Ultrasonics Sonochemistry 17 (2010) 9901003

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Advanced oxidation processes (AOPs) involving ultrasound for waste water treatment: A review with emphasis on cost estimation
Naresh N. Mahamuni, Yusuf G. Adewuyi *
Department of Chemical Engineering, North Carolina Agricultural and Technical State University, Greensboro, North Carolina 27411, United States

a r t i c l e

i n f o

a b s t r a c t
Two things are needed for any technology to be suitable for use in the industry, viz. 1. Technical feasibility and 2. Economical feasibility. The use of ultrasound for waste water treatment has been shown to be technically feasible by numerous reports in the literature over the years. But there are hardly any exhaustive reports which address the issue of economical feasibility of the use of ultrasound for waste water treatment on industrial scale. Hence an attempt was made to estimate the cost for the waste water treatment using ultrasound. The costs have been calculated for 1000 L/min capacity treatment plant. The costs were calculated based upon the rate constants for pollutant degradation. The pollutants considered were phenol, trichloroethylene (TCE) and reactive azo dyes. Time required for ninety percent degradation of pollutant was taken as the residence time. The amount of energy required to achieve the target degradation was calculated from the energy density (watt/ml) used in the treatability study. The cost of treatment was calculated by considering capital cost and operating cost involved for the waste water treatment. Quotations were invited from vendors to ascertain the capital cost of equipments involved and operating costs were calculated based on annual energy usage. The cost was expressed in dollars per 1000 gallons of waste water treated. These treatment costs were compared with other established Advanced Oxidation Process (AOP) technologies. The cost of waste water treatment for phenol was in the range of $89 per 1000 gallons for UV/US/O3 to $15,536 per 1000 gallons for US alone. These costs for TCE were in the range of $25 per 1000 gallons to $91 for US + UV treatment and US alone, respectively. The cost of waste water treatment for reactive azo dyes was in the range of $65 per 1000 gallon for US + UV + H2O2 to $14,203 per 1000 gallon for US alone. This study should help in quantifying the economics of waste water treatment using ultrasound on industrial scale. We strongly believe that this study will immensely help the researchers working in the area of applications of ultrasound for waste water treatment in terms of where the technology stands today as compared to other available commercial AOP technologies. This will also help them think for different ways to improve the efciency of using ultrasound or search for other ways of generating cavitation which may be more efcient and help reduce the cost of treatment in future. 2009 Elsevier B.V. All rights reserved.

Article history: Received 5 January 2009 Received in revised form 4 September 2009 Accepted 21 September 2009 Available online 29 September 2009 Keywords: Cost estimation AOP Ultrasound Sonochemistry Waste water treatment

1. Introduction It has been many years since Richards and Loomis [1] rst used ultrasound for producing cavitation, degassing of water and for accelerating chemical reactions. Ultrasound has since been used for many applications such as cell disruption, crystallization, atomization, degassing, polymerization, emulsication, nanotechnology, waste water treatment, chemical reactions, food preservation, drug delivery, cleaning, drilling, cutting, welding, ow measurements, aw detection, ultrasonic imaging, sonar detection and many more [2]. There have been many reviews on the subject of sonochemistry spanning from themes based on particular
* Corresponding author. Tel.: +1 336 334 7564x107; fax: +1 336 334 7417. E-mail address: adewuyi@ncat.edu (Y.G. Adewuyi). 1350-4177/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.ultsonch.2009.09.005

application to general in nature. Recently, Bruce and Nareddy [3] and Thompson and Doraiswamy [2] gave a very good review of sonochemistry in general whereas Adewuyi [46] critically covered the subject of waste water treatment using ultrasound. In recent years, ultrasound has been extensively used as an advanced oxidation process (AOP) for waste water treatment. This is owing to the production of OH radicals in aqueous solutions and subsequent oxidation of pollutants in the presence of ultrasound.

H2 O ! H OH H O2 ! HOO

1 2 3 4

Pollutants OH ! Degradation products Pollutants HOO ! Degradation products

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

991

Nomenclature CA0 CA k Sf St 1.2S initial concentration in ppm nal concentration in ppm rate constant, in ppm min1 for zero order and min1 for rst order reaction sampling frequency sampling time total capital cost (Table 4) A r n Pelec t V amortized annual capital cost annual discount rate (assumption = 7%) life of project (assumption = 30 years) EE/O is kWh/m3/order is the input power (kW) to the AOP system is the irradiation time (min) is the volume in liter of water in the reactor

The formation of OH radicals by decomposition of water was rst proposed by Weiss [7] and later conrmed by Makino et al. [8]. The formation of OH radicals takes place inside the cavity in the presence of ultrasound by pyrolysis. The pyrolysis takes place inside the cavity and near the interface of the cavity and surrounding liquid at the time of collapse of the cavity in the presence of ultrasound. Pyrolysis takes place because of the very high temperatures reached during cavitation. Suslick et al. [9,10] have found that these temperatures are in the range of 5200 K and 1900 K in the cavity and interfacial region, respectively. The formation of hydrogen peroxide was observed by Fitzgerald et al. [11]. This hydrogen peroxide also helps in the degradation of pollutants in wastewater.

Pollutants H2 O2 ! Degradation products

Since then ultrasound has been studied for the waste water treatment of various pollutants such as aromatic compounds, chlorinated aliphatic compounds, explosives, herbicides and pesticides, organic dyes, organic and inorganic gaseous pollutants, organic sulfur compounds, oxygenates and alcohols, pharmaceuticals, personal care products, pathogens and bacteria in water [4]. It has virtually been proved beyond doubt that ultrasound can be used for the treatment of any kind of wastewater. But due to the inefcient conversion of energy in producing ultrasonic cavitation and possible difculties in its scale up, no industrial installations for waste water treatment have been reported in the literature. Researchers are trying to circumvent these difculties by using hybrid techniques for waste water treatment using ultrasound. Gogate [12] has reviewed such efforts in his recent paper in ultrasonic sonochemistry. There are other reports in the literature where efforts have been made to use ultrasound in the presence of ozone [13], hydrogen peroxide [14], Fentons reagent [14], photocatalysts [15] and enzymes [16]. The intensication of ultrasonic waste water treatment with such hybrid techniques might help reduce the cost of waste water treatment. An attempt has been made to estimate the cost for the waste water treatment using ultrasound. The cost has been calculated for 1000 L/min capacity treatment plant. The cost is expressed in US dollars (USD) per 1000 gallons of waste water treated (1 US gallon = 3.79 L). These treatment costs are compared with other established AOP technologies. Candidates from three types of pollutants were selected as model pollutants for cost estimation because they are widely studied in the literature; they are the most common organic pollutants in waste water; and are among the most recalcitrant and harmful in nature. The three candidates are phenol, trichloroethylene (TCE) and reactive azo dyes. Phenol has been ranked 182 in the 2007 the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) Priority List of Hazardous Substances. Phenol is released to the air and water as a result of its manufacture and use in phenolic resins, organic synthesis, petroleum products such as coal tar and creosote. It can also be released by combustion of wood and auto exhaust. Phenol is also produced by the natural degradation of organic wastes including benzene. Phenol mainly enters the water

