TECHNICAL PAPER

ISSN:1047-3289 J. Air & Waste Manage. Assoc. 61:201210 DOI:10.3155/1047-3289.61.2.201

Copyright 2011 Air & Waste Management Association

Treatment of Benzene and n-Hexane Mixtures in Trickle-Bed Air Biolters

Ashraf Aly Hassan and George A. Sorial Environmental Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, College of Engineering and Applied Science, University of Cincinnati, Cincinnati, OH

ABSTRACT Trickle-bed air biolters (TBABs) are suitable for treatment of hydrophilic volatile organic compounds, but they pose a challenge for hydrophobic compounds. Three laboratoryscale TBABs were used for the treatment of an airstream contaminated with different ratios of n-hexane and benzene mixtures. The ratios studied were 1:1, 2:1, and 1:3 n-hexane:benzene by volume. Each TBAB was operated at a pH of 4 and a temperature of 20 C. The use of acidicbuffered nutrient solution was targeted for changing the microorganism consortium to fungi as the main biodegradation element. The experimental plan was designed to investigate the long-term performance of the TBABs with an emphasis on different mixture loading rates, removal efciency with TBAB depth, volatile suspended solids, and carbon mass balance closure. n-Hexane loading rate was kept constant in the TBABs for comparison reasons and ranged from 4 to 22 g/(m3 hr). Corresponding benzene loadings ranged from 4 to 43 g/(m3 hr). Generally, benzene behavior in the TBAB was superior to that of n-hexane because of its higher solubility. n-Hexane showed improved performance in the 2:1 mixing ratio as compared with the other two ratios. INTRODUCTION Biological systems are remarkable for the treatment of dilute volatile organic compounds (VOCs). They have the advantage of being cheap and environmentally friendly. Other methods of treatment include incineration, catalytic oxidation, and adsorption, which could be considered to be rather expensive for dilute systems. Biological systems work best for the treatment of large volumes of off-gases that contain low concentrations of biodegradable contaminants.13 Bioltration is a type of biological

IMPLICATIONS The use of biolters is a cheap and attractive option; however, their application is limited because of several challenges. One of them is the reluctance of hydrophobic compounds for biodegradation and the coexistence of other compounds in air emissions. This paper evaluated the impact of different mixing ratios of two hydrophobic compounds and the effect of increasing inuent concentration. Finally, a comparison is provided on the best performance attained for these hydrophobic compounds as single solutes. The results of this study will aid in the design and operation of full-scale biolters.

