations used in the calculations was
thus 0.015-0.439 ng/L. The total estimated PFO inventory
variance in the assumed depth of the surface mixed layer.
concentrations (104, 106, 108, 110, 113-116). The most
comprehensive survey of freshwaters was undertaken in
lakes were sampled. This survey showed that PFO concen-
trations in Japanese surface waters could be as low as 0.1
ng/L in remote areas and about 2-10 ng/L in urban areas.
reported, but these were shown to be near point sources.
(113, 114). The data from ref 114 reporting 40 ng/L of PFO
in Lake Ontario have been questioned on the grounds of
data quality (117). Furdui et al. (113) claim not to have the
same blank problems that were alleged to prejudice data
quality in ref 114 and report concentrations of PFO of 2-8
ng/L in several of the Great Lakes. Similar low ng/L levels
have been reported in Scandinavia (110) and in the Elbe
For the calculation of PFO in freshwater, it is assumed
areas) and 10 ng/L (high end of concentrations reported in
rivers or lakes). Using estimated freshwater surface area for
the northern hemisphere of 4 × 1012m2and an assumed
average depth of 20 m taken from a global model (112), the
inventory is estimated as 4-800 t.
Sediments. Fresh and coastal water sediment concentra-
collected sediments from a small U.S. city (Port St. Lucie,
FL), The Netherlands, several Scandinavian countries, San
Francisco Bay, and the Niagara River. Reported PFO con-
centrations in sediments were 24 pg/g to 18 ng/g. Samples
with concentrations of over 1 ng/g were atypical (possibly
in vicinity of point source) with the majority of reported
concentrations being in the hundreds pg/g range. For
20 pg/g (lowest reported) to 500 pg/g (high end of concen-
taken from a global model (112) and values for typical sedi-
ment particle density (2.4 g/cm3), bioturbated mixing depth
(5 cm), and surface sediment porosity (0.7) were used (97,
112). The estimated PFO sediment inventory is 3-340 t.
PFO in precipitation from Finnish and Swedish locations
Scott et al. (122) found PFO as high as 50 ng/L (but generally
less than 10 ng/L) in precipitation samples from 3 different
U.S. sites during 1998. Loewen et al. (123) reported PFOS in
rainfall collected in Winnipeg, MB but no PFCAs were
389ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 40, NO. 1, 2006
detected. Young et al. (124) reported PFOA levels of about
2-3 ng/L in snow and ice caps in the High Arctic.
The presence of PFO in rainfall and snow indicates the
atmospheric presence of PFCAs. This could be the result of
point sources in the immediate vicinity of the sampling
stations, or the atmospheric transport of PFCAs themselves
or volatile precursors which undergo transformation to
PFCAs. More research on this topic is highly recommended.
is not currently possible due to lack of data. It is expected,
however, that the total mass would be low compared to the
masses in surface waters and sediments.
Other Media. Due to lack of data for PFO in background
soils, it was not possible to calculate a soil inventory. Soils
and possibly dry deposition, but retention by the soil is
expected to be low compared to other well-known hydro-
phobic organics. Monitoring of PFCAs in backgrounds soils
is needed to test this hypothesis.
in biota and humans (5-15). However, it is difficult to use
these data to calculate an inventory for biota. It was not
mass of PFCAs compared to masses in surface waters and
Environmental Sinks. Degradation. PFCAs are stable to
acids, bases, oxidants, and reductants and are generally not
believed to undergo metabolic or other degradation in the
environment (17). Historical losses through degradation are
assumed to be negligible.
of water containing them or through sedimentation on
sinking particles (125). The residence time of the mixing of
the surface mixed layer with the deeper ocean water is
between 300 and 500 years (111). The estimated removal
an estimated current annual removal rate of 0.2-33 t/year.