from industrial efuent discharges. Phenol has been measured in efuents (up to 53 ppm), ambient water (1.5 P 100 ppb), drinking water (not quantied), groundwater (1.9 P 10 ppb), rain (0.075 1.2 ppb), sediment (>10 ppb) and ambient air (0.0344 ppb). The United States EPA lifetime health advisory for phenol in water is two milligrams per liter (2 mg/L) [17]. Trichloroethylene (TCE) is reasonably anticipated as a human carcinogen [18]. The largest releases of TCE generally come from metalworking facilities, plastics and plastic products facilities, electron tubes facilities and aircraft facilities. Because TCE is pervasive in the environment, most people are likely to be exposed to TCE by simply eating, drinking and breathing in the nearby area of source. As per Safe Drinking Water Act, Maximum Contaminant Level (MCL) for TCE in water is 0.005 mg/L [19]. Textile industries consume large volumes of water and chemicals for wet processing of textiles. The chemical reagents used are very diverse in chemical composition, ranging from inorganic compounds to polymers and organic products. The presence of even very low concentrations of dyes in the efuent is highly visible and undesirable. There are more than 100,000 commercially available dyes with over a million ton of dye-stuff produced annually [20]. Due to their chemical structure, dyes are resistant to fading on exposure to light, water and many chemical treatments. Decoloration of textile dye efuent does not occur when treated aerobically by municipal sewerage systems. Over 90% of some 4000 dyes tested in the Ecological and Toxicological Association of Dyes and Organic Pigments Manufacturers (ETAD) survey had LD50 values greater than 2000 mg/kg [21]. Acute toxicity involves oral ingestion and inhalation, skin and eye irritation and skin sensitization. There is evidence that some reactive azo dyes cause contact dermatitis, allergic conjunctivitis, rhinitis, occupational asthma or other allergic reactions in plant workers [20]. Many dyes are difcult to decolorize due to their complex structure and synthetic origin. Brightly colored, water-soluble reactive azo and acid dyes are the most problematic, as they tend to pass through conventional treatment systems unaffected. Municipal aerobic treatment systems, dependent on biological activity, were found to be inefcient in the removal of these dyes [21]. Hence, advanced oxidation processes (AOPs) are needed for their treatment. Reactive azo dyes are by far the most important class of dye, accounting for over 50% of the world annual production. Hence we selected reactive azo dyes as model candidate for the cost estimation study. 2. Theory of AOPs Advanced oxidation processes (AOPs) are those processes which are based on production and utilization of hydroxyl radicals. AOPs have considerable similarities due to the participation of hydroxyl radicals in most mechanisms that are operative during the reaction. Hydroxyl radicals are extremely unstable and reactive because of their high oxidation potential. Since the reactions between hydroxyl radicals and organic species are extremely fast and nonspecic, these reactions are almost always controlled by the mass transfer of hydroxyl radical to the organic species or

992 Table 1 Various AOPs and their principle reactions. Process O3

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

Principle reactions

Reference

O3 OH ! O3 HO ! 2

HO O2 2 HO2 O 3

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Belran [50]

US/O3

O3 ! O2g O3 Pg O Pg H2 Og ! 2 OH
3

Destaillats [51]

O3/H2O2 UV/O3 UV/H2O2 US/H2O2/CuO

H2 O2 2O3 ! 2OH 3O2 O3 H2 O ! 2OH O2 H2 O2 ! 2OH M H2 O ! M OH OH H2 O OH ! H2 HO2 HO2 ! H O 2 M O ! M O2 2 M HO2 ! M HO 2

hm hm

Glaze and Kang, [52] Glaze et al. [53]; Peyton and Glaze, [54] Legrini et al. [55] Drijvers et al. [56]; Weiss, [57]

O3/UV/H2O2 Fentons reagent US/Fenton

O3 H2 O2 H2 O ! 4OH O2 H2 O2 Fe2 ! Fe3 OH OH Fe2 H2 O2 ! Fe3 OH OH Fe

2

hm

Mokrini et al. [58]; Beltran, [50] Walling and Goosen, [59] Neppolian et al. [60]

H2 O2 ! Fe OOH

Fe OOH2 ! Fe2 isolated HO2 Fe2 isolated H2 O2 ! Fe3 OH OH

Photocatalysis

TiO2 ! e h TiO2 h TiO2 h TiO2 h

hm

Legrini et al. [55], Adewuyi, [5,6]

H2 Oad ! TiO2 HOad HOad ! TiO2 HOad RXad ! TiO2 RX ad

24 25 26

production of hydroxyl radicals. The kinetics seems to be rst order with respect to hydroxyl radical concentration and to the pollutant [22,23]. Kinetic constants are in the range of 1081010 M1 s1, whereas radical concentration, even in steady state, in these processes is between 1012 and 1010 M. Therefore, the pseudo rst order constant is in the range of 104.1 s1. Given that the hydroxyl radical is such an unstable and reactive species, it must be generated continuously in situ through chemical or photochemical or sonochemical reactions. The main processes and their mechanisms to obtain these radicals are summarized in Table 1, Eq. (6-26). Andreozzi et al. [24] have made a survey of various AOPs and described their general mechanisms. 3. Cost estimation methodology A very simple methodology was developed to arrive at the treatment costs of the various AOPs studied. First of all, data were collected from the published literature for all the AOPs involving the use of ultrasound and some standard commercial AOPs. Table 2 shows the various studies considered for this investigation along with their operating conditions. From this data, the kinetics of pollutant removal was found. If the kinetics is reported then it was taken from the literature as such; otherwise it was calculated from the data given in the literature using standard methods of nding kinetics [25]. By kinetics, we mean the order of degradation and the rate constant. Table 3 depicts the kinetic data collected from these studies. These rate constants were then used to calculate the time required for 90% degradation of the pollutant from its initial concentration. This time was assumed as the residence time for the reactor for waste water treatment using the given AOP. The cost estimation was done for the assumed ow rate of 1000 L/min.

The reactor capacity was calculated by multiplying the residence time with the design ow rate (1000 L/min). From the treatability study in the literature, the energy consumption data was then collected as energy dissipated per unit volume (watt/ml). The total amount of energy required to treat the waste water at the designed ow rate for given residence time was then calculated. From the quotations, which we had invited from manufacturers, we knew the amount of energy supplied by one commercial unit. Hence the number of such commercial units required for dissipating the required energy was calculated. From the number of commercial units required, the capital cost of the waste water treatment unit was calculated (AOP unit cost). This AOP unit cost was used to calculate the total capital cost using certain standard assumptions. These assumptions are described in the next section. Similarly total annual operating and maintenance cost was also calculated. The total capital cost was amortized at a rate of 7% over a period of 30 years to arrive at total amortized annual capital cost. Sum of the annual operating and maintenance cost and annual capital cost gave the total annual operating cost. Dividing this cost with the amount of gallons of waste water treated in a year gave us the cost of waste water treatment per 1000 gallons of water treated. It was assumed that the plant is running throughout the year (52 weeks) continuously. The cost estimation of various ultrasonic AOPs for the elimination of phenol, reactive dyes and TCE was performed on the basis of the rate constants. Since the rate of degradation changes signicantly with the experimental system, the reactor conguration and the operating conditions such as pH, UV intensity or US intensity etc., limited number of sources having similar operating conditions were considered. Kinetic data was collected from a limited number of sources in the literature (as shown in Table 3). Five

Table 2 The operating conditions in treatability studies. Process For phenol UV, US, O3, UV + US US + O3, UV + O3, US + UV + O3 US + H2O2 + CuO Fenton and US + Fenton Photocatalysis and US + Photocatalysis For reactive azo dye UV, US, O3, UV + US, US + O3, UV + O3, US + UV + O3 US + H2O2, UV + H2O2, US + UV + H2O2 Photocatalysis and US + Photocatalysis For TCE UV, UV + H2O2 Reaction volume 100 ml Initial concentration UV source US source Ozone SOURCE Oxidant Catalyst Reference

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

2.5 mM (235.275 mg/L)

254 nm, ULTRAMAX STL 257, 15 W MP-UV mercury vapor quartz lamp 450 W 254 nm, Philips, PL-L 18 W TUV two lamps 254 nm, Philips, PL-L 11 W TUV six lamps MP-UV U-mercury vapor quartz lamp 500 W 254 nm, OSRAM, HNS 20 W/U 20 W LP mercury vapor lamp 254 nm, 100 W MP-UV mercury vapor lamp 450 W HANOVIA MP-UV mercury vapor quartz lamp

300 kHz, Undatim ultrasonics, 25 W 520 kHz Undatim ortho reactor 18.2 W 35 kHz SODEVA 50 W 20 kHz UWR ultrasonic 75 W 520 kHz, Undatim Ultrasonics, 600 W Specications not given (20 kHz, 120 W assumed) 47 kHz Branson 1200 model 30 W

Ozonelab OL-100 model, 36 W at 0.75 L/min ow

O3 4.4 mg/L

Kidak and Ince, [38] Drijvers et al. [56] Entezari et al. [61] Chen and Smirniotis, [15] Tezcanli-Guyer and Ince, [62] Fung et al. [63] Taicheng et al. [64] Hirvonen et al. [65] Distaillates et al. [28] Nakano et al. [66] Sato et al. [67] Crittenden et al. [68]

150 ml 350 ml 100 ml

0.6 mM (56.47 mg/L) 0.67 mM (63.05 mg/L) 1 mM (94.11 mg/L)