system that has proven to work with high efciency. It has been successfully tested and applied for several VOCs such as benzene, toluene, and p-xylene.4 6 However, several challenges face bioltration technology. The main challenges are (1) variable ow rate and concentrations of contaminants, (2) varying contaminants in the feed, and (3) that hydrophobic compounds are reluctant to biodegrade. Several researchers tried to study the behavior of several mixtures of contaminants in biolter systems.7,8 The variability of ow rate and contaminant concentrations have been addressed by several studies9 11 for overcoming the erratic performance of the biolter during transient loads. The hydrophobicity of VOCs plays an important factor in biodegradation. The solubility of hydrophobic compounds in water and their Henrys law constant (HLC) are the most important characteristics that affect the performance of the biolters.12 Because microorganisms responsible for the degradation are present in the biomass, transport of the VOC from the gas phase to the liquid phase can be rate limiting. A challenge facing the bioltration process is that VOCs with low water solubility could be present in waste gaseous streams. A previous study12 found that the presence of a hydrophilic VOC in a waste stream signicantly decreased the removal rate of a hydrophobic compound in the biolter. Maximum removal performance of classes of organic compounds in the biolter followed the sequence of alcohols esters ketones aromatics alkanes. The sequence well correlates with their HLC.13 Thus, an increase in the bioavailability of VOCs may enhance the rate of biodegradation if mass transfer is limiting. Researchers have investigated several methods to increase the bioavailability of VOCs in the liquid phase through the use of surfactants,14 16 two-phase systems (water and oil),17 and changing the water chemistry. According to Van Groenestein,18 replacing the working consortium in a biolter from bacteria to fungi has several advantages: (1) fungi are more resistant to acidication and drying out, which is a major advantage of the natural media biolters but does not necessarily count as an advantage in trickle-bed air biolters (TBABs); and (2) the aerial mycelia of fungi form a larger surface area in the gas phase than bacterial biolms, which may facilitate the uptake of hydrophobic volatile compounds overtaking the rate-limiting step. In the same study, fungi were utilized in the operation of a traditional biolter for the treatment of toluene. In a later study,19 the degradation of
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alkylbenzenes in a TBAB was performed using new isolated fungal strains. It was proven that n-hexane as a single VOC running on a fungal microorganism consortium behaves better than on bacterial microorganisms.15,20,21 In another study, the same techniques were studied on the performance of benzene. The biodegradation performance of benzene was very similar at neutral and acidic pH.22,23 Therefore, the experimental plan was designed to investigate the performance of a mixture of n-hexane and benzene fed to TBABs under acidic pH.4 The same mixture has been proven to perform better at acidic pH if compared with neutral pH.24 Different mixing ratios of nhexane and benzene were applied to TBABs to study the effect of mixture on performance behavior. MATERIALS AND METHODS VOCs Two VOCs were used in this study. n-Hexane was obtained from Fisher Scientic with 85% purity. HLC for hexane was reported at 20 C by different authors as 0.883 atm m3/mol,25 0.014 atm m3/mol,26 and 0.122 atm m3/ mol.27 Benzene was obtained from Fisher Scientic with 99% purity. HLC for benzene at 25 C is 5.42 10 3 3 28 atm m /mol. TBABs Three TBABs were run in parallel in this study: A, B, and C. The TBABs had similar operating conditions but a different VOC ratio of n-hexane to benzene. TBABs A, B, and C were operated at an n-hexane:benzene ratio of 1:1, 2:1, and 1:3 by volume, respectively. The three TBABs were loaded with pellets used in previous runs and were acclimated to the mixtures. Each TBAB is constructed of seven cylindrical glass sections with an internal diameter of 7.6 cm and a total length of 130 cm. They are packed with pelletized diatomaceous earth biological support media to a depth of approximately 60 cm (Celite 6 mm R-635 Bio-Catalyst Carrier; Celite Corporation). The TBABs ran at a constant operating temperature of 20 C and operated in a ow switching mode from concurrent gas ow with the liquid nutrient ow to countercurrent gas ow. Flow switching of the gas ow direction was applied weekly with the purpose of redistribution of the biomass along the biolter depth. The TBABs were run by using a stagnation technique for a period of 2 days/week as a means of biomass growth control within the bed. This was proven to be the most effective technique for benzene removal.22 The stagnant technique could be explained as no ow (VOC, nutrient, or air) passing through the TBAB. A schematic of the TBAB setup is found elsewhere.29 The airow was set up at the rate of 1.36 L/min with a corresponding empty bed retention time of 120 sec. Liquid n-hexane and benzene were injected via a syringe pump loaded with the VOC mixture and vaporized into the prepuried airstream. The airstream was puried using an electronic air cleaner to remove any impurities including VOCs, particulates, water, and carbon dioxide (CO2). Buffered nutrient solution was supplied at a rate of 2 L/day. The solution was intermittently sprayed over the biolter bed. It was supplied for 2 sec every minute. The composition of the nutrient solution is similar to that
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reported by Sorial.30 A nutrient spike solution (2 M sodium nitrate and 0.22 M sodium dihydrogen phosphate H2O) was added to the feed solution so that the chemical oxygen demand:nitrogen:phosphorus ratio was 200:4:1. Nitrate (NO3) was used as the sole source of nutrient nitrogen because it was found to be effective in reducing the observed biomass yield and provided better biolter performance as compared with ammonia.31 The nutrient feed was buffered at a pH of 4 using sodium formate. The efuent liquid was recovered daily and analyzed frequently. The efuent volume collected per day had a minimum of 85% of the inuent volume. The growth of fungi within the TBAB bed was examined and identied using dichloran rose bengal chloramphenicol.32 The average number of colony forming units (CFUs) was determined to be 185,000 CFU/100 mL in the efuent nutrient solution. The method favors the growth of fungi by providing nitrogen, vitamins, minerals, and carbohydrate while suppressing the growth of bacteria. Analytical Methods The concentrations of VOCs in the gas phase were measured using a gas chromatograph (GC; HP 5890, series II, Hewlett-Packard) equipped with a ame-ionization detector (FID). The GC oven was programmed as isothermal at 70 C. The carrier gas (He) ow rate was set at 4 mL/min. The FID was used with He makeup gas at a ow rate of 20 mL/min, a fuel gas ow (H2) of 30 mL/min, and an oxidizing gas ow (air) of 300 mL/min. The detector temperature was 250 C. The column used for the GC was HP-5 (30 m 0.32 mm 0.25 m). Retention times of 0.9 and 1.1 min were obtained under conditions used for benzene and n-hexane, respectively. An efuent gas-phase sample for CO2 analysis was also taken by using gas-tight syringes through sampling ports in the TBAB. A GC (HP 5890, series II; Hewlett-Packard) equipped with a thermal conductivity detector was used for determining the CO2 concentrations in the efuent gas phase. Liquid-phase samples were analyzed for NO3 -N, total carbon (TC), inorganic carbon (IC), and volatile suspended solid (VSS) concentration. NO3 -N was determined according to standard method 4500-NO3 32 using a Shimadzu ultraviolet mini 1240 UVvisible spectrophotometer (Shimadzu Corporation). TC and IC were determined using a Shimadzu TOC 5050 analyzer (Shimadzu Corporation) according to standard method 5310.32 The VSS concentrations in the efuent were determined according to standard method 2540 G.32 RESULTS AND DISCUSSION TBAB Performance Performance of TBAB A. The results shown in Figure 1 provide the performance of TBAB A under the operating conditions mentioned in Table 1. Figure 1 illustrates the inuent and efuent concentration of n-hexane and benzene on the different days of operation and presents the removal efciency as a box plot for the different phases of operation. A box plot is a summary plot that plots graph data as a box representing statistical values. The boundary of the box closest to zero indicates the 25th percentile, a line within the box marks the median, and the boundary
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Figure 1. Performance of TBAB A degrading n-hexane and benzene (1:1 by volume).

