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09575820/03/$23.50+0.00 # Institution of Chemical Engineers Trans IChemE, Vol 81, Part B, March 2003

THE DESIGN OF AN INDUSTRIAL WASTE-WATER TREATMENT PROCESS USING ADSORBED OZONE ON SILICA GEL
C. TIZAOUI and M. J. SLATER
School of Engineering, Design and Technology, University of Bradford, Bradford, UK

new technique using ozone loaded on adsorbents for industrial waste-water treatment has been investigated. This is a three-step process: ozone adsorption on a xed bed column; water treatment on the bed loaded with ozone; and nally drying= regeneration of the wet bed. Silica gel of mean particle size of 1.5 mm has been tested for ozone loading capacities followed by water treatment, both at ambient temperature. The mechanisms of the mass transfer process during ozone loading and water treatment have been established. The drying of the adsorbent using vacuum and dry air is feasible, but it is a timeconsuming operation. A design procedure is described for the whole system. Keywords: water treatment; environment; adsorbents; reactive dye; ozone; silica gel.

INTRODUCTION During the past few years there have been numerous statements by regulatory bodies worldwide calling for the gradual banning of the use of chlorine and its derivatives in water treatment and replacement by ozone. In many cases it is found that oxidants such as chlorine, hypochlorite and chlorine dioxide, which are widely used in water treatment, generate compounds of higher toxicity than the original ones (LaGrega et al., 1994). Ozone is increasingly used in drinking water sterilization, waste-water treatment, food and agricultural industries, the textile industry for colour removal, and pulp bleaching. Most processes apply the gas as it is produced diluted in a mixture of oxygen or air by simply bubbling it into water. The direct contact of liquid and ozone at low concentrations suffers from various problems: ozone solubility in water is low and total destruction of the pollutant and total utilization of ozone may not be achieved. In many cases reactions involving ozone are not selective and=or have slow kinetics. Usually pollutants are found at low levels dissolved in water and in most cases the kinetics of pollutant oxidation include both ozone and pollutant concentrations with positive reaction orders (vonGunten and Laplanche, 2000). Therefore increasing the concentration of ozone in water will enhance the kinetics. A new concept consists of loading ozone on a bed of an adsorbent such as silica gel then passing polluted water through the bed. Sites of high ozone concentration are created and enhancement in the mass transfer and in the chemical reaction kinetics with adsorbed or unadsorbed pollutants is thought to be possible due to localized higher ozone concentration. Some control over the contact time of ozone with pollutants may also prove bene cial for pollutants that react only slowly with ozone; this can be achieved by using a packed bed and water ow rates to match reaction 107

rates. With direct gasliquid contact, long contact times require a stirred or loop reactor in which gravity does not control gas bubble relative velocities and in that case backmixing is deleterious compared with a plug ow reactor or counter-current contact system. The counter-current ow of adsorbent is possible but not usually an attractive proposition, so a xed-bed system operating cyclically is investigated. The last step in this cyclic packed bed process is to dry the bed (vacuum followed by dry air) and then ozone ow is recommenced. Any pollutant residues on the dry adsorbent may be oxidized during ozone loading (Tizaoui and Slater, 2001a). ADSORBENTS The adsorbent should have high ozone adsorption capacity at ambient temperature, and be able to adsorb the initial pollutants and=or by-products if possible. It is known that silica gel can adsorb ozone, but previous studies have concentrated on sub-zero Centigrade temperatures to obtain substantial ozone loading (Cook et al., 1959). The adsorbent should be strong enough to withstand repeated wetting and drying and also be suitable for use in a packed bed (pellet form not powder). Various adsorbents were batch or semibatch tested for ozone adsorption (metal oxides mainly). It was determined that materials containing either strong Lewis acids such as alumina or strong Lewis bases destroy ozone (Bulanin et al., 1995; Bulanin et al., 1997; Li and Oyama, 1998; Thomas et al., 1997; Tizaoui, 2001). In contrast, silica gel adsorbs ozone physically without promoting its decomposition at higher levels (Ouederni et al., 1996; Tizaoui, 2001). Therefore silica gel obtained from Gjay Chemicals Company was chosen to carry out this investigation. The equilibrium adsorption and desorption of ozone in oxygen was studied at ambient temperature and a moisture content of the adsorbent of about 2% H2O by loading a xed

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Figure 3. Drying of silica gel. Figure 1. Equilibrium lines for ozone adsorption=desorption on 2% H2O silica gel at ambient temperature.