H2O2 100 mM H2O2 60.5 mM O2 500 ml/ min O3 40 mg/L

CuO 1 mg/ml CuSO4 2.39 mM HOMBIKAT TiO2 UV-100 0.25 g/L

1200 ml

57 lM (19.95 mg/L)

Ozonelab OL-100 model, 36 W at 0.25 L/min ow

4500 ml 700 ml

0.1 g/L (100 mg/L) 0.5 mM (393.75 mg/L)

H2O2 6.53 mM Air 0.1 m3/h

CuO 1 mg/ml Degussa P-25 TiO2 0.75 g/L

5000 ml

US O3 US + UV Photocatalysis

600 ml 150 ml 4100 ml 7200 ml

12.6 lM for UV(1.66 mg/L) 16.7 lM for UV + H2O2 (2.194 mg/L) 250 lM (32.85 mg/L) 2.5 mg/L 0.102 mM (13.40 mg/L) 15 mg/L

H2O2 5 mM

520 kHz, Undatim ultrasonics, 50 W 20 kHz, Model XL2020 Misonix 330 W

Equipment not given ow rate 500 ml/min

H2O2 6.53 mM O3 20 mg/L Dissolved oxygen 9 mg/L

CuO 1 mg/ml 1% Pt on TiO2 from Aldrich 0.5 g/L

993

994 Table 3 Rate constants of various AOPs for degradation. Process For phenol UV (254 nm) US (300 kHz) O3 (2 mg/L) US + UV US + O3 UV + O3 US/UV/O3 US/H2O2/CuO Fenton SonoFenton UV/H2O2 Photocatalysis Sonophotocatalysis For reactive azo dye UV (254 nm) US (300 kHz) O3 (12.4 mg/L) US + UV US + O3 UV + O3 US/UV/O3 US/H2O2 UV/H2O2 US/UV/H2O2 Photocatalysis Sonophotocatalysis For TCE UV (254 nm) US (500 kHz) O3 (6 mg/L) US + UV UV/H2O2 Photocatalysis k 0.0021 min1 0.0008 min1 0.0279 min1 0.005 min1 0.0326 min1 0.0869 min1 0.1793 min1 0.0149 min1 0.0106 min1 0.058 min1 0.0524 min1 0.433 ppm min1 0.712 ppm min1

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

Reference Kidak and Ince [38] Kidak and Ince [38] Kidak and Ince [38] Kidak and Ince [38] Kidak and Ince [38] Kidak and Ince [38] Kidak and Ince [38] Drijvers et al. [56] Entezari et al. [61] Entezari et al. [61] Primo et al. [69] Chen and Smirniotis [15] Chen and Smirniotis [15] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Tezcanli-Guyer and Ince [62] Fung et al. [63] Fung et al. [63] Fung et al. [63] Taicheng et al. [64] Taicheng et al. [64] Hirvonen et al. [65] Destaillats et al. [28] Nakano et al. [66] Sato et al. [67] Hirvonen et al. [65] Crittenden et al. [68]

No degradation observed 0.00175 min1 0.01108 min1 0.0055 min1 0.01674 min1 0.02064 min1 0.02171 min1 0.0032 min1 0.0124 min1 0.0357 min1 0.0207 ppm min1 0.0757 ppm min1 0.0589 min1 0.0457 min1 0.0209 min1 0.181 min1 0.4418 min1 Apparent rate constant = 49.57 lg/L s1 adsorption equilibrium constant = 0.000466 l/lg

Adewuyi [4] has summarized results of a number of studies of waste water treatment using ultrasonic processes. They have reported the rates of degradation for phenol, TCE, reactive dyes and a number of other hazardous compounds. Kidak and Ince [26] have recently reviewed the subject of phenol degradation using ultrasonic processes. Beckett et al. [27] have described the degradation of phenols and chlorinated compounds and their mixtures using ultrasonic cavitation. They have reported that TCE has the degradation rate in the range of 0.01970.0617 min1. Destaillats et al. [28,29] have reported the scale up of sonochemical reactors for waste water treatment. They have reported the rates of degradation of TCE in a number of sonochemical reactors and the rate of TCE degradation was in the range of 0.0330.203 min1. They have also reported the rates of degradation for reactive dyes. It lies in the range of 0.0020.045 min1. Lesko [30] have reported the rates of degradation of phenol using a pilot station sonochemical reactor. The authors found that the rate of phenol degradation was in the range of 0.00110.063 min1. Zheng et al. [31] have reported the rates of sonochemical degradation of phenol in the range of 0.0140.061 min1. Lesko et al. [13] have reported the rate of phenol degradation in the presence of ozone and ultrasound to be in the range of 0.137 min1. One can observe from Table 3 that the reported rates of degradation of phenol, TCE and reactive dyes are in the same range as are considered in this study. Hence it can safely be said that the results of cost estimation of this study can at least provide an order of magnitude glimpse of the economics involved in the waste water treatment using ultrasonic processes. 3.1. General procedure for calculation of capital cost Most investigators have observed the kinetics of sonodegradation of pollutants to be either rst order or zero order [4]. A general procedure is given below to calculate the capital cost for a given AOP. Using k to denote the rate constant for degradation and t90 for time required for 90% degradation of the pollutant, the rst-order degradation of pollutants is given by [25]

ln

C A0 kt CA

27

For 90% degradation, this equation is converted to

t90

2:3025851 k

28

For zero order degradation of pollutants [25],

C A C A0 kt
Table 4 General calculation of capital costa. Item AOP reactor Piping, valves, electrical (30%) Site work (10%) Subtotal Contractor O&P (15%) Subtotal Engineering (15%) Subtotal Contingency (20%) Total capital Cost (USD) P 0.3 P 0.1 P 1.4 P = Q 0.15 Q 1.15 Q = R 0.15 R 1.15 R = S 0.2 S 1.2 S

29

For 90% degradation, this equation is converted to

t90

0:9C A0 k

30

a The % values are taken from vendor data in the MTBE report from NWRI (National Water Research Institute, USA) Melin, [33].

sources were considered for phenol and TCE whereas three sources were considered for reactive dyes. The collected data was then compared with the kinetic data available for a number of other similar treatability studies in the literature to make sure that it is comparable with the reported values.

From the design ow rate of 1000 L/min, the capacity of the waste water treatment reactor (AOP reactor) is given by = 1000 * t90 = X liters. From the referred publications or calculations from the data in the publications (energy density, e), the total energy requirement in the AOP reactor is given by X e watt. From the manufacturer quotations, the energy supplied by single unit of AOP = E watt. The number of such standard commercial units required, N = X e/E. Cost of each unit from the manufacturer = C USD. Total cost of N units = cost of AOP reactor = P = N C. From this the capital cost of the equipment was calculated. The general calculation of capital cost is presented in Table 4. The capital cost is amortized over a span of years at given amortization rate. Amortized capital cost (A) is given by following formula [32]:

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003 Table 5 Summary of cost estimation of various AOPs for degradation. Process k Pelec (kW) t (min) V (liter) C0 C Energy density used in treatability study (watt/ml) 0.15 0.25 0.36 0.4 0.61 0.51 0.76 0.182 ** 0.5 0.15 0.45 0.52 0.03 0.5 0.03 0.53 0.53 0.06 0.56 0.027 0.0147 0.0413 0.7143 0.7571 0.004 0.0833 0.36 0.1049 0.004 0.0625 EE/O or EE/M

995

Cost $/ 1000 gallon

For phenol UV (254 nm) US (300 kHz) O3 (2 mg/L) US + UV US + O3 UV + O3 US/UV/O3 US/H2O2/CuO Fenton SonoFenton UV/H2O2 Photocatalysis Sonophotocatalysis For reactive azo dye UV (254 nm) US (300 kHz) O3 (12.4 mg/L) US + UV US + O3 UV + O3 US/UV/O3 US/H2O2 UV/H2O2 US/UV/H2O2 Photocatalysis Sonophotocatalysis For TCE UV(254 nm) US (500 kHz) O3 (6 mg/L) US + UV UV/H2O2 Photocatalysis