of the box farthest from zero indicates the 75th percentile. The error bars above and below the box indicate the 90th and 10th percentiles, respectively. During phase I of TBAB A, the inlet concentration was 56 and 83 parts per million by volume (ppmv) for nhexane and benzene, respectively. The stagnation technique (no VOC, air, or nutrient ow for a period of 2 days/week) with ow switching for the gas phase was used as a means for controlling the biomass retained within the bed. This phase is characterized by a very low concentration of n-hexane, which is mainly used for stabilizing the biolter performance. After 18 days of acclimation to the mixture, the removal efciency of n-hexane was stable at 73% with a standard deviation of 24%, whereas benzene was almost depleted at an average removal efciency of 98%. Although the benzene inuent concentration was higher than n-hexane, the superior behavior of benzene was expected. Previous studies in the authors laboratories have shown the higher performance of benzene as compared with n-hexane in single-solute runs.14,15 The reported removal efciency of n-hexane as a sole feed to TBABs at an inuent concentration of 50 ppmv was 82%.15 On the

other hand, the average removal efciency obtained for benzene in this mixture study is similar to the reported values of 98% for inuent concentrations up to 200 ppmv for TBABs only treating benzene vapors.22 In phase II, the inuent concentration was increased to 101 ppmv n-hexane and 150 ppmv benzene. The total loading rate for this phase was 25 g/(m3 hr). The average removal efciency of benzene was not seriously affected; it held an average value of 97%. On the other hand, n-hexanes removal efciency decreased to 60%. On day 40, phase III, the inuent concentration of n-hexane was increased to 155 ppmv and that of benzene to 230 ppmv. The total loading rate for this phase was 39 g/(m3 hr). Although the benzene removal efciency was still stable at 98%, n-hexane performance decreased by 12 48% with a standard deviation of 31%. This high standard deviation is a common characteristic of n-hexane degradation that occurred in other studies without known reason.33 In phase IV, n-hexane concentration was increased to 210 ppmv and benzene to 310 ppmv. n-Hexane removal dropped further to 40% with a standard deviation of 36%,

Table 1. Operating condition for TBAB A degrading n-hexane and benzene (1:1 by volume). Phase I Condition Inlet concentration, ppmv Loading rate, g/m3 hr kg COD/m3 day Days of operation Average removal efciency (%) Standard deviation (%) Elimination capacity, g/m3 hr kg COD/m3 day Notes: H n-hexane, B H 56 6.0 0.58 124 73 24 4.4 0.43 98 2 7.9 0.58 60 21 6.6 0.64 B 83 8.0 0.59 H 101 10.7 1.04 2539 97 2 14.1 1.04 48 31 8.1 0.79 Phase II B 150 14.4 1.06 H 155 16.7 1.62 4052 98 3 22.3 1.64 40 36 9.0 0.87 Phase III B 233 22.4 1.65 H 210 22.3 2.17 5366 87 10 26.0 1.92 Phase IV B 310 29.9 2.20

benzene, COD

chemical oxygen demand.

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Figure 2. Performance of TBAB B degrading n-hexane and benzene (2:1 by volume).

and benzene removal efciency dropped to 87%. The data clearly indicate that the presence of n-hexane affected the performance of the TBAB in the treatment of benzene because previous studies showed that benzene as a single VOC source could go up to 800 ppmv with a removal efciency greater than 80%.22 Performance of TBAB B. TBAB B followed a similar n-hexane inuent concentration as TBAB A. The main difference is the corresponding benzene concentration. Figure 2 shows the performance and removal efciency of the TBAB with respect to time at the different phases. Phase I as shown in Table 2 operated under 56 and 41 ppmv for n-hexane and benzene, respectively. The average removal efciencies for this phase were 85 and 95% for n-hexane and benzene, respectively. In phase II, the inlet concentration for n-hexane was increased to 101 ppmv to be similar to that of TBAB A, and the corresponding benzene inuent concentration was 74 ppmv. The average removal efciencies were 73 and 96% with a standard deviation of 20 and 4% for nhexane and benzene, respectively. In phase III, the inlet

concentration was increased to 150 and 111 ppmv for n-hexane and benzene, respectively. The average removal efciencies were 69 and 98% for n-hexane and benzene, respectively. n-Hexane performance was affected by the increase in inuent concentration with a continuous drop in the removal efciency in addition to high uctuations of removal efciency providing a standard deviation of 33%. In phase IV, the inlet concentration was raised to 199 and 147 ppmv under the same operating conditions for n-hexane and benzene, respectively. TBAB B behaved erratically at this loading rate with respect to n-hexane; however, it maintained a stable removal efciency of benzene at 99% with 1% standard deviation. Performance of TBAB C. Figure 3 shows the performance and the removal efciency of the TBAB with respect to time for the different phases studied. Phase I shown in Table 3 operated at 38 and 168.5 ppmv n-hexane and benzene, respectively. The average removal efciencies for this phase were 88 and 97%. In phase II, the inlet concentration was increased 1.5-fold following the

Table 2. Operating condition for TBAB B degrading n-hexane and benzene (2:1 by volume). Phase I Condition Inlet concentration, ppmv Loading rate, g/m3 hr kg COD/m3 day Days of operation Average removal efciency (%) Standard deviation (%) Elimination capacity, g/m3 hr kg COD/m3 day H 56 5.9 0.58 136 85 15 5.1 0.49 95 6 3.8 0.28 73 20 6.4 0.55 B 41 4.0 0.29 H 101 10.7 1.04 3757 96 4 6.9 0.51 69 33 9.2 0.80 Phase II B 74 7.1 0.53 H 150 15.9 1.54 5875 98 2 10.6 0.78 59 37 10.3 0.90 Phase III B 111 10.6 0.78 H 199 21.1 2.06 7694 99 1 14.1 1.04 Phase IV B 147 14.2 1.05

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Figure 3. Performance of TBAB C degrading n-hexane and benzene (1:3 by volume).

