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Environ Monit Assess (2007) 128:343349 DOI 10.



Determination of Henry_s Law Constant of Formaldehyde as a Function of Temperature: Application to AirWater Exchange in Tahtali Lake in Izmir, Turkey
Remzi Seyfioglu & Mustafa Odabasi

Received: 13 March 2006 / Accepted: 8 May 2006 / Published online: 21 October 2006 # Springer Science + Business Media B.V. 2006

Abstract The Henry_s law constant (H) is an important parameter in predicting the transport, behavior and fate of organic compounds in environment. H is also required to model the airwater exchange of chemicals. Henry_s law constant of formaldehyde (HCHO) was determined at six temperatures (50, 40, 30, 20, 10, and 5C) using a bubble-column technique. The apparent Henrys law constant (H*) values were strongly correlated to inverse of temperature (1/T, K) and the following relationship was obtained: ln H* 1; 641:3=T 3:089 Seven concurrent ambient air and aqueous samples were also collected between October 1117, 2005 at a sampling site located on the shoreline of Tahtali dam Lake in Izmir, Turkey to determine the magnitude and direction (deposition or gas-out) of HCHO flux. In all cases, the modeled gas-phase flux was positive (average SD, 3,181 408 g m2 day1) indicating that atmospheric HCHO deposited to the Tahtali Lake. Keywords airwater exchange . formaldehyde . gas stripping technique . Henry_s law constant
R. Seyfioglu : M. Odabasi (*) Faculty of Engineering, Department of Environmental Engineering, Dokuz Eylul University, Kaynaklar Campus, 35160 Buca, Izmir, Turkey e-mail: mustafa.odabasi@deu.edu.tr

1 Introduction Formaldehyde (HCHO) is released into the atmosphere as a result of incomplete combustion of fossil fuels. It is a widely used industrial chemical to manufacture building materials and numerous household products. Vegetation and photochemical reactions are other identified sources of formaldehyde. Therefore, it is present in substantial concentrations in ambient air. Formaldehyde is a labile compound that is involved in several important processes within the troposphere (Economou & Mihalopoulos, 2002). Following its release or formation, formaldehyde is transported through the atmosphere where it is subject to chemical and physical transformations (Finlayson-Pitts & Pitts, 1986). Removal of formaldehyde from the atmosphere can occur by chemical transformations, rain and snow scavenging of vapors and particles, by dry deposition of particles, and by vapor exchange across the air water interface. Wet deposition may be a significant source of HCHO to aquatic systems since concentrations in rainwater are expected to be higher than in surface waters (Economou & Mihalopoulos, 2002; Kieber, Rhines, Willey, & Brooks Avery, 1999). The Henry_s law constant (H) is an important parameter that plays a fundamental role in predicting the transport, behavior and fate of organic compounds in the environment and it is required to model the chemical transfer between air and water. The objective of this study was to determine the Henry_s law


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constant of HCHO as a function of temperature. Determined Henry_s law constants, meteorological parameters, and concurrently measured ambient air and aqueous concentrations were used along with the two-film model to determine the magnitude and direction (deposition or gas-out) of HCHO flux to the Tahtali dam Lake in Izmir, Turkey.

