Results and Discussions

The fluorinated compounds used for the study were perfluorododecanoic acid (CF3(CF2)ioCOOH, denoted PFDDA), which is the perfluorinated analog of dodecanoic acid, and a partially fluorinated telomer alcohol containing 8 carbons that are fully fluorinated and 2 carbons that are hydrogenated with the formula CF3(CF2)7CH2CH2OH (denoted 8-2 FTOH). These compounds were chosen because they are used industrially and also, because they have been observed in the atmosphere.

Experiments were conducted using a Langmuir trough with two mechanical barriers that compress the film. The results of these experiments is a known as a surface pressure-area isotherm which is a plot of surface pressure as a function of the surface area of the surfactants. The shape of the isotherm corresponds to the molecular orientation of the surfactant as a function of barrier position. In the disordered state, the barriers just begin to compress the film and very weak interactions exist between the hydrophobic tails and the subphase surface. As the film is continued to be compressed, the molecules experience more intermolecular attractions with one another and are in closer contact with one another; this is known as the liquid-expanded state. In the liquid-condensed state, the molecules are in rigid contact with one another. Compression beyond this state leads to the phenomenon of collapse where disordered multilayers form. Linear regression of the steep portion of the isotherm (i.e. the liquid-condensed state) to zero surface pressure gives the molecular footprint of the surfactant which is the surface area a single molecule occupies.

Surface pressure-area isotherms of varying concentrations of the compounds in pure and binary mixed films with octadecanoic acid (denoted stearic acid) and dodecanoic acid (denoted lauric acid) were collected. The film properties investigated were stability, miscibility, and evaporation from the subphase. Further details of the experimental procedures and conditions can be found in references 17 and 18.

Perfluorododecanoic Acid

Single Component Systems

Pure systems of three carboxylic acids were studied first to better understand and characterize their individual properties. Figure 1 shows the surface pressure-area isotherms of pure equimolar (10"3 M solutions) samples of stearic, lauric, and PFDDA collected at room temperature. The three isotherms have different shapes, collapse pressures, and molecular footprints. As illustrated, the perfluorocarboxylic acid has the largest molecular footprint and collapse pressure.

Stearic acid, with the longest carbon chain length studied here, has a textbook example of an isotherm, clearly showing the disordered (0-0.1 mN/m), liquid-expanded (0.1-27 mN/m), and liquid-condensed phases (27-63 mN/m) (18). Linear regression of the steep, liquid-condensed part of its isotherm yields a molecular footprint of 22 A2/molecule (18) which is in excellent agreement with the literature value (40) as is the collapse pressure of the film at approximately 60 mN/m (40). PFDDA, with six fewer carbons in its backbone than stearic acid, has a molecular footprint of 31.6 A2/molecule and collapse pressure of approximately 65 mN/m (18). The hydrocarbon analog of PFDDA, lauric acid, has a much smaller molecular footprint (16.6 A2/molecule) and

Stearic Acid Laurie Acid PFDDA

Figure 1. Isotherms of eqimolar samples of stearic acid, lauric acid, and PFDDA. (Reproduced from reference 18. Copyright 2007 American Chemical Society.)

Stearic Acid Laurie Acid PFDDA

2 6 10 14 18 22 26 30 34 38 42 46 50 54 58 62 66 70 74 78 82 86 90 94! Surface area per molecule (A2)

Figure 1. Isotherms of eqimolar samples of stearic acid, lauric acid, and PFDDA. (Reproduced from reference 18. Copyright 2007 American Chemical Society.)

collapse pressure (approximately 37 mN/m), and also, its isotherm is less structured (18) than both stearic acid and PFDDA. The larger molecular footprint of PFDDA occurs because fluorocarbons are known to form more expanded monolayers (41-43). Since perfluorocarbon chains are highly rigid, apolar and known to interact only by dispersive forces, they experience much smaller van der Waals interaction energy per molecular contact area.

Generally, the hydrophobic tail group determines the efficiency of a surfactant to lower the surface tension. For the PFDDA film, the higher collapse pressure results from the strong electronegative nature of the fluorine atoms (2, 44). Also, the low polarizability of perfluorocarbon chains causes weaker interactions with water as compared to that of hydrocarbon chains. As a result, the low cohesive energy per volume of fluorocarbons yields surface tension values which are approximately an order of magnitude smaller than their hydrocarbon analogs (45); consequentially, higher surface pressure values are reflected for perfluorocarbons. Thus, in comparison to lauric acid-the hydrocarbon analog of PFDDA, the perfluorocarboxylic acid has a much larger collapse pressure and acts a better surfactant as expected.

Multi Component Systems

The impetus of this work was to understand the behavior of PFDDA in mixtures with other organics since realistically, the surfaces of atmospheric aerosol particles are coated with a mixture of many amphiphiles. Miscibility of PFDDA with stearic and lauric acid was studied by varying its concentration in three combinations in the binary mixtures: 25%, 50%, and 75% PFDDA.