same operating conditions of TBAB A. The average removal efciencies were 92 and 97% with a standard deviation of 15 and 7% for n-hexane and benzene, respectively. In phase III, the inlet concentration was increased to 84.8 and 374.7 ppmv for n-hexane and benzene, respectively. The average removal efciencies were 72 and 81% for n-hexane and benzene, respectively. n-Hexane performance was affected by the increase in inuent concentration with a sharp drop in the removal efciency in addition to very high uctuations of removal efciency with a standard deviation of 33%. In phase IV, the inlet concentration was raised to 101.3 and 445.1 ppmv under the same operating conditions for n-hexane and benzene, respectively. TBAB C behaved erratically at this loading rate with respect to n-hexane. In addition to the continuous drop of n-hexane removal efciency, the total VOC load fed to the TBAB reached the maximum allowable loading rate as identied in an earlier study.15 Performance Comparison for TBABs A, B, and C. TBABs A and B had similar inuent n-hexane concentrations. The

corresponding benzene concentration was the highest for TBAB C followed by A and B. Thus, the highest total loading rate was in TBAB C. Benzene removal efciency was greater than 95% for TBABs A and B at all concentration levels with one exception: In phase IV for TBAB A, it dropped below the 90% level when the total loading rate was 52 g/(m3 hr). At a total loading rate of 44 g/(m3 hr) in TBAB C, benzene removal efciency dropped to the 80% level. This shows that the existence of n-hexane negatively affects the biodegradation of benzene at higher loading rates. Benzene as a single substrate was mainly studied in traditional biolters.34 37 The maximum elimination capacity found was 45 g/(m3 hr) with 65% removal efciency. This behavior shows the superiority of the results obtained in the study presented here over traditional biolters. In a previous study22 using TBAB for treating only benzene vapors, an elimination capacity of 50 g/(m3 hr) with a removal efciency greater than 90% was obtained. The removal behavior of benzene in the two mixtures conducted in the study presented here was thus similar to the single-solute study. In recent studies, biodegradation of benzene in TBABs was mainly studied

Table 3. Operating condition for TBAB c degrading n-hexane and benzene (1:3 by volume). Phase I Condition Loading rate, g/m3 hr kg COD/m3 day Days of operation Average removal efciency (%) Standard deviation (%) Elimination capacity, g/m3 hr kg COD/m3 day Inlet concentration, ppmv H 38 4.0 0.39 18 88.1 9.6 3.6 0.35 97.4 2.4 16.0 1.18 92.1 14.6 5.6 0.54 B 168.5 16.2 1.97 H 56 6.0 0.58 920 97.4 6.8 23.7 1.75 71.3 33.3 6.5 0.63 Phase II B 250 24.0 1.77 H 84.8 8.9 0.87 2143 80.7 27.3 29.4 2.17 60.4 27.4 6.5 0.63 Phase III B 374.7 36.0 2.65 H 101.3 10.7 1.04 4460 85.1 14.5 36.8 2.71 Phase IV B 445.1 42.7 3.15

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in a mixture of benzene, toluene, and xylene38 or benzene, toluene, ethyl benzene, and xylene (BTEX).36,39,40 The maximum elimination capacity for benzene found in the literature was 34 g/(m3 hr). On comparing the three TBABs, it is seen that the existence of benzene affected the biodegradation of nhexane. In TBAB B, the removal efciency of n-hexane at the same loading rate of TBAB A was higher. This could be explained by the lower total loading rate of TBAB B as compared with TBAB A because of the lower loading rate of benzene. The same applies if TBAB C is compared with any of the other two. Generally, for the three TBABs, uctuations in the performance of nhexane were noticed that were reported previously by other authors.33 The overall standard deviation in the removal efciency was 28% for TBAB A, 26% for TBAB B, and 21% for TBAB C. Figure 4 shows the elimination capacity versus loading rate for the three TBABs in addition to other previous reported results for a volume ratio of 1:2.41 Figure 4a shows the combined performance of n-hexane and benzene. It is seen in the gure that n-hexane and benzene performance at the different mixing ratios are very close to each other. It is further seen that the higher the concentration of benzene in the mixture, the more deviation is seen from the 100% line. The deviation started after approximately 34 g/(m3 hr). Figure 4b focuses on n-hexane alone, in which a zoomed performance shows the difference of performance among the three TBABs, a mixture ratio of 1:2,41 and n-hexane as a single solute.14 It is clearly seen from the gure that the elimination capacity for treating n-hexane alone is much higher than that obtained in the mixtures studied. Furthermore, it is seen that nhexane in the different mixtures studied reached a maximum elimination capacity of 8 g/(m3 hr), whereas for the single solute n-hexane, the elimination capacity was still increasing with loading rate, indicating that a maximum elimination capacity is not yet attained. Figure 4c represents the performance of benzene in the different mixtures studied together with benzene treated alone.22 It can be seen that benzene treated alone behaved slightly better than benzene in the different mixture ratios with n-hexane. This clearly indicates that the loading rates of n-hexane studied did not signicantly impact the performance of benzene. Figure 5 gives an overview of the total elimination capacities for n-hexane and benzene. In this gure, loading rates and elimination capacities are totaled for comparative purposes. The gure includes the three mixtures under study, the 1:2 mixture,42 and single-fed benzene22 and n-hexane.14 It is seen that the best performance was obtained when benzene was fed separately. This was followed with 1:2 and 1:3 mixtures, which showed very similar behavior up to 55 g/(m3 hr). The 1:3 ratio was not studied beyond this loading rate because of oxygen limitation within the biolm. It is very difcult to pinpoint the single n-hexane in the gure because it coincides with mixture ratios of 1:2 and 1:3. These mixture ratios were followed in performance by the 1:1 mixture ratio. The worst performance that could be seen in the gure is the 2:1 mixture. An
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Figure 4. TBAB performance under continuous loading condition: (a) overall total results, (b) n-hexane results, and (c) benzene results. Source for data for 1:2 mixture from ref 41; for 1:3, 1:1, and 2:1 mixture from this study; for *n-hexane from ref 14; and for **benzene from ref 22.