0.0021 min1 0.0008 min1 0.0279 min1 0.005 min1 0.0326 min1 0.0869 min1 0.1793 min1 0.0149 min1 0.0106 min1 0.058 min1 0.0524 min1 0.433 ppm min1 0.712 ppm min1 No degradation observed 0.00175 min1 0.01108 min1 0.0055 min1 0.01674 min1 0.02064 min1 0.02171 min1 0.0032 min1 0.0124 min1 0.0357 min1 0.0207 ppm min1 0.0757 ppm min1 0.0589 min1 0.0457 min1 0.0209 min1 0.181 min1 0.4418 min1 Apparent rate constant = 49.57 lg/L s1 Adsorption equilibrium constant = 0.000466 l/lg

0.015 0.025 0.036 0.04 0.061 0.051 0.076 0.0182 ** 0.05 0.15 0.45 0.52 0.036 0.6 0.036 0.636 0.636 0.072 0.672 0.066 0.186 0.186 0.5 0.53 0.02 0.05 0.036 0.43 0.02 0.45

1096.47 2878.23 82.53 460.52 70.63 26.5 12.842 136 218 39.69 90 180 145.18 60 1315.76 207.814 418.65 137.55 111.56 106.06 60 60 60 111.24 30.41 30 90.61 25 29.9 14.84 30

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.15 0.35 0.35 0.75 0.1 0.1 1.2 1.2 1.2 1.2 1.2 1.2 1.2 4.5 4.5 4.5 0.7 0.7 5 0.6 0.1 4.1 5 7.2

235.28 235.28 235.28 235.28 235.28 235.28 235.28 58.1 63 63 1100 100 100 20 20 20 20 20 20 20 100 100 100 402.6 402.6 1.66 32.85 2.2 13.4 2.194 15

23.528 23.528 23.528 23.528 23.528 23.528 23.528 8.82 6.3 6.3 5.53 2.36 3.02 20 2 2 2 2 2 2 45.65 84.35 9.13 40.26 40.26 0.291 0.4376 1.3 1.49 0.003 0.21

2741.2 11993 495.18 3070.1 718.07 225.25 162.67 335.92 ** 94.5 130.51 138263 129741 1.38E+09 10964.69 103.91 3698.09 1215.02 111.56 989.9 43.07 559.2 39.76 3654.68 1059.08 2.64 67.1 656.51 54.78 0.35 2112914

1520.86 15536.59 1.2023 3127.51 384.431 38.648 89.7851 429.185 14.2829 137.626 308.482 8648.79 7337.33 14203.7 4.0839 4639.155 1492.066 34.02462 1187.477 416.491 74.613 65.172 739.8451 234.2085 4.668 91.14 2.3549 25.8247 3.3266 15.0993

1:2S r  n
1 1r

31

3.2. General procedure for calculation of O&M cost The O&M (operating and maintenance cost) consists of part replacement costs, labor costs, analytical costs, chemical costs and electrical costs. (1) Part replacement cost: Part replacement cost may include bulb replacements for UV systems, ozone generator parts for ozone system, catalyst holder replacements for catalytic systems, tip replacements or electronic circuit replacements or transducer element replacements for ultrasound systems. For ultrasonic systems, the part replacement costs were assumed to be 0.5% of the capital cost. This assumption was made based upon the vendor data in the MTBE report from NWRI (National Water Research Institute, USA) [33]. For UV systems, the part replacement costs were assumed to be 45% of the annual electrical power consumption costs [34,35]. For ozone systems, the annual part replacement cost was assumed to be 1.5% of the capital cost [33]. (2) Labor cost: The labor costs consisted of water sampling cost, general and specic system O&M costs. System specic operation and maintenance consisted of inspection, replacement and repair based on hours of service life. General O&M annual labor consists of general system oversight and

maintenance such as pressure gauges, control panels, leakages etc. General O&M labor was assumed to be 312 h/year for all the systems. The labor rate was assumed to be $80/ h [33]. For ultrasonic systems, it was assumed that (based on vendor data in [33]) sampling frequency (Sf) = 3 samples/week; sampling time (St) = 1 h per sample or 3 h/week and time required for O&M = 128 h/year. Operation and maintenance consisted of inspection, replacement and repair based on 1000 h of service life. For UV systems, it was assumed that (based on vendor data in [33]) Sf = 3 samples/week; St = 1 h per sample or 3 h/ week; and time required for O&M = 18 h/year. Operation and maintenance consisted of change outs of lamps every 3000 h of service. For ozone systems, it was assumed that (based on vendor data in [33]) Sf = 4 samples/week; St = 1 h per sample or 4 h/week; time required for O&M = 48 h/year. Operation and maintenance consisted of change outs of damaged parts, repairing of electrodes etc. during the year and ozone generator replacement every year. For H2O2 systems, no labor costs were considered as we believe that it involves just the use of a metering pump and a reservoir for H2O2 storage. For catalyst systems, no labor costs were considered. (3) Analytical costs: Analytical costs were based upon sampling frequency, the labor required to do the analysis of the samples and the cost of chemicals required for analysis. These costs were considered at a rate of $200/h [33].

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N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

Table 6 Capital cost estimation ($) of various AOPs for degradation. Item AOP reactor Piping, valves, electrical (30%) 7.40E+07 2.70E+09 1.02E+04 4.63E+08 6.66E+07 1.82E+06 1.31E+07 7.05E+07 *** 2.14E+07 3.96E+06 4.21E+08 6.14E+08 2.47E+09 6.12E+04 7.91E+08 2.59E+08 1.51E+06 2.02E+08 7.20E+07 1.23E+07 1.08E+07 3.60E+07 1.49E+07 7.04E+05 1.57E+07 3.06E+04 4.03E+06 9.40E+04 7.03E+05 Site work (10%) Subtotal Contractor O&P (15%) Subtotal Engineering (15%) Subtotal Contingency (20%) Total capital Amortized annual capital cost 4.42E+07 1.61E+09 a 7.55E+04 2.77E+08 b 3.98E+07 b 1.12E+06 b 7.83E+06 4.21E+07 *** 1.28E+07 2.36E+06 2.51E+08 3.67E+08 1.47E+09 a 4.53E+05 4.72E+08 b 1.55E+08 b 1.16E+06 b 1.21E+08 4.30E+07 7.33E+06 6.44E+06 2.15E+07 8.92E+06 4.20E+05 9.39E+06 a 226623.6 2.41E+06 5.61E+04 4.20E+05

For phenol UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis
a b

2.47E+08 9.00E+09 3.40E+04 1.54E+09 2.22E+08 6.08E+06 4.36E+07 2.35E+08 *** 7.14E+07 1.32E+07 1.40E+09 2.05E+09 8.23E+09 2.04E+05 2.64E+09 8.63E+08 5.04E+06 6.74E+08 2.40E+08 4.09E+07 3.60E+07 1.20E+08 4.98E+07 2.35E+06 5.24E+07 1.02E+05 1.34E+07 3.13E+05 2.34E+06

2.47E+07 9.00E+08 3.40E+03 1.54E+08 2.22E+07 6.08E+05 4.36E+06 2.35E+07 *** 7.14E+06 1.32E+06 1.40E+08 2.05E+08 8.23E+08 2.04E+04 2.64E+08 8.63E+07 5.04E+05 6.74E+07 2.40E+07 4.09E+06 3.60E+06 1.20E+07 4.98E+06 2.35E+05 5.24E+06 1.02E+04 1.34E+06 3.13E+04 2.34E+05

3.46E+08 1.26E+10 4.76E+04 2.16E+09 3.11E+08 8.51E+06 6.10E+07 3.29E+08 *** 1.00E+08 1.85E+07 1.97E+09 2.87E+09 1.15E+10 2.86E+05 3.69E+09 1.21E+09 7.06E+06 9.43E+08 3.36E+08 5.73E+07 5.04E+07 1.68E+08 6.98E+07 3.28E+06 7.34E+07 1.43E+05 1.88E+07 4.38E+05 3.28E+06

5.18E+07 1.89E+09 7.14E+03 3.24E+08 4.66E+07 1.28E+06 9.15E+06 4.94E+07 *** 1.50E+07 2.77E+06 2.95E+08 4.30E+08 1.73E+09 4.28E+04 5.54E+08 1.81E+08 1.06E+06 1.41E+08 5.04E+07 8.59E+06 7.55E+06 2.52E+07 1.05E+07 4.93E+05 1.10E+07 2.14E+04 2.82E+06 6.58E+04 4.92E+05