of each experiment. Experimental procedure was applied at six different temperatures (50, 40, 30, 20, 10 and 5C) and replicated three times for each temperature. Runtime was 60 min for the experiment at 50C while it was 120 min for other temperatures. 2.2 Field sampling Seven concurrent ambient air and aqueous samples were collected between October 11 and 17, 2005 at a sampling site located on the shoreline of Tahtali dam lake in Izmir, Turkey. Tahtali Lake is a significant reservoir for drinking water supply in Izmir. The sampling site is located approximately 20 km southwest of Izmir_s center and it is relatively far from any settlement zones or industrial facilities. Meteorological data was obtained from Adnan Menderes airport located a few kilometers away from the sampling site. 2.2.1 Air sampling Atmospheric gas-phase HCHO was collected using a sampling train consisting of a filter holder, two impingers in series, a vacuum pump, a rotameter, and a gas meter. Air was first drawn through a 47 mm glass fiber filter to remove particles and then, through two impingers connected in series. Gaseous HCHO is absorbed in the first and second impingers filled with 75 and 50 ml deionized water, respectively. Then, air flowed through a rotameter and a dry gas meter used for flow rate and sampling volume monitoring. Average sampling duration was 24 h. Sampling flow rate and average volume was 1,500 ml min1 and 2.2 0.40 m3, respectively. 2.2.2 Water sampling Water samples were collected at the beginning of air sampling (at 9.00 A.M.) manually from a depth of 30 cm using high density polyethylene (HDPE) containers without leaving a headspace in the container. Aqueous samples were filtered through a 0.45 m membrane filter before they were analyzed. 2.3 Sample analysis Samples were analyzed for formaldehyde using the Nash method. This technique has been commonly used

2 Experimental 2.1 Gas-stripping experiments The gas-stripping apparatus consisted of a 75 by 5 cm diameter water-jacketed glass reactor filled with 1l deionized water at a depth of 50 cm (Cetin & Odabasi, 2005; Odabasi, Cetin, & Sofuoglu, 2006). The water depth was selected based on previous studies indicating that the equilibrium between gas and aqueousphases is achieved at less than 50 cm of water depth (Sahsuvar, Helm, Jantunen, & Bidleman, 2003; Harrison, Cape, & Heal, 2002; Jantunen & Bidleman, 2000; Bamford, Poster, & Baker, 1999; Bamford, Poster, & Baker, 2000; Betterton & Hoffman, 1988). The formaldehyde was added into the reactor to obtain an aqueous concentration of 35 mg l1. Then, 200 ml min1 compressed chromatographic grade N2 was passed through a 40-m fritted glass diffuser from the bottom of the reactor. Prior to the reactor, the N2 purge gas was saturated with water vapor using a gas washing bottle filled with deionized water. A 5-cm section of the tube exiting the inner chamber was plugged with pre-baked silanized glass wool to prevent the escape of the water droplets that may be produced during the bubbling process. Gas-phase HCHO was captured by 50 ml deionized water in an impinger. A backup impinger was placed into the sampling train to check if there was a breakthrough. In all cases HCHO in the second impinger was below the detection limit. Flow rates of N2 were measured using a flow meter (rotameter) and the temperature was controlled by a constant-temperature circulated water bath. The rotameter calibration was checked occasionally (at three flow rates in duplicate, n = 6) using a primary standard (soap-bubble meter). The average percent difference between two flow meters was <3.0% (2.4 1.8%, average SD). Water samples (1 ml) were drawn through a valve located at the base of the reactor at the start and end

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in the past (Sanhueza, Ferrer, Romero, & Santana, 1991; Khare, Satsangi, Kumar, Maharajkumari, & Srivastava, 1997; Economou & Mihalopoulos, 2002). Analyses were performed with a 1:8 mixture of the Nash reagent (0.02 M acetylacetone, 0.05 M acetic acid, 2 M ammonium acetate buffer) and sample. The yellow colored product diacetyl dihydrolutidin (DDL) formed by the reaction of Nash reagent with formaldehyde is determined by spectrophotometry at the maximum of its absorption (at 412 nm). Reagent and sample mixtures were hand mixed and placed into a water bath maintained at 50C. The reaction is completed after 2 h. The interference of higher aldehydes is negligible, since they react with the Nash reagent more slowly and also their absorption spectra are shifted with respect to 412 nm (Klippel & Warneck, 1980). Calibration curves prepared daily using seven concentration levels (0.0, 0.1, 0.3, 0.5, 1.0, 2.0, 3.0 g ml1). In all cases, the r2 of the calibration curves was >0.999. Field blanks (impingers filled with 75 ml deionized water that were transported to the field but not used in air sampling) were analyzed (n = 3) to determine the amount of contamination from sample collection and preparation. Field blank concentrations were below the detection limit of the method. The detection limit of the method was determined as 0.0075 g ml1 similar to one reported by Economou and Mihalopoulos (2002) (0.0051 g ml1). Sample amount to detection limit ratios were significantly higher than 1.0 for all samples indicating that the sensitivity of the method was sufficient to analyze the samples. 2.4 Data analysis The Henry_s Law constant is often expressed as (Bamford et al., 1999):  H Pg Cw 1 where Pg is the gas-phase partial pressure (atm) and Cw is the dissolved concentration (mol l1). Using the ideal gas law [ p = (nRT)/V] to convert partial pressure to moles per liter (mol l1) of air, dimensionless Henry_s law constant (H) can be obtained as: H 0 H =RT 2