alternative way for observing the effect of benzene on n-hexanes performance is the graph presented in Figure 6, which represents the n-hexane removal efciency as a function of the total loading rate. The removal efciency of n-hexane as a single feed and at a mixture ratio of 1:3 coincides with a total loading rate of 30 g/(m3 hr), but a sharp decline was noticed in both curves, with the mixture ratio of 1:3 providing a steeper decline in performance. Generally, Figure 6 shows that the performance of the TBAB declines as the benzene ratio in the mixture decreases.
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relative difference is very small, with an average difference of 7%. To study the carbon cycle within the bed for the liquid and gaseous phases, all of the anticipated carbon sources and products were measured. The inuent consists of inuent gaseous concentrations of n-hexane and benzene in addition to inuent aqueous IC and organic carbon (OC). The efuent includes the efuent aqueous IC and OC, efuent carbon equivalence of VSS, gaseous CO2, and the efuent carbon equivalence of n-hexane and benzene concentration. It is assumed that the inuent gas stream does not contain any CO2. This assumption was validated by frequently measuring CO2 concentrations in the inuent, which were always undetectable. The average carbon recovery rate varied among the three TBABs. The carbon recovery rate is calculated as the average value of the ratio of the sum of efuent carbon in gaseous and liquid phases by the sum of the inuent carbon for the same phases. The values of the separate sources and products of carbon were normalized to the units of milligrams carbon per day. The recovery rates were found to be 75, 93, and 81% for TBABs A, B, and C, respectively. The differences in recovery rates are due to several reasons, the most important of which is the different ratios of n-hexane to benzene. Other reasons are the range of loading rate applied to each TBAB. It is postulated that the loss in carbon between the inuent and efuent was retained as biomass within the TBAB. This hypothesis was tested by comparing the loss in carbon to the biomass amount accumulated in the TBAB, which was calculated using the daily NO3 consumption for all loading rates for the different biomass control strategies. A typical cellular composition for a heterogeneous microorganism is represented as C9H15O5N,42,43 which was used as the basis for relating the NO3 consumed in building up new biomass to estimate the amount of biomass retained within the TBAB. The results of the t test indicated that the difference between the losses in carbon to the biomass accumulated in the TBAB was highly signicant with a P value 0.05.

Figure 5. Combined n-hexane and benzene elimination capacities at different combined loading rates.

CO2 The amount of CO2 generated in the TBAB follows the simple biodegradation reaction (a) n-Hexane (b) benzene (c) oxygen 3 (e) water vapor

(1)

(d) CO2

The reaction parameters could be estimated based on two assumptions. First, n-hexane and benzene biodegradation mechanisms occur independently and the only source of CO2 is the degradation of both compounds. The second assumption was that the CO2 concentration in the inuent feed was equal to zero. This assumption was validated by continuously monitoring the feed. The molar ratio in the inuent feed of n-hexane:benzene was calculated to be 1:1.52, 1:0.68, and 1:4.5 for TBABs A, B, and C, respectively. The complete combustion reaction is given below for each contaminant: C 6H 6 C 6 H 14 7.5 O 2 3 6 CO 2 9.5 O 2 3 6 CO 2 3 H 2O 7 H 2O (2) (3)

Following the reaction parameters, the amount of CO2 produced in the TBAB could be individually estimated in every phase for every compound. The sum of the total theoretical CO2 generated could be compared with the actual CO2 measured in the TBAB. The measured CO2 was determined from the gas and the liquid phase. On average, the CO2 in the gas phase in phases I, II, III, and IV was found to be 646, 1215, 1659, and 2250 ppmv for TBAB A; 405, 576, 997, and 1153 ppmv for TBAB B; and 1400, 1728, 2126, and 2522 ppmv for TBAB C, respectively. Liquid CO2 is measured using the IC in the efuent samples. It was found that the average values for theses four phases were 158, 172, 187, and 200 mg/L for TBAB A; 158, 187, 190, and 200 mg/L for TBAB B; and 217, 224, 227, and 261 mg/L for TBAB C, respectively. Comparison between the theoretical CO2 concentration and the actual measured concentration is presented in Table 4. It could be seen the absolute
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Figure 6. n-hexane removal efciency at different combined loading rates.