It is currently not possible to calculate the sedimentation
particulate concentrations in the open ocean are unknown.
below the bioturbated mixed layer that is available for
exchange with the overlying water column. The burial loss
is computed using knowledge of the sediment inventory
estimated here, sedimentation rate (0.1-0.3 cm/year) (97),
time period (50 years), and bioturbated mixing depth (5 cm,
SummarysInventories and Sinks. The calculations in
this section suggest that oceans contain the majority of PFO
historically released. This is consistent with our knowledge
The only environmental sinks for PFO are considered to be
sediment burial and transport to the deep oceans, implying
a very long environmental residence time. It is believed that
direct comparison of inventories and emissions provides an
approximate mass balance since only a small percentage of
the PFO historically released is expected to have been
removed from the environment. The total environmental
release of PFO can be estimated as 85% (see Figure 4) of the
total PFCA releases (3200-7300 t) which is 2700-6200 t. It
inventories (120-11 000 t) is in the same range, but due to
large uncertainty boundaries the current mass balance is
inconclusive. To provide improved mass balances in the
future, more monitoring data are needed to lower the
uncertainty boundaries in the inventory estimates and to
identify other possible reservoirs for PFO (e.g., soil).
It is worthy of additional note that levels of PFN in the
open oceans are about an order of magnitude lower than
those of PFO (105-110, 126). Providing that oceans are the
major repository of PFCAs, the lower levels of PFN relative
to PFO provide support for our estimate that the historical
cumulative emissions of APFN/PFNA are an order of
magnitude lower than those of APFO/PFOA (Figure 4).
Environmental Transport Pathways
Atmospheric Transport of Volatile Precursors. The deg-
radation and transport of volatile precursor chemicals such
as FTOHs have been hypothesized as the main source of
long-chain PFCAs in remote regions such as the Arctic (63,
84). Not considered and yet to be investigated are potential
precursors such as fluorotelomer olefins (FTOs) and per-
fluorosulfonyl chemicals and potential local sources. More
physical-chemical data for FTOHs as well as information
on gas-particle partitioning and atmospheric deposition
would improve calculations of atmospheric transport.
that APFO/PFOA is directly released to the atmosphere at
fluoropolymer manufacturing facilities (127). Air samples
taken at locations surrounding one manufacturing facility
revealed on analysis levels of APFO/PFOA in atmospheric
unlikely that it is present on atmospheric particulates. The
compound detected on the particulates may therefore be
solid APFO, which is consistent with the use of APFO in the
was detected above a detection limit of 0.07 µg/m3. The
lifetime of these particulates in the atmosphere and, thus,
their travel distance will depend on the particle size. Less
than 6% of particles were >4 µm, while almost 60% of the
particles were below 0.3 µm. As the vent gases are diluted by
ambient air and the APFO particles move away from the
source, they may sublime to form gaseous PFOA further
can arise from the atmospheric degradation of precursors,
from emission of APFO followed by sublimation, and from
carbon PFCAs (128) and PFOA (129) have previously been
examined and are thought to be dependent on removal by
hydroxyl radicals. Atmospheric lifetimes for gaseous PFOA
of a few days to several weeks have been estimated (129).
Further studies are required to determine whether direct
for long-range transport.
Atmospheric Transport of PFO on Marine Aerosols.
Marine aerosol (a significant part of atmospheric aerosol) is
generated through gas-bubble production and collapse
sea surface micro-layer can, thus, supply the atmosphere
with organic-rich particles that should be considered as a
possible contributor to the long-range transport and wide-
for surfactants such as PFCAs based on the fact that high
concentrations of water-soluble hydrocarbon surfactants
sea surface (130-135). Studies are needed to determine
whether and to what extent marine aerosols contain PFCAs
and may contribute to their global transport.
Aquatic Transport. There is strong evidence for the
importance of aquatic transport of hexachlorocyclohexanes
to the Arctic (136, 137). These chemicals are semi-volatile,
are hypothesized to have a high potential for long-range
aquatic transport to the Arctic. To explore this hypothesis,
VOL. 40, NO. 1, 2006 / ENVIRONMENTAL SCIENCE & TECHNOLOGY939
we have used the approach presented in Macdonald et al.
(137) to estimate the quantity of PFO that is transported to
the Arctic by the oceans. The total flow of water entering the
Arctic surface ocean (mainly through West Spitzbergen
Current, Barents Sea, Norwegian Current, and Bering Strait)
is approximately (4.86 ( 1.3) × 106m3/s (137). By taking the
lowest reported open ocean PFO water concentrations of
0.015-0.062 ng/L (central Pacific Ocean) as representative
of background levels in the northern hemisphere (107) and
multiplying by the water flow rate, the PFO that reaches the
Arctic is calculated to be between 2 and 12 t per year.