(Figure 2) so moisture content less than about 2% is needed in order to achieve best ozone loading on silica gel. Particles of 1.5 mm gave a drying time of more than 2 h to reach 1% moisture (Figure 3). This long time for drying poses an economic problem; an acceptable adsorbent would be the one that achieves high ozone loading at high moisture contents. The use of vacuum (by jet ejector) to remove interstitial water after water treatment is helpful, but it is not suf cient by itself to achieve low moisture levels of less than about 30%. Ozone Loading on a Fixed Bed Breakthrough curves for ozone loading were obtained using gas velocities of 16 m min1. Roughly spherical particles of Sauter mean diameter of 1.5 mm were used. Bed lengths varying between 30 cm and 2 m were used. Breakthrough curves of constant pattern behaviour type were obtained. It was found that particle rate control governs the process; ozone has to diffuse into particles and the gas phase causes no rate limits (Tizaoui and Slater, 2001b). A few minutes only were required to obtain full loading so ozone decay is not a problem. Figure 4 shows correlation of the number of transfer units Np with a slope equal to the apparent particle diffusion coef cient, De (Slater, 1991). A value of De of 25.4 109 m2 s1 48% was found (L=Np, derivable from the plot is the height of a transfer unit, just a few cm). The process parameters needed to de ne Np are bed length (L),

Figure 2. Effect of moisture content on O3 equilibrium constant at ambient temperature.

bed with different ozone concentrations in oxygen and checking the loading by desorbing with pure oxygen (Figure 1). An on-line ozone analyser was used. The effect of the silica gel moisture content was found (Figure 2) and it is seen that the moisture causes a dramatic decrease in the loading capacity. The parameter Kvp in Figure 2 is the ratio of ozone concentration on silica gel (g m3) to that of the gas (g m3); it represents the equilibrium constant for ozone adsorption on silica gel. Average values of the bed density and voidage are respectively 0.744 g cm3 and 0.40. Thorough drying of silica gel to a few percent moisture is therefore required. DETERMINATION OF THE PROCESS BEHAVIOUR FOR INDIVIDUAL STEPS Drying of Adsorbent The drying process was expected to be economically critical so experiments of silica gel drying with dry air and vacuum were rst performed in a small column. Ozone loading decreased markedly as moisture content increased

Figure 4. Number of particle transfer units for ozone loading.

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voidage (e), particle size (dp), gas velocity (u) and equilibrium line slope (Kvp). The variables were L and u. More detailed analysis concerning ozone loading on a xed bed of silica gel can be found in Tizaoui and Slater (2001b). Water Treatment The pilot plant comprises a column formed by four modules (QVF glass) each 75 cm in height and 50 mm in diameter. The silica gel used is of 1.5 mm mean particle size and containing moisture content of about 4% (minimum moisture content that can be achieved by the available drying system). The water contained 50 mg l1 of a reactive dye Drimarene Brilliant Red (DBR) (CI 147) supplied by Clariant UK Ltd. Water treatment breakthrough curves were obtained for super cial ow rates of 468 m h1. A model for particle rate control based on Ficks law was used to t the experimental data at high uid velocities and a lm model was used for low velocities. Detailed description of these models can be found in (Heister and Vermeulen, 1952; Ruthven, 1984; Slater, 1991). Good agreement between the models used and the experimental results has been obtained. Rate parameters are physically realistic in value. We have chosen a process parameter, G, to lump many of the operating conditions and bed characteristics. In the same way as a stoichiometric time is de ned in an ion exchange process, we use: (i) dye input (g), Qw Cd0 t; (ii) ozone on bed (g), qvp (1 7 e) Vb;

Figure 6. Particle rate control.