where R is the ideal gas constant (0.08205 l atm mol1 K1) and T is the absolute temperature (K). Formaldehyde (HCHO) reacts substantially and reversibly with water to form methane diol [CH2(OH)2] (Schwarzenbach et al., 1993): HCHO H2 O

kh kd 2

where kh is the hydration rate constant (s1), kd is the dehydration rate constant (s1), and Kh = kh/kd, is the equilibrium constant. Since formaldehyde is hydrated in water, there is a distinction between the apparent Henry_s law constant (H*) and the intrinsic Henry_s law constant (H) (Betterton & Hoffman, 1988). The experimentally determined value is the apparent Henry_s law constant, and this includes a term for the equilibrium constant (Kh). H*0 was calculated as follows:   H*0 Cg Cwn Cwn1 2 4 where Cg (g ml1) is the time-integrated gas-phase HCHO concentration and Cw(n) and Cw(n+1) (g ml1) are the dissolved formaldehyde concentrations measured at the beginning and end of gas-phase sampling period, respectively. The three constants H*0, H 0 and Kh are related by the following equations: . H 0 HCHOg HCHOaq H*0 HCHOg .n o HCHOaq CH2 OH2 5

6 (6) 7

. Kh CH2 OH2 HCHOaq

where [HCHO]aq is the concentration of free unhydrated formaldehyde dissolved in the aqueous phase and [HCHO]g is the gas-phase formaldehyde concentration. Total formaldehyde concentration in the aqueous phase is the sum of [HCHO] aq and the concentration of formaldehyde present in methane diol form [CH2(OH)2]. Rearrangement of Equations (5)(7) gives a direct relationship between H*0 , H 0 and Kh (Betterton & Hoffman, 1988): H 0 H*0 1 Kh 8

346 Figure 1 Variation of H* with temperature.

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-7.0 ln H* = -1641.3 (1/T) - 3.089 r2 = 0.99


ln H (L atm mol )

-1 *





-10.0 0.003








1/T (K)

The equilibrium constant (Kh) can be calculated as a function of temperature ( T, K ) (Winkelman, Voorwinde, Ottens, Beenackers, & Jansen, 2002): Kh exp3769=T 5:494 3 Results and Discussion 3.1 Henrys law constants Henry_s law constant of HCHO has a crucial importance in determining its air-water exchange. Therefore, it has been determined in this study at six temperatures (50, 40, 30, 20, 10, and 5C) using a bubble column technique to establish its temperature dependence. Three replicate experiments were conducted at each temperature. These replications provide a measure of the precision of the experimental method. The relative standard deviations associated with the mean H value were less than 20%, and no systematic differences, within experimental variability, were observed among the different temperatures. The Henry_s law is valid for dilute concentrations. For compounds that are slightly or even moderately soluble in water, with a reasonable accuracy H can be approximated by the ratio of the compound_s vapor 9