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Table 4. CO2 measured and calculated in the three TBABs in mol/(m3 hr). CO2 Generated by n-Hexane 0.53 0.62 0.84 1.26 0.35 0.44 0.64 0.72 0.25 0.39 0.45 0.75 0.1 0.3 0.6 0.8 0.1 0.1 0.3 0.4 0.0 0.1 0.1 0.1 CO2 Generated by Benzene 0.58 0.98 1.39 1.91 0.29 0.48 0.91 0.96 1.23 1.82 2.26 2.83 0.1 0.3 0.6 0.3 0.0 0.1 0.3 0.3 0.0 0.1 0.6 0.4 Total CO2 Generated 1.11 1.6 2.23 3.17 0.64 0.92 1.55 1.68 1.48 2.21 2.71 3.28 CO2 Measured (gas) 0.83 1.56 2.13 2.89 0.52 0.74 1.28 1.48 1.30 1.70 2.00 2.40 CO2 Measured (liquid) 0.11 0.12 0.13 0.14 0.11 0.13 0.13 0.14 0.15 0.16 0.16 0.18 Total CO2 Measured 0.94 1.68 2.26 3.03 0.63 0.87 1.41 1.62 1.45 1.86 2.16 2.58 Relative Difference (%) 15.32 5.00 1.35 4.42 1.56 5.43 9.03 3.57 1.89 15.75 20.23 21.25

TBAB A

Phase I II III IV I II III IV I II III IV

Figure 7 shows the different components of the carbon in the inuent and efuent streams for the TBABs. It is worthwhile to note that the main key players in carbon contribution are the gas-phase concentrations: inuent and efuent n-hexane and benzene concentration and efuent gaseous CO2. The total VOCs in the efuent gas phase (the sum of n-hexane and benzene) for the TBABs were 21% with 11% standard deviation, whereas the total VOCs in the inuent were 70% with 15% standard deviation. The share of carbon in the liquid phase due to the amount calculated from VSS and inuent and efuent OC in the aqueous phase can be considered to be negligible because the total aqueous carbon did not exceed 5% of the TC in the system (gaseous and liquid phases). Flow switching of the gas ow did not cause loss of n-hexane and benzene in the liquid phase when the gas and liquid phases were run countercurrently. Kinetics of TBAB Performance The removal performance as a function of depth was measured weekly (1 day after stagnation and owswitching techniques) at the sampling ports, located along the depth at 7.6, 23, 38, 53, and 60 cm measured from the media top. These data were used to develop the pseudo-rst-order reaction rate constant as a function of time. To avoid misinterpretation of data, the kinetic analyses were conducted using the data from sampling ports within the media because there is a possibility of biodegradation on the top portion of the TBAB above the media or at the bottom disengagement chamber used for separation of liquid and gas efuents. The reaction rate constant is calculated assuming pseudorst-order reaction occurring in a plug ow reactor. All sampling data at every concentration level (minimum of three datasets) were t with a linear model with the independent variable of time (sec) and the dependant variable of log(C/Co), where C is the efuent concentration and Co is the inuent concentration. In Figure 8, the reaction rate constant for nhexane and benzene is plotted at different n-hexane concentrations for TBABs A and B. TBAB C is not included because the n-hexane concentration does not follow the same trend as the other two biolters. It can
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be seen that benzenes reaction rate constant is generally higher than that of n-hexane at the concentration ratios of 1:1 and 2:1. Furthermore, n-hexanes reaction rate constant at the ratio of 1:1 is higher than that at the ratio of 2:1. This could be explained because the excess benzene in the mixture helped the biodegradation of n-hexane. Benzenes reaction rate constant at 2:1 is close to the corresponding value at 1:1 except at the highest concentration level. This is despite the benzene concentration in the 2:1 ratio being less than the corresponding concentration in the 1:1 ratio. The reaction rate constant values for n-hexane ranged from 0.007 to 0.009 1/sec for the 1:1 ratio, 0.004 to 0.007 1/sec for the 2:1 ratio, and 0.004 to 0.008 1/sec for the 1:3 ratio. The reaction rate constant reported for n-hexane in a single feed ranges from 0.009 to 0.03 1/sec.15 This shows clearly that for the 1:1 ratio the rate constant for n-hexane was similar to that at the low end for n-hexane fed alone. On the other hand, benzene ranged from 0.012 to 0.021 1/sec for the 1:1 ratio, 0.013 to 0.021 1/sec for the 2:1 ratio, and 0.008 to 0.022 1/sec for the 1:3 ratio. Similar values were reported for the biodegradation of benzene in the BTEX mixture in a TBAB.30 The reported values were in the range of 0.0196 1/sec at a loading rate of 14 g/(m3 hr) to 0.0448 1/sec at a loading rate of 42 g/(m3 hr).