3.97E+08 1.45E+10 5.47E+04 2.49E+09 3.58E+08 9.78E+06 7.01E+07 3.78E+08 *** 1.15E+08 2.13E+07 2.26E+09 3.30E+09 1.32E+10 3.28E+05 4.25E+09 1.39E+09 8.11E+06 1.08E+09 3.86E+08 6.59E+07 5.79E+07 1.93E+08 8.02E+07 3.78E+06 8.44E++07 1.64E+05 2.16E+07 5.04E+05 3.77E+06

5.96E+07 2.17E+09 8.21E+03 3.73E+08 5.36E+07 1.47E+06 1.05E+07 5.68E+07 *** 1.72E+07 3.19E+06 3.39E+08 4.95E+08 1.99E+09 4.93E+04 6.37E+08 2.08E+08 1.22E+06 1.63E+08 5.80E+07 9.88E+06 8.69E+06 2.90E+07 1.20E+07 5.67E+05 1.27E+07 2.46E+04 3.25E+06 7.56E+04 5.66E+05

4.57E+08 1.67E+10 6.30E+04 2.86E+09 4.11E+08 1.12E+07 8.06E+07 4.35E+08 *** 1.32E+08 2.44E+07 2.60E+09 3.79E+09 1.52E+10 3.78E+05 4.88E+09 1.60E+09 9.33E+06 1.25E+09 4.44E+08 7.58E+07 6.66E+07 2.22E+08 9.22E+07 4.34E+06 9.71E+07 1.89E+05 2.49E+07 5.80E+05 4.34E+06

9.14E+07 3.33E+09 1.26E+04 5.72E+08 8.22E+07 2.25E+06 1.61E+07 8.71E+07 *** 2.64E+07 4.89E+06 5.20E+08 7.58E+08 3.05E+09 7.55E+04 9.77E+08 3.19E+08 1.87E+06 2.49E+08 8.89E+07 1.52E+07 1.33E+07 4.44E+07 1.84E+07 8.69E+05 1.94E+07 3.78E+04 4.98E+06 1.16E+05 8.68E+05

5.48E+08 2.00E+10 7.55E+04 3.43E+09 4.93E+08 1.35E+07 9.68E+07 5.22E+08 *** 1.59E+08 2.93E+07 3.12E+09 4.55E+09 1.83E+10 4.53E+05 5.86E+09 1.92E+09 1.12E+07 1.50E+09 5.33E+08 9.09E+07 7.99E+07 2.67E+08 1.11E+08 5.21E+06 1.17E+08 2.27E+05 2.99E+07 6.96E+05 5.21E+06

Since ozone generator is assumed to be replaced every year, amortized cost is taken as the same as that of the capital cost. Cost of ozone generator is added to the amortized cost of UV and US system amortized over 30 years at 7% rate.

(4) Chemical costs: The chemical costs include the costs of consumables such as hydrogen peroxide and chemicals involved with the AOP such as catalysts like CuSO4, CuO and TiO2 etc. The price of hydrogen peroxide (50%) was considered to be $4 per gallon. The price of CuO was considered to be $3.42 per kg. The price of TiO2 was assumed to be $300 per kg. The price of CuSO4 was considered to be $2.2 per kg. These prices were obtained from standard industrial suppliers such as ICIS Pricing and Inframat Advanced Materials [36]. (5) Electrical costs: Electrical costs were based on the power consumption by a given AOP. The electricity cost was calculated at a rate of $0.08/kWh. Power consumption was calculated for each AOP based upon the power consumed in a year multiplied by the electricity rate. 3.3. General procedure for calculation of EE/O or EE/M Electric energy per order (EE/O) is the electric energy in kilowatt hours [kWh] required to degrade a contaminant by one order of magnitude in a unit volume [e.g., 1 m3 (1000 L)] of contaminated water or air [37]. This gure-of-merit is best used for situations where [CA] is low (i.e., cases that are overall rst-order in concentration of pollutant) because the amount of electric energy required to bring about a reduction by one order of magnitude in concentration is independent of [CA]. Thus, it would take the same amount of electric energy to reduce the contaminant concentration from 10 mg/L to 1 mg/L in a given volume as it would to reduce it from 10 lg/L to 1 lg/L. EE/O is, in general, a measure of operating

cost. It allows for easy and accurate scale up to a full scale design and costs. EE/O is dened as:

EE=O

Pelec t 1000 V 60 logC A0 =C A

32a

For zero order degradations, EE/M (electrical energy per unit mass) is used instead of EE/O. EE/M is dened as:

EE=M

Pelec t 1000 V M 60 C A0 C A

32b

4. Sample calculations 4.1. Sample calculations (O3 + US + UV treatment) for phenol degradation A sample calculation for the hybrid process of O3 + US + UV for the degradation of phenol is shown below. Cost estimations for all other processes were done similarly. Table 5 summarizes the results of these calculations. All the calculations done for the estimation of cost of waste water treatment using ultrasound for phenol, reactive azo dye and TCE are tabulated in Table 612. 4.1.1. Capital cost calculations The work of Kidak and Ince [38] was used as the treatability study for phenol. From their published data, the rst-order degradation rate constant for phenol was 0.1793 min1. One can easily

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003 Table 7 Annual O&M cost estimation ($) of various AOPs for degradation. Item For phenol UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis Part replacement cost 5.19E+07 4.50E+07 5.10E+02 2.90E+07 1.11E+06 1.28E+06 8.19E+05 1.18E+06 0.00E+00 3.57E+05 2.78E+06 2.95E+08 1.86E+08 4.11E+07 3.06E+03 1.71E+07 4.32E+06 1.06E+06 4.36E+06 1.20E+06 8.60E+05 4.09E+05 2.52E+07 7.07E+06 4.93E+04 2.62E+05 1.53E+03 1.47E+05 6.58E+03 4.93E+05 Labor cost 3.89E+04 4.77E+04 4.54E+04 6.16E+04 6.82E+04 5.94E+04 8.21E+04 4.77E+04 4.77E+04 4.77E+04 3.89E+04 3.89E+04 6.16E+04 4.77E+04 4.54E+04 6.16E+04 6.82E+04 5.94E+04 8.21E+04 4.77E+04 3.89Ev04 6.16E+04 3.89E+04 6.16E+04 3.89E+04 4.77E+04 4.54E+04 6.16E+04 3.89E+04 4.30E+04 Analytical cost 3.12E+04 3.12E+04 4.16E+04 6.24E+04 7.28E+04 7.28E+04 1.04E+05 3.12E+04 3.12E+04 3.12E+04 3.12E+04 3.12E+04 6.24E+04 3.12E+04 4.16E+04 6.24E+04 7.28E+04 7.28E+04 1.04E+05 3.12E+04 3.12E+04 6.24E+04 3.12E+04 6.24E+04 3.12E+04 3.12E+04 4.16E+04 6.24E+04 3.12E+04 4.16E+04 Chemical cost 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 3.15E+06 1.91E+06 1.91E+06 3.15E+07 1.56E+04 9.53E+03 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 2.06E+05 2.06E+05 2.06E+05 2.52E+04 6.98E+03 0.00E+00 0.00E+00 0.00E+00 0.00E+00 3.15E+05 7.50E+03 Electrical cost 1.15E+08 5.04E+08 4.09E+03 1.29E+08 1.24E+07 2.84E+06 3.65E+06 1.32E+07 0.00E+00 4.00E+06 6.17E+06 6.56E+08 4.67E+08 4.61E+08 2.45E+04 1.56E+08 4.84E+07 2.38E+06 3.98E+07 1.35E+07 1.91E+06 1.88E+06 5.61E+07 1.64E+07 1.10E+05 2.94E+06 1.23E+04 9.14E+05 1.46E+04 1.10E+06