pressure and its aqueous solubility (Schwarzenbach, Gschwend, & Imboden 1993). Previous studies reviewed by Schwarzenbach et al. (1993) indicated that there were no significant effects of solute concentration on measured H values. Betterton and Hoffman (1988) found no effect of aqueous HCHO concentration on H* over the range they studied (30 330 mg l1). In the present study, the initial aqueous HCHO concentration was also dilute (35 mg l1) corresponding to 0.008% of its aqueous solubility (4.4 105 mg l1) (Grtzner & Hasse, 2004). The H* values were strongly correlated to inverse of temperature (1/T, K) (Figure 1) and the following relationship was obtained: ln H * L atm mol1 1641:3=T 3:089 10 H* increases with temperature 2.3 times over the studied temperature range. Figure 2 compares results of this study to those reported in the literature. H* was 1.85 104 l atm mol1 (at 25C) and it was in reasonably good agreement with previously reported values of 3.37 104, 3.16 104, 2.94 104, and 1.0 104 l atm mol1 (Betterton & Hoffman, 1988; Dong & Dasgupta, 1986; Zhou & Mopper, 1990; Kim, Kalis, DeWulf, & Andrews, 2000). Measured to

Environ Monit Assess (2007) 128:343349 Figure 2 Comparison of H* determined in this study with literature values.
0.0010 0.0009 0.0008 0.0007 H (L atm mol ) 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001 0.0000 0 10 20 30 T (C) 40 50


This study Betterton and Hoffman, 1988 Blair and Ledbury, 1925 Dong and Dasgupta, 1986 Kim et al., 2000 Zhou and Mopper, 1990


literature value ratios ranged between 0.3 and 3.8 for H values at different temperatures (Figure 2). The agreement between the H* values determined in this study and those reported in the literature was better for the temperatures below 25C (Figure 2). The previously determined Henry_s law constants of HCHO by Betterton and Hoffman (1988) did not show a clear temperature-dependence. However, H values reported by Zhou and Mopper (1990) showed a strong temperature-dependence (Figure 2). It is not possible to offer an explanation for the difference between the experimental values determined in this study and those previously reported. These results demonstrate the importance of experimental determination of the temperature dependence of H for HCHO to accurately predict of its fate and transport under different environmental conditions. 3.2 AirWater exchange The stagnant two-film model has been commonly used to estimate airwater gas exchange of semivolatile organic compounds (SOCs). According to the two-film model, mass transfer is limited by the rate of molecular diffusion through thin films of air and water on either side of the surface (Schwarzenbach,

Gschwend, & Imboden, 2003). The net flux (Fg, g m2 day1) is driven by the fugacity difference between air and surface water: Fg Kg Cg Cw H =RT 11 where Cw and Cg are the water and air concentrations (g m3), H is the Henry_s law constant (l atm mol1), R is the universal gas constant (0.08205 l atm mol1 K1), and T is temperature at the airwater interface (K). The gas phase overall mass transfer coefficient (Kg) is related to individual mass transfer coefficients for the liquid and gas films, kw and kg, as follows:  1 Kg 1=kg H =RTkw 12

Mass transfer coefficients of water vapor, oxygen (O2) and carbon dioxide (CO2) have been related to wind speed by many researchers. According to the two-film model, mass transfer is limited by the rate of molecular diffusion through thin films of air and water on either side of the surface. Thus, mass transfer coefficients for water vapor and oxygen can be adjusted for other compounds using their diffusivities in air and water. The following equations can be used to estimate kg and kw for organic compounds (Schwarzenbach et al., 2003; Mackay & Yeun, 1983):


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Table I Meteorological parameters, gas-phase and aqueous HCHO concentrations, and calculated fluxes Sampling date Water temperature (C) 21.0 21.0 21.0 21.0 21.0 21.0 21.0 21.0 21.0 21.0 0.0 Air temperature (C) 17.1 16.8 16.3 16.0 16.3 15.4 14.2 14.2 17.1 16.0 1.0 Relative humidity (%) 60 59 72 74 66 60 64 59 74 65 6 Wind speed (m s1) Cg (g m3) Cw (g l1) Kg (enhanced) (cm s1) Fg (g m2 day1)

10.11.2005 10.12.2005 10.13.2005 10.14.2005 10.15.2005 10.16.2005 10.17.2005 Min. Max. Average SD