Figure 7. Number of particle transfer units for water treatment with adsorbed ozone on silica gel.

and since we do not know the stoichiometric amount of ozone for dye destruction (a complex series of reactions) required to balance these equations, we adopt the ratio of xed process parameters (excluding time t). G
Qw Cd0 uws Cd0 qvp (1 e)Vb qvp (1 e)L
(1)

which can be used to interpret performance data. This parameter, G, limits two regions, one for low values (G < 2 h1) which means low liquid velocities, and a second region of high values (G > 2 h1) for high liquid velocities. The inverse of the parameter G is the time calculated to be required to input suf cient pollutant into a bed loaded with ozone to be able to react with all the ozone. The super cial water velocity uws in this parameter tends to determine whether the mass transfer process is rate-controlled by the water or the adsorbent. For small values of G (< 2 h1),

which means small water velocities, good agreement between the uid rate control model and the experimental data is obtained (Figure 5). For high values of G (> 2 h1), which means high water velocities, good agreement between the particle rate control model and the experimental data is obtained (Figure 6). Model tting for a wide range of water velocities was used to reach this conclusion (Tizaoui, 2001). The models are discussed below in the design procedure paragraph. At low G (low water velocity) the resistance to the mass transfer is located in the liquid lm and for high G values, it is the diffusion within the particle that controls the performance. For high G, the results can be expressed on Figure 7 as the number of particle transfer units (Np). In Figure 7, Kdd is the amount of dye removed by a given volume of silica gel

Figure 5. Fluid rate control.

Figure 8. Ozone loading.

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Figure 9. Variation of kf with the uid velocity. Figure 11. Relationship between t0.1, t0.5 and t0.9 with G.

:5 Figure 10. Variation of Nf with L=u0 ws .

loaded with ozone, divided by the feed concentration of dye in water. The diffusion of ozone out of particles into the water appears rate-controlling, not any chemical reaction rate in this particular case for the chosen reactive dye. This conclusion is enforced also by the fact that the reactive dye DBR (CI 147) reacts very fast with ozone (Tizaoui, 2002). The ozone loading time of a few minutes (Figure 8) and water treatment time of the order of the hour (Figure 5) in this case are well-suited to a xed bed process. For experiments at G less than 2 h1 the liquid lm mass transfer coef cient, kf, was determined and found proportional to the square root of super cial water velocity (Figure 9). The experimental data were used to determine the number of liquid lm transfer units (Nf), which depends :5 linearly on the quotient L=u0 ws as expected (Figure 10). The slope of the line can be used to determine the surface area per unit volume of the column, ap. A value of ap of 1100 288 m2 m3 has been obtained. The theoretical value of ap for spherical particles of diameter dp is 6(1 7 e)=dp which is equal to 2500 305 m2 m3 if we consider an average particle diameter of 1.5 mm as in the present case. The difference between the two values is due to many factors such as experimental errors, the formation of gas pockets surrounding the adsorbent particles as observed during experimentation which reduces the available area for transfer, and the distribution of the liquid inside the column affecting the true liquid velocity.

and equivalent dye destruction capacity of the adsorbent (qvp) [equation (1)]. Figure 11 gives data depending on what level of water treatment breakthrough is assumed (0.1, 0.5 and 0.9 on the dimensionless dye concentration scale). This gure shows that lower values of G give higher values for t0.1, t0.5 and t0.9. Therefore, it is concluded that good performance of the system is obtained in this region of G. The outlet dye concentration remains low for longer treatment times. Depending on the process parameter G, the two regions of mass transfer can be seen; particle diffusion control in the region G > 2 h1 and liquid lm rate control in the region G < 2 h1. Integration of the ozone adsorption breakthrough curve gives the value of the mass of ozone that has been loaded on silica gel and integration of the water treatment breakthrough curve gives the mass of the dye that has been destroyed by ozone. Thus the ozone demand can be calculated as the ratio of the two masses, (g O3 g1 dye). The effect of the process parameter G on ozone demand has been studied. Figure 12 shows a decrease of the ozone demand (O3D) with increasing G. O3D decreases until reaching a limit of 0.5 g O3 g1 dye. This value represents the minimum ozone demand that can be obtained for this chemical system (ozone, DBR) as shown in a previous study (Tizaoui, 2002). This lowest value of ozone demand serves only for the colour removal without any further destruction of the dye. A complete demineralization of the dye would result in an ozone demand of about 2 g O3 g1 dye (calculated value). This represents an acceptable likely ozone energy cost of only a few pence per m3 of water. When ozone is in high concentration (high qvp) in the adsorbent and water velocity

THE COMBINED PROCESS: PROCESS TIME PARAMETER AND OZONE UTILIZATION For process comparisons the process parameter G is used based on water velocity (uws), initial dye concentration (Cd0)
Figure 12. Effect of G on O3 demand.