997

Total annual O&M cost 1.67E+08 5.49E+08 9.16E+04 1.58E+08 1.37E+07 4.25E+06 4.65E+06 1.76E+07 1.99E+06 6.35E+06 4.05E+07 9.51E+08 6.54E+08 5.02E+08 1.15E+05 1.73E+08 5.28E+07 3.57E+06 4.43E+07 1.49E+07 3.05E+06 2.62E+06 8.14E+07 2.36E+07 2.29E+05 3.28E+06 1.01E+05 1.18E+06 4.06E+05 1.68E+06

calculate the time required for 90% degradation of phenol using Eq. (28) as t90 = 12.8413 min. We assume that the residence time for the proposed waste water treatment plant = 13 min. With a design ow rate of 1000 L/min and ultrasonic power density of 250 watt/L, the amount of ultrasonic energy needed for the plant = 3250 kW. From the quotation received from a leading ultrasonic device manufacturer (Hielscher USA, Inc., Ringwood, NJ 07456, USA), the amount of energy supplied by the ultrasonic device is 16 kW. The device is claimed to be by far the most powerful ultrasonic processor world-wide providing a continuous power of 16,000 watts at an efciency of more than 80%. The frequency of ultrasonic device is 20 kHz. As there are no industrial ultrasonic devices to the best of our knowledge which work at 300 kHz, it was assumed that the available ultrasonic device will produce the same results as in the treatability study. This assumption may be valid as the amount of ultrasonic energy provided by both devices is the same (although it is generally known that effect of high frequency is slightly better than low frequency ultrasound). The quoted cost of this device is 200,000 USD. The number of such standard device needed for the plant will be 204. The cost of ultrasonic devices required = 204 * 200,000 = 4.08 107 USD. The power density used for UV energy in the treatability study = 150 watt/L. The amount of energy needed in the form of UV energy for the plant = 13000 * 150 = 1950 kW. From the quotation received from a leading LP-UV Lamp provider (Emperor Aquatics, Inc., Pottstown, PA 19464, USA) the amount of energy supplied by the LP-UV Lamp is 200 W. The quoted cost of this device is 300 USD. The number of such standard device needed for the plant = 1950000/200 = 9750.

The cost of UV device required = 9750 * 300 = 2.925 106 USD. The dissolved concentration of ozone used in the treatability study = 2 mg/L. We have to continuously maintain similar concentration in the plant reactor of 13,000 L capacity. Hence the amount of dissolved ozone needed = 13000 * 2 = 26 g. This is the amount of ozone needed during start up. Once the dissolved concentration reaches a steady state of 2 mg/L, the demand for dissolved ozone is only for 1000 L/min waste water. Hence, at steady state, the demand for ozone = 2000 mg/ min = 6.3648 lb/day. The solubility coefcient of ozone at 20 C is 0.31 mg/L in water per 1 mg/L in gas [39]. Hence, to obtain a dissolved concentration of 2 mg/L in the reactor, the concentration of ozone required in the ozone/air mixture at 20 C = 2/0.31 = 6.45 mg/L. From the quotation received from a leading Ozone Generator manufacturer (Spartan Environmental Technologies, L.L.C. Mentor, OH 44060, USA), the capacity of ozone generator was 7.5 lb/day. The concentration of ozone in the ozone air mixture was 5% by weight. This comes out to be 70 mg/L ozone in the ozoneair mixture. Thus one unit of ozone generator is sufcient to meet our ozone demand in this case. The quoted cost of this device is 34000 USD. Since it was assumed that ozone generator is replaced every year, its cost was not amortized. The energy consumption of this device (including other accessories such as air compressor etc.) was 5.83 kW. Thus the cost of ozone system required = 34000 USD. Hence, the total capital cost of the AOP unit for (O3 + US + UV) treatment = P = cost of ultrasonic system + cost of UV system = 40625000 + 2925000 = 4.3550E+07. From Table 4, total capital cost of waste water system = 1.2 S = 9.68E+07 USD. Using Eq. (31), amortized capital cost, A = 7797491 USD.

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Table 8 Breakdown of labor costs ($) of various AOPs for degradation. Item For phenol UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis
a b

Sampling frequency (Samples/Week) 3 3 4 6 7 7 10 3 3 3 3 3 6 3 4 6 7 7 10 3 3 6 3 6 3 3 4 6 3 4

Sampling annual labor (h)a 156 156 208 312 364 364 520 156 156 156 156 156 312 156 208 312 364 364 520 156 156 312 156 312 156 156 208 312 156 208

AOP system O&M (h/year) 18 128 48 146 176 66 194 128 128 128 18 18 146 128 48 146 176 66 194 128 18 146 18 146 18 128 48 146 18 18

General O&M whole treatment plant (h/year) 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312 312

Total annual labor (h) 486 596 568 770 852 742 1026 596 596 596 486 486 770 596 568 770 852 742 1026 596 486 770 486 770 486 596 568 770 486 538

Total annual labor cost ($)b 38880 47680 45440 61600 68160 59360 82080 47680 47680 47680 38880 38880 61600 47680 45440 61600 68160 59360 82080 47680 38880 61600 38880 61600 38880 47680 45440 61600 38880 43040

It is assumed that the plant is working the whole year. Also there are 52 weeks in a year. Labor rate is assumed to be $80 per hour.

Total amortized capital cost = A + cost of ozone generator = 7797491 + 34000 = 7831491 USD. 4.1.2. Operating and maintenance cost calculations (1) Labor cost: For US systems and UV systems, the sampling frequency was taking 3 samples per week. For ozone systems, it was 4 samples per week. It was assumed to be 52 weeks in a year. It was assumed that sampling labor takes 1 h per sample. a) For UV system: Annual sampling labor = 3 * 52 = 156 h; UV system O&M = 18 h/year; total annual labor hours = 156 + 18 = 174. b) For US system: Annual sampling labor = 3 * 52 = 156 h; UV system O&M = 128 h/year; total annual labor hours = 156 + 128 = 284 h. c) For OZONE system: Sampling labor = 4 * 1 = 4 h/week; Annual sampling labor = 4 * 52 = 208 h; ozone system O&M = 48 h/year; Total annual labor hours = 208 + 48 = 256. d) For General O&M of the waste water treatment plant = 312 h per year. Thus, the total annual labor hours = 174 + 284 + 256 + 312 = 1026. Total annual labor cost = 1026 * 80 = 82080 USD (2) Analytical cost: a) For UV system: Annual analysis labor = 3 * 52 = 156 h; total annual labor hours = 156 h.

b) For US system: Annual analysis labor = 3 * 52 = 156 h; total annual labor hours = 156 h. c) For OZONE system: Annual analysis labor = 4 * 52 = 208 h; total annual labor hours = 208 h. Total annual analysis labor hours = 156 + 156 + 208 = 520. Total annual analysis cost = 520 * 200 = 104000 USD. (3) Chemical cost: Since there is no other chemical consumption (as per treatability studies) in O3 + US + UV process. This cost is considered as zero. (4) Electrical cost: Power consumption in the O3 + US + UV system = sum of power consumed by each system = 5.83 + 3250 + 1950 = 5205.83 kW. Total energy consumed in a year = 31536000 * 5205.83 = 164171054880 kJ = 45603070.8/ kWh. Rate of electricity = $0.08/kWh. So, the total annual electrical cost = 0.08 * 45603070.8 = 3.648245664 106 USD. (5) Part replacement cost: a) For UV system: Part replacement cost = 45% of electrical cost = (0.45 * 1950 * 31536000 * 0.08)/3600 = 614952 USD. b) For US system: Part replacement cost = 0.5% of capital cost of ultrasonic system = 0.005 * 40625000 = 203125 USD. c) For ozone system: Part replacement cost = 1.5% of capital cost of ultrasonic system = 0.015 * 34000 = 510 USD. So, total part replacement cost = 614952 + 203125 + 510 = 818587 USD.