2.7 3.2 1.8 2.2 3.0 5.6 3.4 1.8 5.6 3.1 1.2

8.9 10.1 10.4 8.5 7.5 7.1 9.0 7.1 10.4 8.8 1.2

33.5 34.8 42.1 42.1 46.5 42.1 72.5 33.5 72.5 44.8 13.0

0.42 0.45 0.35 0.38 0.44 0.58 0.46 0.35 0.58 0.44 0.07

3,136 3,841 3,100 2,694 2,707 3,386 3,400 2,694 3,841 3,181 408

kgcompound cm s1  0:67 0:2 u10 0:3 Dacompound DaH2O 13 kwcompound cm s1 h i 1104 1:75104 6:1 0:63 u10 0:5 u10 14  0:5 Dwcompound DwO2 (14) where Da (0.172 cm2 s1 at 25C for HCHO) and Dw (1.95 105 cm2 s1 at 25C for HCHO) are the diffusivities in air and water, respectively, and u10 is the wind speed 10 m above the water surface (m s1). Formaldehyde (HCHO) reacts substantially and reversibly with water to form methane diol. These reactions occur over time periods similar to those required for diffusive transfer across the water boundary layer resulting in a flux enhancement of formaldehyde. The flux enhancement coefficient of formaldehyde () due to chemical reaction can be calculated as follows (Schwarzenbach et al., 2003): Kh 1=1Kh =q:tanh q 15

1=Kgenhanced 1=kg H =RTkw


The hydration rate constant (kh) and the dehydration rate constant (kd) can be calculated as a function of temperature ( T, K) (Winkelman, Ottens, & Beenackers, 2000; Winkelman et al., 2002): kh 2:05 105 exp 2936=T kd 4:96 107 exp6705=T 17 18

where q = (2tw/tr)1/2 is a non-dimensional parameter (reaction/diffusion parameter), tw = (Dw/2kw2), tr = 1/ (kh+kd) is the time of reaction (s), Dw (cm2 s1) is the diffusivity in water, kw is the water-side individual mass transfer coefficient (cm s1). The enhanced gas phase overall mass transfer coefficient (Kg(enhanced), cm s1) can be calculated as (Schwarzenbach et al., 2003):

A recent experimental study have shown that at low to moderate wind speeds (13.5 m s1) the overall flux enhancement of HCHO mass transfer due to chemical reaction ranges between 2.8 and 4.1 times (Seyfioglu & Odabasi, 2006). Ambient temperature ranged between 14.217.1C (16 1C) and the wind speed ranged between 1.8 5.6 m s1 (3.1 1.2 m s1). Surface water temperature remained constant at 21C during the sampling period. Gas-phase formaldehyde concentrations (Cg) measured in this study ranged from 7.1 to 10.4 g m3 (8.8 1.2 g m3, average SD) (Table I). These concentrations were similar to those recently measured at a suburban sampling site in Izmir, Turkey (7.3 6.5 g m3, average SD) (Odabasi & Seyfioglu, 2005). Aqueous formaldehyde concentrations (Cw) ranged from 33 to 72 g l1 (45 13 g l1, average SD). Gas phase fluxes were calculated using the measured ambient and aqueous HCHO concentrations, meteorological data and the Equations (2), (8)(18). In all cases the modeled gas-phase flux (calculated using Kg(enhanced) in Equation (11) instead of Kg) was

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positive indicating that atmospheric HCHO deposited to the Tahtali Lake. HCHO flux ranged between 2,6943,841 g m2 day1 (average SD, 3,181 408 g m2 day1) (Table I). The only previously reported value for gas phase HCHO deposition to the water surfaces under field conditions is 197 g m2 day1 (Zhou & Mopper, 1997). This flux is lower than the minimum value determined in this study because as indicated by calculations it corresponded to a relatively lower ambient air (0.5 g m3) and aqueous (15 g l1) concentrations.
Acknowledgement This work was supported in part by the research fund of Dokuz Eylul University (Project No. 03.KB. FEN.063).

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