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porosity e is 0.37 and the Sauter mean particle size dp of silica gel particles is 1.5 mm. The following design equations assume that: (i) ow rates and temperature are constant; (ii) adsorbent particles have spherical uniform size and do not break up; (iii) adverse axial mixing in xed beds is ignored; (iv) kinetic coef cients are constant along the bed length; (v) simpli ed rate models are acceptable for particle rate control; (vi) entry effects to a xed bed are ignored; (vii) initial concentration conditions in the bed are uniform. The column length and diameter are calculated from the prescribed ow rate of water and its suggested velocity (S Qw =uws ) The speci c capacity of the adsorbent is qvp Kvp CO3in The length of the xed bed is then determined by L uws Cd0 =[qvp (1 e) G] (5) (4) (3)

Figure 13. Effect of G on O3 utilization.

is low (high residence time), the ozone molecule has enough time to solubilize in water and perhaps is involved in other chemical reactions rather than eliminating the colour of the dye only. However, there can be an economic con ict between high ozone utilization and relative amount of dye (colour) destruction for this particular system since Figure 13 shows that ozone utilisation varies with G. The ozone utilization, O3U, is de ned as the ratio between the ozone demand for a given experimental conditions to that needed only to remove the dye colour (minimum ozone demand, 0.5 in this case), equation (2). O3U O3D=(O3D)min BY-PRODUCTS Spectra of the ozonated water during the course of water treatment have been obtained with changing time for high and low values of G. These show that after breakdown of the colour molecule various by-products of oxidation are also being oxidised at low G; in some cases the reaction is violent, producing detectable heat. This has implications for setting the level of ozone utilization and value of G in a real process and the use of following biological treatment. There has been no problem of re-use of the adsorbent due to poisoning with by-productsthe reloading with ozone destroys any residual adsorbed compounds. PROCEDURE TO DESIGN A FIXED BED COLUMN LOADED WITH OZONE FOR WATER TREATMENT Suppose it is required to design a xed bed column loaded with ozone to treat a given ow rate of water Qw polluted with the reactive dye DBR at an initial concentration Cd0 to be reduced to a nal concentration Cd. It is supposed that the ozone generator delivers a xed concentration CO3in. The gas velocity u for ozone loading is set in the range 16 m min1. The aim of this design is to determine the column dimensions, the weight of the adsorbent, and the ow rate of oxygen to the ozone generator. It may be advantageous to work in a region of low values of G, therefore G can be xed for example to 1 h1. The water velocity, uws, is initially set for example to 5 m h1. Ozone concentration CO3in (using oxygen) is typically 50 g m3 NTP. The equilibrium coef cient for ozone adsorption on the silica gel, Kvp, depends on its moisture content achieved after drying (Figure 2). The packed bed
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(2)

At low water velocity the mass transfer process is subject to uid lm rate control. The expression that gives the number of uid lm transfer units, Nf, for the dye destruction is:
:5 Nf 53L=u0 ws

where L is in m and uws is in m h1 (6)

The dimensionless time, t, needed to reach a prescribed relative output dye concentration (Cd=Cd0) likely to have a value of say 0.05 or less (95% removal) is calculated by resolving the equation:
Cd 7 7 0:5 1 erf Nf0:5 (Nf t)0:5 0 Cd0 8 8 (Ruthven, 1984) (7)

From the value and de nition of t, the actual time t is calculated using t
L [tKdd(1 e) e] uws (8)

The weight of ozone needed is calculated from mO3 Qw Cd0=G (9)

The ow rate of oxygen to feed the ozone generator is calculated from a mass balance and the derived equation QO2
m O3 CO3in tf
0

CO3 1 dt CO3in

(10)

and the integer [equation (12)] can be determined using the model of particle rate control [equation (11)], which is