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003 Table 9 Breakdown of analytical costs ($) of various AOPs for degradation. Item Sampling frequency (samples/week) 3 3 4 6 7 7 10 3 3 3 3 3 6 3 4 6 7 7 10 3 3 6 3 6 3 3 4 6 3 3 Sampling annual labor (h) 156 156 208 312 364 364 520 156 156 156 156 156 312 156 208 312 364 364 520 156 156 312 156 312 156 156 208 312 156 156 Total annual labor cost ($)a Table 10 Breakdown of chemical costs ($) of various AOPs for degradation. Item Chemicals Amount of chemicals consumed (g) Cost of chemicals (USD)

999

Total cost of chemicals ($)

For phenol UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis
a

31200 31200 41600 62400 72800 72800 104000 31200 31200 31200 31200 31200 62400 31200 41600 62400 72800 72800 104000 31200 31200 62400 31200 62400 31200 31200 41600 62400 31200 31200

UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3 US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis

NA NA NA NA NA NA NA H2O2 CuO CuSO4 H2O2 CuSO4 H2O2 H2O2 TiO2 TiO2 NA NA NA NA NA NA NA H2O2 H2O2 H2O2 TiO2 TiO2 NA NA NA NA H2O2 TiO2

3.57E+09 1.55E+05 1.31E+05 2.16E+09 2.40E+04 2.16E+09 3.57E+10 5.20E+04 3.18E+04

3.15E+06 5.30E+02 2.88E+02 1.91E+06 5.28E+01 1.91E+06 3.15E+07 1.56E+04 9.53E+03

3.15E+06 1.91E+06 1.91E+06 3.15E+07 1.56E+04 9.53E+03

2.33E+08 2.33E+08 2.33E+08 8.40E+04 2.33E+04

2.06E+05 2.06E+05 2.06E+05 2.52E+04 6.98E+03

2.06E+05 2.06E+05 2.06E+05 2.52E+04 6.98E+03

Analytical labor rate was assumed to be $200 per hour.

3.57E+08 25000

315179.9 7500

315179.9 7500

Total O&M cost = part replacement cost + labor cost + analytical cost + chemical cost + electrical cost. Thus, total O&M cost = 818587 + 82080 + 104000 + 0 + 3648245.664 = 4652912.664 USD. Total annual operating cost for O3 + US + UV system = total amortized annual capital cost + annual O&M cost = 7831491 + 4652912.664 = 12484403.664 USD. Total amount of water treated in a year = 1000 * 60 * 24 * 365 = 525600000 liter = 139047.619 thousand US gallons. Hence, cost of waste water treatment = 12484403.664/139047.619 = 89.78509661 USD per thousand gallon. 4.2. Sample EE/O calculation For O3 + US + UV process the total electrical energy utilized in the treatability study [38] was 76 watts. The amount of treatment volume was 100 ml. The treatment time was 12.84 min. The initial concentration was 235.28 ppm and nal concentration was 23.528 ppm in this much treatment time. The EE/O is calculated using Eq. (32). Thus, EE/O = (0.076 * 12.84 * 1000)/(0.1 * 60 * log (235/23.5)) = 162.67 kWh/m3/order. 5. Results and discussion All the costs are expressed in terms of amount in dollars needed to treat 1000 gallons of phenolic waste water for 90% degradation. These costs are calculated for the conditions described in the treatability studies. Pilot plant studies can give much closer conditions

to estimate accurate costs. But still, the costs estimated in this study using the lab scale treatability studies can be used as a useful guide as to what may be the order of magnitude of the treatment cost for ultrasonic waste water treatment systems. Table 5 shows the summary of the cost estimation of various AOPs along with EE/O values for phenol, reactive azo dye and TCE. It can be seen from Table 5 that the cost of phenolic waste water treatment using ultrasound is $15536.6 for US process alone. It is $3127.51 for combinative US + UV process. The cost of combinative US + O3 process is $384.43. It is $89.79 for US + UV + O3 combinative process, $429.19 for US + H2O2 + CuO, $137.63 for US + Fenton and $7337.33 for US + photocatalysis combinative processes. These costs are plotted in Fig. 1. At the rst glance of the Fig. 1, one can observe that the cost of treatment for ultrasound alone is very high ($15536.6). But the cost of ultrasonic waste water treatment reduces when it is combined with other sources of producing oxidizing species such as photocatalysis ($7337.33), UV ($3127.51), H2O2/CuO ($429.19), O3 ($384.431), Fenton ($137.63) and UV + O3 ($89.79). The lowest cost ($89.79) is achieved when ultrasound is used in combination of UV and ozone for phenol degradation. A similar trend is observed for the reactive azo dyes and TCE degradation in the presence of ultrasonic processes. Table 5, Figs. 2 and 3 show how the costs of waste water treatment for reactive azo dyes and TCE have decreased when combination of AOPs was used instead of single AOP. The lowest cost for ultrasonic reactive azo dye degradation was $65.17 for US/UV/H2O2 process and it was $25.82 for TCE degradation using US + UV process. But still the cost of treatment is not practically implementable.

1000

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003 Table 12 Breakdown of electrical costs ($) of various AOPs for degradation. Item Power consumed (kW) Total annual power consumed (kWh) 1.44E+09 6.31E+09 5.11E+04 1.62E+09 1.56E+08 3.55E+07 4.56E+07 Power cost ($)a

Table 11 Breakdown of part replacement cost ($) of various AOPs for degradation. Item For phenol UV (45% of electrical cost) US (0.5% of capital cost) O3 (1.5% of capital cost) US + UV US + O3 UV + O3 US + UV + O3 Part replacement cost ($) 5.19E+07 4.50E+07 5.10E+02 US UV US O3 UV O3 UV US O3 1.18E+06 NA 3.57E+05 2.78E+06 2.95E+08 US UV 4.11E+07 3.06E+03 US UV US O3 UV O3 UV US O3 1.20E+06 8.60E+05 US UV 2.52E+07 US UV 4.93E+04 2.62E+05 1.53E+03 US UV 6.58E+03 4.93E+05

7.20E+06 2.18E+07 1.11E+06 5.10E+02 1.28E+06 5.10E+02 6.15E+05 2.03E+05 5.10E+02

2.90E+07 1.11E+06 1.28E+06 8.19E+05

For phenol UV US O3 US + UV US + O3 UV + O3 US + UV + O3

US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV (45% of electrical cost) US (0.5% of capital cost) O3 (1.5% of capital cost) US + UV US + O3 UV + O3 US + UV + O3

5.95E+06 1.80E+08

1.86E+08

US + H2O2 + CuO Fenton US + Fenton UV + H2O2 Photocatalysis US + photocatalysis For reactive azo dye UV US O3 US + UV US + O3 UV + O3 US + UV + O3

1.65E+05 7.20E+05 5.83E+00 UV 6.92E+04 US 1.15E+05 US 1.78E+04 5.83E+00 O3 UV 4.05E+03 5.83E+00 O3 US 3.25E+03 UV 1.95E+03 5.83E+00 O3 1.88E+04 NA 5.71E+03 8.80E+03 9.36E+05 UV 5.72E+05 US 9.53E+04 6.58E+05 34.98 UV 1.26E+04 US 2.10E+05 US 6.90E+04 34.98 O3 UV 3.36E+03 34.98 O3 US 5.35E+04 UV 3.21E+03 34.98 O3 1.92E+04 2.73E+03 US 1.73E+03 UV 9.53E+02 8.00E+04 UV 2.21E+04 US 1.33E+03 156.4 4195.831 17.49 UV 260 US 1043.796 20.88 1562.5

1.15E+08 5.04E+08 4.09E+03 1.29E+08 1.24E+07 2.84E+06 3.65E+06

1.65E+08 NA 5.01E+07 7.71E+07 8.20E+09 5.84E+09

1.32E+07 NA 4.00E+06 6.17E+06 6.56E+08 4.67E+08

1.31E+07 3.96E+06 4.31E+06 3.06E+03 1.06E+06 3.81E+03 1.01E+06 3.34E+06 3.06E+03

1.71E+07 4.32E+06 1.06E+06 4.36E+06

5.76E+09 3.06E+05 1.95E+09 6.05E+08 2.97E+07 4.97E+08

4.61E+08 2.45E+04 1.56E+08 4.84E+07 2.38E+06 3.98E+07

US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV (45% of electrical cost) US (0.5% of capital cost) O3 (1.5% of capital cost) US + UV UV + H2O2 Photocatalysis

1.08E+05 3.01E+05 8.30E+04 6.98E+06

4.09E+05

US + H2O2 UV + H2O2 US + UV + H2O2 Photocatalysis US + photocatalysis For TCE UV US O3 US + UV UV + H2O2 Photocatalysis

a

1.68E+08 2.39E+07 2.35E+07 7.01E+08 2.06E+08

1.35E+07 1.91E+06 1.88E+06 5.61E+07 1.64E+07

7.07E+06

6.52E+04 8.20E+04

1.47E+05

1370064 36755485 153212.4 11421253 182908.8 13687500

109605.12 2940438.8 12256.992 913700.24 14632.704 1095000

It can be seen that even the lowest cost of waste water treatment containing phenol using ultrasonic processes is one or two order of magnitudes higher than the cost of phenol degradation using other AOPs. Esplugas et al. [22] have shown that these costs range from $1.09 per kg of phenol removed for ozonation to $293.1 for UV for 75% degradation of phenol. The lowest cost of phenol treatment using an ultrasonic process (O3 + US + UV) is $89.79 for 1000 gallons. This converts to 263.56 dollars/kg of phenol. Also if one looks at the cost of treatment of commercial processes such as ozonation, UV + H2O2 or H2O2 + O3 for ground water treatment containing volatile organic compounds such as TCE, the cost of ultrasonic treatment is at least one order of magnitude higher. Amiri [40] from Hydroxyl Systems Inc. (9800 McDonald Park Rd., Sidney, BC, CanadaV8L5W5) has shown that the cost of waste water treatment for volatile compounds in ground water is in the range of $0.681.14/1000 gallons for H2O2 + O3 and UV + H2O2, respectively. James and Kovalick [41] have shown that the cost of waste water treatment containing chlorinated VOCs such as TCE, PCE and DCA range from $7 to $11 per 1000 gallons for a commercial process called Perox-pure from Calgon Carbon Oxidation
TM

Electricity rate was assumed to be $0.08 per kWh.