Figure 7. Different element contributions in the carbon cycle for the TBABs.
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5. Lee, J.-Y.; Choi, Y.-B.; Kim, H.-S. Simultaneous Biodegradation of Toluene and p-Xylene in a Novel Bioreactor: Experimental Results and Mathematical Analysis; Biotechnol. Progr. 1993, 9, 46-53. 6. Lee, J.-Y.; Roh, J.-R.; Kim, H.-S. Metabolic Engineering of Pseudomonas putida for the Simultaneous Biodegradation of Benzene, Toluene, and p-Xylene Mixture; Biotechnol. Bioeng. 1994, 43, 1146-1152. 7. Fitch, M.W.; England, E.; Zhang, B. 1-Butanol Removal from a Contaminated Airstream under Continuous and Diurnal Loading Conditions; J. Air & Waste Manage. Assoc. 2002, 52, 1288-1297. 8. Mohseni, M.; Allen, D. Transient Performance of Biolters Treating Mixtures of Hydrophilic and Hydrophobic Volatile Organic Compounds; J. Air & Waste Manage. Assoc. 1999, 49, 1434-1441. 9. Kim, D.; Cai, Z.; Sorial, G.A. Evaluation of Trickle-Bed Air Biolter Performance under Periodic Stressed Operating Conditions as a Function of Styrene Loading; J. Air & Waste Manage. Assoc. 2005, 55, 200-209. 10. Kim, D.; Cai, Z.; Sorial, G.A.; Shin, H.; Knaebel, K. Integrated Treatment Scheme of a Biolter Preceded by a Two-Bed Cyclic Adsorption Unit Treating Dynamic Toluene Loading; Chem. Eng. J. 2007, 130, 45-52. 11. Aly Hassan, A.; Zehraoui, A.; Sorial, G. Achieving Stable Biological Oxidation of Erratic Waste Gas Streams by Utilizing Cyclic Adsorption/Desorption Beds; J. Adv. Oxidation Technol. 2010, 13, 9-14. 12. Zhu, X.; Suidan, M.T.; Pruden, A.; Yang, C.; Alonso, C.; Kim, B.J.; Kim, B.R. Effect of Substrate Henrys Constant on Biolter Performance; J. Air & Waste Manage. Assoc. 2004, 54, 409-418. 13. Deshusses, M.; Johnson, C.T. Development and Validation of a Simple Protocol to Rapidly Determine the Performance of Biolters for VOC Treatment; Environ. Sci. Technol. 2000, 34, 461-467. 14. Aly Hassan, A.; Sorial, G. n-Hexane Biodegradation in Trickle Bed Air Biolters; Water Air Soil. Poll. 2008, 8, 287-296. 15. Aly Hassan, A.; Sorial, G.A. A Comparative Study for Destruction of n-Hexane in Trickle Bed Air Biolters; Chem. Eng. J. 2010, 162, 227233. 16. Mireles, J.R., II; Toguchi, A.; Harshey, R.M. Salmonella enterica Serovar Typhimurium Swarming Mutants with Altered Biolm-Forming Abilities: Surfactin Inhibits Biolm Formation; J. Bacteriol. 2001, 183, 5848-5854. 17. Van-Groenestijn, J.W.; Lake, M.E. Elimination of Alkanes from OffGases Using Biotrickling Filters Containing Two Liquid Phases; Environ. Prog. 1999, 18, 151-155. 18. Van-Groenestijn, J.W.; Van-Heininge, W.N.; Kraakm, N.J. Biolters Based on the Action of Fungi; Water Sci. Technol. 2001, 44, 227-232. 19. Kennes, C.; Veiga, M.C. Fungal Biocatalysts in the Bioltration of VOC-Polluted Air; J. Biotechnol. 2004, 113, 305-319. 20. Arriaga, S.; Revah, S. Improving Hexane Removal by Enhancing Fungal Development in a Microbial Consortium Biolter; Biotechnol. Bioeng. 2005, 90, 107-115. 21. Arriaga, S.; Revah, S. Removal of n-Hexane by Fusarium solani with a Gas-Phase Biolter; J. Ind. Microbiol. Biotechnol. 2005, 32, 548-553. 22. Aly Hassan, A.; Sorial, G. Biological Treatment of Benzene in a Controlled Trickle Bed Air Biolter; Chemosphere 2009, 75, 1315-1321. 23. Aly Hassan, A.; Sorial, G. Removal of Benzene under Acidic Conditions in a Controlled Trickle Bed Air Biolter; J. Hazard. Mater. 2010, 184, 345-349. 24. Aly Hassan, A.; Sorial, G. Trickle Bed Air Biolter Treating a Mixture of n-Hexane and Benzene. Presented at the A&WMA 103rd Annual Conference, Detroit, MI, 2009. 25. Montgomery, J.H.; Welkom, L.M. Groundwater Chemicals Desk Reference 3rd ed.; CRC: Boca Raton, FL, 2000; p 1345. 26. Superfund Chemical Data Matrix (SCDM); available at http://www. epa.gov/superfund/sites/npl/hrsres/tools/scdm.htm (accessed 2010). 27. Preferred and Alternative Methods for Estimating Air Emissions from Wastewater Collection and Treatment; Point Sources Committee; Emission Inventory Improvement Program: Morrisville, NC, 1997; p 98. 28. Shiu, W.-Y.; Ma, K.-C. Temperature Dependence of Physical-Chemical Properties of Selected Chemicals of Environmental Interest. I. Mononuclear and Polynuclear Aromatic Hydrocarbons; J. Phys. Chem. Ref. Data 2000, 29, 41-130. 29. Cai, Z.; Kim, D.; Sorial, G.A. Removal of Methyl Isobutyl Ketone from Contaminated Air by Trickle-Bed Air Biolter; J. Environ. Eng. ASCE 2005, 131, 1322-1329. 30. Sorial, G.A.; Smith, F.L.; Suidan, M.T.; Biswas, P.; Brenner, R.C. Evaluation of Trickle Bed Biolter Media for Toluene Removal; J. Air & Waste Manage. Assoc. 1995, 45, 801-810. 31. Smith, F.L.; Sorial, G.A.; Suidan, M.T.; Breen, A.W.; Biswas, P.; Brenner, R.C. Development of Two Biomass Control Strategies for Extended, Stable Operation of Highly Efcient Biolters with High Toluene Loadings; Environ. Sci. Technol. 1996, 30, 1744-1751. 32. Eaton, A.D.; Clesceri, L.S.; Rice, E.W.; Greenberg, A.E.; Franson, M.A.H. Standard Methods for Examination of Water & Wastewater, 21st ed.; American Public Health Association; American Water Works Association; Water Environment Federation: Washington, DC, 2005. Journal of the Air & Waste Management Association 209

Figure 8. Reaction rate constant for n-hexane and benzene.