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appropriate for the ozone adsorption process at the gas velocity suggested: CO3 1 0 :5 1 0 :5 0:5 1 erf Np (Np t) CO3in 2 2
(Heister and Vermeulen, 1952) tf
0

(11)

CO3 1 dt CO3in tf 1 0:5 1 0:5 1 0:5 1 erf Np (Np t) dt 2 2 0

(12)

where Np
60De (1 e)LKvp 2 eu dp (13)

The de nition of the number of particle mass transfer units, Np, follows from lumping parameters in the differential equations describing xed bed processes. It can be understood in terms of a transfer unit height containing the elements [10De=dp], which is an approximate mass transfer coef cient and [6(1 7 e)=dp] the speci c interfacial area of uniform spherical solids in the bed. The value of De was determined experimentally for ozone adsorption on silica gel and is 25.4 109 m2 s1. The dimensionless time t for the ozone-loading step is determined by resolving the equation: C 1 0:5 1 y O3 0:5 1 erf Np (Np t)0:5 (14) CO3in 2 2
where the value of y is xed for example to 0.9 (or less, to reduce ozone wastage in the off-gas if it is not recycled to the ozone generator). The actual time is calculated as given by equation (8) but changing Kdd to Kvp. Thus the diameter and height of the packed bed and the operating times of the ozone and water treatment steps can be calculated at speci ed breakthrough points. By changing gas and water ow operating velocities and breakthrough points the design can be changed and a suitable design ascertained and costing carried out. PROCESS COMPARISONS A batch system was set up to compare direct ozone contact with polluted water and use of adsorbents loaded with ozone. Direct contact offers faster overall kinetics but ozone utilization is poorer and the oxidation process is different since the ozone demand is different. It was not possible to draw conclusions about the effect of ozoneloaded adsorbents on the chemical reaction kinetics as the system considered in this study presents fast kinetics (Tizaoui, 2002). A rigorous analysis should consider systems of slow kinetics to eliminate the effect of mass transfer limitations. DISCUSSION The effect of water velocity, input dye concentration, height of the bed and its ozone loading on the performance of the process can all be made through the process parameter

G. It is seen that working at low values of G gives sharper breakthrough curves and cleaner water is generated ( at spectra) because the ozone demand is relatively high. The ozone demand decreases with increasing G to reach a minimum of 0.5 g O3 g1 DBR dye. An economic balance between ozone demand and an extent of destruction of dye (colour removal) and oxidation of the consequent byproducts is therefore required. By-products of the refractory dye destruction by ozone may be more economically treated by a subsequent biological process. It is now required to amass data on other pollutants and to test further adsorbents which can be dried more quickly, such as pellicular materials, and pollutants which adsorb. A better material than silica gel has been patented (Tizaoui and Slater, 2002). The chemical oxidation and adsorption mechanisms may be complex and multi-component but have so far been treated successfully using simple mass transfer theory. Every pollutant is expected to show different chemical behaviour so detailed chemical studies are not expected to be very helpful in design work or in showing process potential. CONCLUSIONS A procedure has been presented that can be used for designing and costing a xed bed column system for water treatment with adsorbed ozone. There is no scale-up problem to be solved. A thorough understanding of the system has been achieved using one pollutant, which can serve as a basis for treatment of other pollutants, with the help of small-scale laboratory test-work. Numerous unique problems exist for smaller chemical companies and this is mainly where the process should be aimed. The roughly estimated running costs of ozone treatment seem acceptable for waste-waters from chemical plants. NOMENCLATURE
ap Cd Cd0 CO3
CO3in dp De kf Kdd
Kvp
L mO3 Nf Np O3D O3U qvp QO2 Qw S t ti
u uws Vb

surface area per unit volume of particle, m2 m 3 dye concentration at any time, mg l 1 initial dye concentration, mg l 1 ozone concentration in gas exiting bed at any time, g m 3 at NTP ozone concentration in feed gas, g m 3 at NTP Sauter mean particle diameter, m molecular diffusion coef cient, m2 s 1 lm mass transfer coef cient, m s 1 coef cient used in the water treatment model, m3 water m 3 silica gel equilibrium coef cient of ozone on silica gel, g m 3=ozone in gas, g m 3 bed length, m weight of ozone, g number of uid lm mass transfer units number of particle mass transfer units ozone demand, g O3 g 1 dye ozone utilization de ned in equation (2) ozone concentration on silica gel, g O3 m 3 of particles ow rate of oxygen to feed the ozone generator, m3 s 1 ow rate of water, m3 s 1 column area, m2 time, s, min or h time at which the breakthrough curve based on dimensionless dye concentration reaches the value i (i 0.1, 0.5 or 0.9), min gas velocity, m s 1 super cial water velocity, m s 1 bed volume, m3