Technologies (500 Calgon Carbon Drive, Pitttsburgh, PA 15205, USA). The lowest cost for such treatment using ultrasonic process in our study was $25.82 for US + UV. The costs of ultrasonic treatment of waste water containing reactive azo dyes are comparable or an order of magnitude less than the commercial H2O2/UV and ozonation processes. The costs of waste water treatment for reactive azo dyes are of the order of 52/m3 and 45/m3, respectively [42]. This converts to $283.02/1000 gallon and $244.92/1000 gallon for H2O2/UV and ozonation processes, respectively. The lowest cost of ultrasonic process for waste water treatment containing azo dyes was $65.172/1000 gallons for US + UV + H2O2. The higher costs of ultrasonic treatment processes are because of the very high operating costs involved in the use of ultrasound systems in terms of electrical costs and very high capital costs. One reason for this is that the conversion of electrical energy into cavitation energy is very inefcient. About 34% of the electrical energy supplied is actually used for producing desired nal effect [43]. The second reason, we observe, is the use of large amount

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

16000 14000 12000

1001

$ / 1000 gallon

10000 8000 6000 4000 2000 0

C uO

ly si s

U V

U S

on

U S+

U S+

oc at

2O 2+

Fe

Ph

15000 13500 12000

$/1000 gallon

10500 9000 7500 6000 4500 3000 1500 0

IS S V
3 3 2O 2

U S+

Fig. 1. Costs of AOPs involving ultrasound for phenol degradation.

U S+

U S+

S+

S+

V+

YS

AL

S+

S+

AT

TO

Fig. 2. Costs of AOPs involving ultrasound for dye degradation.

100 90 80 70

$/1000 gallon

60 50 40 30 20 10 0

S U

S+

V Ph ot o t ca

al

ys

is

V U H V+

SO

PH

S+

V+

O2

Fig. 3. Costs of AOPs involving ultrasound for TCE degradation.

2O 2

U S+

ot

U V+

nt

O3

1002

N.N. Mahamuni, Y.G. Adewuyi / Ultrasonics Sonochemistry 17 (2010) 9901003

of energy for treating very small reaction volumes. One can observe from the Table 5, that the power densities used for the treatability studies are very high. It ranges from a low of 0.027 watt/ml to a high of 0.76 watt/ml. This when scaled up to industrial scale, becomes huge amount of energy requirement which needs very high energy capacity equipment .This results in very high capital cost of equipment and higher O&M costs. Hence there is an urgent need to use the minimum possible energy density to produce the optimum results while carrying out treatability studies. This can be done using larger treatment volumes in the laboratory with given equipment. We feel that the energy density to be used for ultrasonic processes should not be more than 0.05 watt/ml in order to make the process economically viable at industrial scale. Also all treatability studies should weigh the relative increase in EE/O values with respect to the observed improvements in the rates when one adds more amount of energy to increase the rates of degradation. This will help keep tab on the amount of energy usage in the treatability studies. Also one should look for alternative ways of producing the same cavitational effects as observed in ultrasound with high energy density but at lower energy costs. One of these ways may be the use of hydrodynamic cavitation [44,45], the use of additives [46] or the hybrid methods [47]. It can be observed that the cost of treatment for hydrophilic pollutants such as reactive azo dyes and phenol are relatively higher than that of hydrophobic contaminants such as TCE (Table 5). Whereas the cost of phenol treatment was $15536 using ultrasound alone, it was only $91 for TCE degradation. This has to do with the mechanism of degradation of these two kinds of pollutants. TCE is degraded inside the cavitation bubbles whereas phenol and reactive azo dyes are degraded outside the cavitation bubbles. Hence the mass transport of OH radicals to the contaminant becomes the controlling step of the degradation mechanism. Most of the OH radicals recombine to produce less reactive species such as H2O2 before they can come in contact with the contaminant molecules. Destaillats et al. [48] and Adewuyi [4] have described the detailed mechanism of these processes. One can also observe that the cost of treatment of reactive azo dyes is comparable to that of phenol but more than that of TCE. This is because of the fact that these reactive azo dyes remain in bulk and are very complex high molecular weight chemicals. One should also understand that, this is a new technology and is in developmental stage. As it matures, the cost of treatment will come down. Also there are known detrimental health effects of other low cost waste water treatment technologies such as ozonation and UV processes which make ultrasonic and hydrodynamic cavitation processes even more attractive. Breathing ozone can trigger a variety of health problems including chest pain, coughing, throat irritation, and congestion. It can worsen bronchitis, emphysema, and asthma. Ground-level ozone can reduce lung function and iname the linings of the lungs. Repeated exposure may permanently scar lung tissue. Ground-level ozone can also have detrimental effects on plants and ecosystems. These effects include: (1) interfering with the ability of sensitive plants to produce and store food, making them more susceptible to certain diseases, insects, other pollutants, competition and harsh weather; (2) damaging the leaves of trees and other plants, negatively impacting the appearance of urban vegetation, as well as vegetation in national parks and recreation areas; and (3) reducing forest growth and crop yields, potentially impacting species diversity in ecosystems [35]. UV processes are ineffective when the waste water is opaque to UV or the particle content of the waste water increase as in rainy season. Hence pretreatments of the waste water to be treated are required before it can be passed onto UV process. These limitations can be overcome with the use of ultrasonic technology which does not need any pretreatment of the wastewater. Also current use of Design of Experiment (DOE) optimization techniques such as Tagu-

chi method to understand the effects of multiple parameters on the overall sonication effectiveness and establish optimal conditions for sonochemical and combinative advanced oxidation processes will aid cost effectiveness and commercialization of ultrasonic processes for water and wastewater treatments [49]. Hence this can be an economically viable alternative technology for waste water treatment in the future. 6. Conclusion The following are the main conclusions of this cost estimation study. (1) Combination of ultrasound with different AOPs was economically more attractive than the use of ultrasound alone for waste water treatment. (2) US + UV + O3 process was found to be the most economical ultrasonic process for phenol treatment in this study. The cost of the phenolic waste water degradation using this process was $89.78/1000 gallon. This is at least one order of magnitude higher than available commercial processes. (3) US + UV + H2O2 was found to be the most economical ultrasonic process for waste water treatment containing reactive azo dye. The cost of the waste water treatment containing reactive azo dyes using this process was $65.17/1000 gallon. This is an order of magnitude less than available commercial processes. (4) US + UV was found to be the most economical ultrasonic process for TCE degradation. The cost of the waste water treatment containing reactive azo dyes using this process was $25.82/1000 gallon. This is one order of magnitude higher than available commercial processes. (5) The cost of ultrasonic waste water treatment containing hydrophobic contaminants is found to be an order of magnitude less than that of waste water containing hydrophilic contaminants. (6) As of today, the cost of waste water treatment using hybrid ultrasonic processes is one to two orders of magnitude more than currently established AOPs such as ozonation, O3/H2O2 and UV/H2O2. (7) The high cost of ultrasonic waste water treatment is due to the very high energy densities used in the treatability studies. Acknowledgement The authors acknowledge the funding received from National Science Foundation (NSF) for the nancial assistance via Award No. Grant CBET-0651811. References
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