Unpublished data presented recently (139) demonstrated
that the Pacific Ocean water concentrations used in this
calculation are similar to concentrations of PFO in Arctic
waters (Greenland Sea). PFOA and PFOS were present in all
samples with concentrations ranging between 0.020 and
The flow paths of surface ocean currents and time scale
for the North Atlantic based on studies using radionuclide
tracers (140-142). For example, it takes 5-7 years for137Cs
to travel from the Irish Sea to the entrance of the Arctic
Ocean. Considering that PFCAs have been emitted for
approximately 50 years and accumulating in the oceans,
ocean water transport to the Arctic is likely to be important.
As a point of comparison, between 0.1 and 1 t per year of
PFCAs was estimated to be delivered to the Arctic from the
northern hemisphere from FTOH degradation and subse-
transport is estimated to be more significant as an input
route to the Arctic. We recommend that the relative
importance of these two pathways be further examined.
Ocean transport and degradation of precursor chemicals
detected in water should also be considered.
A complication in comparing these pathways is that in
the environment the pathways will combine. Ocean water
transport of PFCAs is the combination of (a) discharges of
PFCAs to surface waters and subsequent transport, (b)
atmospheric loadings of PFCAs to surface waters and
subsequent transport, and (c) discharge of precursors to
surface waters, transformation to PFCAs, and subsequent
transport, (b) discharge of precursors, transformation to
of PFCAs and subsequent atmospheric transport. These
processes are likely to occur multiple times as these
compounds are transported around the globe, a process
sometimes described as “grasshopping” (144).
Source Patterns. Patterns in chain lengths and the
branching of PFCAs in environmental samples may provide
clues to their sources and transport pathways. Branched
PFCAs are only known to arise from the ECF production
than or equal to 14 are likely to arise from fluorotelomer-
based substances, as a direct source from their use in PFCA
manufacture, or as an indirect source from degradation.
to patterns in sources is complicated because patterns may
become altered as a result of different partitioning and
uptake/clearance rates in biota for the various PFCAs.
However, it is interesting to note that the PFCA emissions
pattern shown in Figure 4, odd-carbon PFCAs 9, 11, and 13
from highest to lowest each being greater than their next-
highest even numbered PFCA homologue 10, 12, or 14,
reported in biota sampled from remote regions (9, 14).
Differences have been observed in chain length patterns
of PFCAs in polar bear livers in the Eastern and Western
Arctic (15); e.g., a higher ratio of PFNA/PFOA in the Western
wind and/or ocean currents, then the prevailing pathways
suggest that the source of PFCAs in the Eastern Arctic is
attributable to transport from Western Europe and Eastern
mainly by Eastern European sources (15). Interestingly, the
higher PFNA/PFOA ratio in the Western Arctic is consistent
with the manufacture and use of PFNA/APFN in Eastern
Time Trends in Biota. Studies that report increasing
concentrations of some PFCAs with time in Arctic ringed
the importance of transport/degradation of precursors as a
mechanism for delivery of PFCAs to the Arctic. It is recom-
mended that these datasets are statistically analyzed to
determine if the upward slopes of concentrations are
significant and to determine confidence intervals for the
reported doubling times. The age of animals studied should
also be taken into account, which is complicated by the
contradictory nature of recent literature studies (147, 148).
One recent study claims no significant change in the
concentrations of PFCAs in polar bear livers with age (147),
whereas another suggests a significant increase in liver
concentrations with age (148). Nevertheless, all the possible
transport pathways discussed in this paper could explain an
water transport is relatively slow compared to atmospheric
transport, it could still explain recent rising Arctic levels in
aquatic wildlife because direct sources of PFCAs to surface
The apparent downturn in perfluorooctane sulfonate
(145, 149) is currently under investigation. It seems unclear
whether (a) the species studied could clear PFOS so rapidly
of these species would have decreased so rapidly even if
atmospheric deposition of PFOS has declined as a result of
We thank ALARM (GOCE-CT-2003-506675) and PERFORCE
(NEST-508967), two research projects funded by the Euro-
pean Union DGXII, for support of this work. We gratefully
McLachlan of Stockholm University.
Supporting Information Available
Details of manufacturing schematics for PFCAs and
fluorotelomer based products, PFCA weight composition of
APFO, and details of all emission, inventory, and sink
calculations. This material is available free of charge via the
Internet at http://pubs.acs.org.
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