CONCLUSIONS This study investigated the effect of different loading rates on the performance of a TBAB under acidic pH for removal of a mixture of n-hexane and benzene mixed in ratios of 1:1, 2:1, and 1:3 by volume. Flow switching accompanied with stagnation for a period of 2 days/week in the TBAB was used as means for biomass control within the bed. Benzene performance in the TBAB was signicantly high as compared with n-hexane. Benzene removal efciency started to decrease at an inuent concentration of 310 ppmv. It declined to 87% in the 1:1 ratio, whereas it was always greater than 95% in the 2:1 ratio and reached 80% at 374 ppmv in the 1:3 ratio. On the other hand, n-hexane removal efciency started at a low level of 75% and continued to decline with increases in concentration until it reached 40% at 210 ppmv for the 1:1 ratio, whereas better n-hexane performance was realized in the 2:1 ratio starting at 85% and declined to 59% at higher concentration levels. n-Hexane performance in the mixture was worse than the performance obtained as a single feed. However, the performance of benzene was very close to the single-fed benzene. This means that the presence of benzene slows the degradation of n-hexane, but the presence of n-hexane has no signicant impact on the performance of benzene at the concentration levels studied. ACKNOWLEDGMENTS The authors thank the nancial support from National Science Foundation (NSF) under award CBET 0852803. The ndings and conclusions expressed in this publication are solely those of the authors and do not necessary reect the views of NSF. REFERENCES
1. Delhomenie, M.; Heitz, M. Bioltration of Air: A Review; Crit. Rev. Biotechnol. 2005, 25, 53-72. 2. Crocker, B.; Schnelle, K. Air Pollution Control for Stationary Sources. In Encyclopedia of Environmental Analysis and Remediation; Meyers, R.A., Ed. John Wiley and Sons: New York, 1998; pp 151-213. 3. Devinny, J.; Deshusses, M.; Webster, T. Bioltration for Air Pollution Control; CRC: Boca Raton, FL, 1999; pp 51-81. 4. Kelly, W.R.; Hornberger, G.M.; Herman, J.S.; Mills, A.L. Kinetics of BTX Biodegradation and Mineralization in Batch and Column Systems; J. Contam. Hydrol. 1996, 23, 113-132. Volume 61 February 2011

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33. Plaggemeier, T. Elimination of the Poorly Water-Soluble Model Exhaust n-Hexane and Toluene in Biorieselbettverfahren (in German); University of Stuttgart: Stuttgart, Germany, 2000. 34. Kim, J.-O. Degradation of Benzene and Ethylene in Biolters; Process Biochem. 2003, 39, 447-453. 35. Zilli, M.; Guarino, C.; Daffonchio, D.; Borin, S.; Converti, A. Laboratory-Scale Experiments with a Powdered Compost Biolter Treating Benzene-Polluted Air; Process Biochem. 2005, 40, 2035-2043. 36. Garci a-Pena, I.; Ortiz, I.; Herna ndez, S.; Revah, S. Bioltration of BTEX by the Fungus Paecilomyces variotii; Int. Biodeter. Biodegr. 2008, 62, 442-447. 37. Mathur, A.K.; Majumder, C.B.; Chatterjee, S. Combined Removal of BTEX in Air Stream by Using Mixture of Sugar Cane Bagasse, Compost and GAC as Biolter Media; J. Hazard. Mater. 2007, 148, 64-74. 38. Maliyekkal, S.M.; Reneb, E.R.; Philip, L.; Swaminathan, T. Performance of BTX Degraders under Substrate Versatility Conditions; J. Hazard. Mater. 2004, 109, 201-211. 39. Lu, C.; Lin, M.-R.; Chu, C. Effects of pH, Moisture, and Flow Pattern on Trickle-Bed Air Biolter Performance for BTEX Removal; Adv. Environ. Res. 2002, 6, 99-106. 40. Sorial, G.A.; Smith, F.L.; Suidan, M.T.; Pandit, A.; Biswas, P.; Brenner, R.C. Evaluation of Trickle Bed Air Biolter Performance for BTEX Removal; J. Environ. Eng. ASCE 1997, 123, 530-538. 41. Aly Hassan, A.; Sorial, G. Bioltration of n-Hexane in the Presence of Benzene Vapors; Chem. Technol. Biotechnol. 2010, 85, 371-377. 42. Symons, J.M.; McKinney, R.E. The Biochemistry of Nitrogen in the Synthesis of Activated Sludge; Sewage Ind. Wastes 1958, 30, 874-890. 43. Rittmann, B.E.; McCarty, P.L. Environmental Biotechnology: Principles and Applications; McGraw-Hill: New York, 2001.

About the Authors Ashraf Aly Hassan is currently an Oak Ridge Institute for Science and Education postdoctoral fellow at the U.S. Environmental Protection Agency in Cincinnati, OH. This work was conducted while he was a Ph.D. student at the University of Cincinnati. George A. Sorial is a professor of environmental engineering in the Environmental Engineering Program at the School of Energy, Environmental, Biological, and Medical Engineering of the College of Engineering and Applied Science at the University of Cincinnati. Please address correspondence to: George A. Sorial, 701 Engineering Research Center, 2624 Clifton Avenue, Cincinnati, OH 45221-0012; phone: 1-513-556-2987; fax: 1513-556-4162; e-mail: George.Sorial@uc.edu.

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