Three different factors were used to determine film miscibility: collapse pressure, the breakpoint Kx which indicates the phase transition from the liquid expanded to the liquid condensed states, and the additivity rule. First, the collapse pressure is a useful guide to determine film miscibility since a truly miscible film has a single collapse pressure. Film components which are immiscible have well defined and different collapse pressures; isotherms of such immiscible films would show collapse at the lower pressure first, followed by collapse at the higher value. Next, if Kx is a function of concentration, it suggests complete miscibility between film components at equilibrium (46). Lastly, the additivity rule states that the average area per molecule of any mixture is the sum of the areas occupied by each species at the surface in an ideal behavior. It is given by Aavg = NjA} + N2A2, where Aavg is the calculated average area occupied per molecule of the mixed monolayer, Nj and N2 represent the corresponding mole fractions of the single components in the mixture, and Aj and A2 are the molecular footprints of the pure components. An immiscible film follows the additivity rule, whereas a miscible film deviates from it, indicating that molecular interactions exist between the film components.

Isotherms of the two component mixture of stearic acid and PFDDA were collected which revealed that the film was miscible. Varying the concentration of PFDDA in the mixture did not affect the shape, collapse pressure, or molecular footprint of the isotherms. The general trend showed that the average molecular footprint of the mixture increased as a function of the percent of stearic acid in the mixture. At 25%, 50%, and 75% stearic acid, the average molecular footprints of the mixtures were determined to be 30.6, 31.7, and 33.8 A2/molecule, respectively (18). Similarly, PFDDA in mixtures with lauric acid produced isotherms which also showed film miscibility. In this case, however, increasing the mole fraction of PFDDA in the mixture generated more structured isotherms with larger molecular footprints. The average molecular footprints of the mixture at 25%, 50%, and 75% lauric acid were shown to be 29.5, 21.1, and 13.1 A2/molecule, respectively (18). Table 1 shows the experimental and calculated average molecular footprints of the stearic acid/PFDDA and lauric acid/PFDDA mixtures. The last column, AEx, shows the excess area of mixing, which measures nonideality and is given by AEx = Aact - Aavg, where Aact represents the actual area per molecule of the binary system.

As shown in the table, the mixture of stearic acid with PFDDA shows a positive deviation from ideality upon increasing the percentage of stearic acid in

Table 1. Comparison of Experimental and Calculated Average Molecular Footprints of Mixtures of Stearic Acid and Laurie Acid with PFDDA

Footprint (A2/molecule)

Calculated Footprint (A2/molecule)

Ab>

Stearic Acid Mixture

25% PFDDA

33.8

24.4

9.4

50% PFDDA

31.7

26.8

4.9

75% PFDDA

30.6

29.3

1.3

Lauric Acid Mixture

25% PFDDA

13.1

20.4

-7.3

50% PFDDA

21.1

24.2

-3.1

75% PFDDA

29.5

27.9

1.6

the mixture. This is a result of repulsive interactions between the two components. For the PFDDA/lauric acid mixture, there is a general negative deviation from ideality at larger concentrations of lauric acid in the mixture, which signifies not only an attractive interaction but also miscibility in both the liquid-expanded and liquid-condensed states.

In the mixture with stearic acid, the presence of PFDDA did not greatly affect the structure of the isotherm, the collapse pressure, or the molecular footprint; therefore, it suggests that the PFDDA acts as a co-surfactant in the mixture. However, since increasing the concentration of PFDDA in the mixture with lauric acid gives the isotherms better structure and larger molecular footprints, it implies that the film is stabilized with the presence of PFDDA in the mixture.

8-2 FTOH

Single Component Systems

To be relevant on an atmospheric time scale, surface pressure-area isotherms of 8-2 FTOH were collected at surface layer ages of 5, 10, 30, and 60 minutes to allow for partitioning. Unlike typical fatty acids and alcohols, the isotherms of the fluorotelomer alcohol studied do not show the three distinct phases as can be seen in Figure 2. However, two very important points can be drawn from the figure. First, the isotherms indicate that 8-2 FTOH does partition to the air-water interface, suggesting that the compound is indeed surface active. Second, and more importantly, there is a shift to a smaller molecular footprint and decreased surface pressure with each isotherm as a function of surface layer age. The molecular footprint, which is a characteristic property of an amphiphile and determines how much surface area a single molecule occupies in a compact film at zero pressure, should not change when the concentration and volume are held constant assuming all film components remain at the interface. However, this is not the case as shown in Figure 2. This behavior is attributed to the fact that fluorotelomer alcohols are volatile (47) and will evaporate from the surface on these timescales. The possibility that the alcohol could have dissolved into the subphase was ruled out due to the fact that they are only sparingly soluble in water (47). Due to evaporation, the isotherms actually show a plot of surface pressure vs. molecular density; thus, the x-axis in Figure 2 is labeled as an uncorrected experimental surface area per molecule.

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

Uncorrected experimental surface area per molecule (A2)

Figure 2. Isotherms of 8-2 FTOH collected at surface layer ages of 5, 10, 30, and 60 minutes. (Reproducedfrom reference 17. Copyright 2007 American

Chemical Society.)