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xw y moisture content of silica gel (%), wet basis CO3=CO3in

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Greek symbols e bed voidage t dimensionless time G process parameter de ned in equation (1), h Indices Ads Des

adsorption desorption

REFERENCES
Bulanin, K.M., Lavalley, J.C. and Tsyganenko, A.A., 1995, Infrared study of ozone adsorption on TiO2 (Anatase), J Phys Chem, 99: 1029410298. Bulanin, K.M., Lavalley, J.C. and Tsyganenko, A.A., 1997, Infrared study of ozone adsorption on CaO, J Phys Chem B, 101(15): 29172922. Cook, G.A., Kiffer, A.D., Klumpp, C.V ., Malik, A.H., and Spence, L.A., 1959, Separation of ozone from oxygen by a sorption process, Adv Chem Ser, 21: 4452. Heister, N.K. and Vermeulen, T., 1952, Saturation performance of ionexchange and adsorption columns, Chem Eng Prog, 48: 505516. LaGrega, M.D., Buckingham, P.L. and Evans, J.C., 1994, Hazardous Waste Management (McGraw-Hill, Singapore). Li, W. and Oyama, S.T., 1998, Mechanism of ozone decomposition on a manganese oxide catalyst. 2. Steady-state and transient kinetic studies, J Am Chem Soc, 120(35): 90479052. Ouederni, A., Limvorapituk, Q., Bes, R. and Mora, J.C., 1996, Ozone decomposition on glass and silica, Ozone Sci Eng, 18: 385415. Ruthven, D.M., 1984, Principles of Adsorption and Adsorption Processes (Wiley Interscience, New York, USA). Slater, M.J., 1991, The Principles of Ion Exchange Technology (ButterworthHeinemann, Oxford, UK).

Thomas, K., Hoggan, P.E., Mariey, L., Lamotte, J., and Lavalley, J.C., 1997, Experimental and theoretical study of ozone adsorption on alumina, Catal Lett, 46(12): 7782. Tizaoui, C., 2001, Investigation of a new technique for water treatment using adsorbed ozone, Ph.D. Thesis, University of Bradford, Bradford, UK. Tizaoui, C., 2002, Kinetic study of ozone degradation of the reactive dye CI 147. Personal communication, University of Bradford, Bradford, UK. Tizaoui, C. and Slater, M.J., 2001a, Reactive solid-desorption for water treatment: ozone as oxidant. Proc 7th Int Conf on Advanced Oxidation Technologies for Water and Air Remediation, Niagara Falls, Canada, p. 74. Tizaoui, C. and Slater, M.J., 2001b, Uses of ozone in a three-phase system for water treatment: ozone adsorption. Proc 15th Ozone World Congress, London, pp. 164173. Tizaoui, C. and Slater, M.J., 2002, Adsorbents, UK Patent Of ce, Application no. GB0209232.8. vonGunten, U. and Laplanche, A., 2000, Oxidation and disinfection with ozone, an overview, Proc Fundamental and Engineering Concepts for Ozone Reactor Design, Toulouse, pp. 3973.

ACKNOWLEDGEMENTS
This project and a previous feasibility study were nanced by EPSRC under the WMR3 programme. The co-operation of Dr M. Webb, Cros eld Chemicals Company is gratefully acknowledged.

ADDRESS
Correspondence concerning this paper should be addressed to Dr C. Tizaoui, School of Engineering, Design and Technology University of Bradford, Bradford BD7 1DP, UK. E-mail: c.tizaoui@bradford.ac.uk The manuscript was received 16 September 2002 and accepted for publication after revision 6 February 2003.

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