In order to determine the amount of surfactant molecules that remained at the interface as a function of time, it was necessary to establish how much of the fluorotelomer alcohol evaporated. To do this, the molecular footprint of 8-2 FTOH was needed, however, to the best of the authors' knowledge, it has not been previously reported. Due to minimal evaporation, the isotherm collected

5-minutes 10-minutes 30-minutes 60-minutes

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

Uncorrected experimental surface area per molecule (A2)

Figure 2. Isotherms of 8-2 FTOH collected at surface layer ages of 5, 10, 30, and 60 minutes. (Reproducedfrom reference 17. Copyright 2007 American

Chemical Society.)

5-minutes 10-minutes 30-minutes 60-minutes after 5-minutes was used as a reference and the molecular footprint of 8-2 FTOH was determined to be 34.5 A2/molecule which is in agreement with the literature for similar systems (48). A correction factor was then applied to the isotherms collected after 10, 30, and 60-minutes to account for evaporation. From this data, the evaporation rate of 8-2 FTOH was established at 0.384% (± 0.002%) per minute (17). Further explanations detailing the methods used to verify the evaporation rate can be found in reference 17.

Multi Component Systems

The fluorotelomer alcohol was also studied in a binary one-to-one molar mixture with stearic acid to investigate its behavior in mixed systems. For consistency with the pure 8-2 FTOH data, experiments were carried out in the same manner using identical volumes, times, and concentrations. Stearic acid was chosen because it is stable at the interface over long periods of time. Figure 3 shows the isotherms of the binary mixture at various surface layer ages. There are no shifts towards decreased molecular footprints and surface pressures with time, unlike in the case of the isotherms of the pure fluorotelomer alcohol. Isotherms of the mixed film retain similar shapes, surface pressures, and limiting

Arachidic Acid Isotherm

Surface area per molecule (A2)

Figure 3. Isotherms of 8-2 FTOH and stearic acid in a binary equimolar mixture at surface layer ages of 5, 10, 30, and 60-minutes. (Reproduced from reference 17. Copyright 2007 American Chemical Society.)

Surface area per molecule (A2)

Figure 3. Isotherms of 8-2 FTOH and stearic acid in a binary equimolar mixture at surface layer ages of 5, 10, 30, and 60-minutes. (Reproduced from reference 17. Copyright 2007 American Chemical Society.)

molecular areas regardless of the surface layer age on the subphase at the times investigated here.

Addition of stearic acid to the fluorotelomer alcohol, regardless of time, consistently formed stable monolayers and significantly reduced evaporation as compared to the pure 8-2 FTOH film. Previous studies have shown that stearic acid helps to form highly stable, compressible monolayer when mixed with surfactants incapable of forming stable monolayer at the air-water interface (49, 50). The outcome of film stability has several consequences in the atmosphere. First, if the fluorotelomer alcohol is present on the surfaces of atmospheric aerosol particles with other organics, it has the potential to not only partition to, but also remain at the air-water interface. Its stability in mixed films makes atmospheric aerosol particles plausible candidates for transporting and distributing this class of compounds in the atmosphere. Also, being present on atmospheric aerosol surfaces can lead to further heterogeneous chemistry of fluorotelomer alcohols, which can possibly be very different from reactions expected to occur in the gas phase, resulting in important atmospheric consequences.

The isotherms of the binary mixture also suggest that the two components form a film that is immiscible. Two distinctly different collapse pressures are shown in Figure 3, at 20 and 55 mN/m, which is a textbook example of immiscibility. While 8-2 FTOH did not collapse on its own, the presence of stearic acid helps to stabilize the fluorotelomer alcohol. Differences in the cohesive forces that exist between 8-2 FTOH and stearic acid prevent the components from mixing well and form islands/aggregates when mixed together. A recent study found that the liquid phase of aerosols is highly concentrated with organics and offers a reaction medium very different from aqueous solutions of fog or rain droplets (51). The surfaces of atmospheric aerosol particles are coated with a mixture of many organics, indicating that if the fluorotelomer alcohol is present in the mixture, it has the potential to partition to and remain at the interface.

Conclusion

Recent field measurements have shown that organics comprise a significant fraction of atmospheric aerosol particles. The detection of perfluorinated compounds in environmental waters and the atmosphere was the impetus for this research since not much data are available regarding the atmospheric transport for this class of compounds. Although much work has been done on understanding the gas phase chemistry of perfluorinated compounds, its heterogeneous chemistry has not been explored to the same depth.

In this study, films of perfluorododecanoic acid (PFDDA) and 8-2 FTOH were studied at the air-water interface using a Langmuir trough as a representative model of atmospheric aerosol particles. PFDDA acid was verified to be a better surfactant than its hydrocarbon analog acid. In mixed films, PFDDA has the ability to act as a co-surfactant and have stabilizing effects. The surface activity of 8-2 FTOH was also studied and confirmed. Evaporation of the pure fluorotelomer alcohol was significantly reduced in the presence of stearic acid. Mixed films are better representations of atmospheric aerosol particles, and if perfluorinated compounds partition to and remain at the air-water interface like the data suggests, further chemistry is possible. Results of this work suggests that aerosol particles are a legitimate candidate for the transport, distribution, and deposition of perfluorinated compounds.

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