Pergamon

P l l : S0043-1354(96)00227-8

War. Res. Vol. 31, No. 3, pp. 391-398, 1997 1997ElsevierScienceLtd Printed in Great Britain. All rights reserved 0043-1354/97 $17.00+ 0.00

CHARACTERISTICS OF ORGANICS REMOVAL BY PACT SIMULTANEOUS ADSORPTION A N D B I O D E G R A D A T I O N

F R I E D A O R S H A N S K Y and N A V A NARKIS*@ Environmental and Water Resources Engineering, Technion--Israel Institute of Technology, Technion City, Haifa 32000, Israel

(First received August 1995; accepted in revised form July 1996)

Abstract--The use of powdered activated carbon treatment (PACT), based on simultaneous adsorption and biodegradation, is effective for treating organic toxic pollutants, present in industrial wastewaters. Removal of phenol and aniline from aqueous solutions by biological treatment alone, by adsorption on powdered activated carbon (PAC) alone and by simultaneous adsorption and biodegradation were compared. In the adsorption experiments, Langmuir adsorption isotherms were obtained, from which Qo, the limiting adsorption capacities, and b, the constant related to the energy of adsorption, were determined. Q values of phenol and aniline were found to be similar, while the energy-related constant for aniline was five times higher than for phenol. Addition of mineral nutrients, needed for the biological treatment, and inactivated microbial cells increased the limiting adsorption capacities and significantly decreased the energy related constants. In biological treatment alone, kinetic studies showed that aniline was more resistant to biodegradation than phenol. In the simultaneous adsorption and biodegradation process, the PAC presence differently affected the biooxidation of phenol and aniline. While the PAC enhanced the microbial respiration in the phenol bioreactor, it significantly reduced the microbial respiration in the aniline bioreactor. Different organic removal mechanisms are suggested in PACT for phenol and aniline, due to their different energy of adsorption. The respirometric studies are recommended as an adequate tool for prediction of toxic organics removal capabilities from industrial wastewaters by PACT. 1997 Elsevier Science Ltd. All rights reserved

Key words--powdered activated carbon treatment (PACT), mechanisms, simultaneous adsorption and biodegradation, phenol, aniline

NOMENCLATURE

Adsorption
b = energy related Langmuir constant (L/rag) C = liquid phase concentration of pollutant at equilibrium (mg/L) q~ = adsorbent phase concentration of pollutant at equilibrium (mg/g) Q" = maximum, or limiting, adsorption capacity (mg/g PAC)

simultaneous adsorption and biodegradation. Wastewater purification, by powdered activated carbon treatment (PACT), which was introduced by D u P o n t (Hutton and Robertaccio, 1975) has been based on these two processes. The mechanisms involved in the complicated simultaneous adsorption and biodegradation process still need to be studied. Two different P A C T mechanisms are found in the literature. The first one (Kalinske, 1972; Perrotti and Rodman, 1974; Spetiel, 1989) suggests a mutual effect of the microbial cells and the powdered activated carbon (PAC). The presence of PAC increases the liquid-solid surfaces, on which microbial cells, enzymes, organic materials and oxygen are adsorbed, providing an enriched environment for microbial metabolism. Surface catalysis o f physico-chemical reactions is also possible on the surface of activated carbon (Kalinske, 1972), Microbial enzymes, excreted into carbon micropores, bring about extracellular biodegradation of adsorbed organics and bioregeneration of the activated carbon. The carbon adsorption capacity, controlled by the bioregeneration, is highly increased and the carbon adsorption column cycle is prolonged, as compared to pure adsorption systems alone. As a result, when simultaneous biodegradation and adsorption occurs, 391

Biodegradation BODr**v= Respirometric Biochemical Oxygen Demand (mgO2 uptake/rag substrate removed) K, = Haldane inhibitor constant (rag/L) #ma~= maximum specific biomass growth rate (h -~) R = respirometric biomass equivalent (mgO2 uptake/ mg biomass formed) Y = cell yield coefficient (mg biomass formed/mg substrate removed)
INTRODUCTION In many natural ecosystems a combination of biological and adsorption processes is a c o m m o n phenomenon. Organic pollutants, discharged from industries, are removed from the environment due to *Author to whom all correspondence should be addressed [Fax: + 972 4 822 8898].

392

F. Orshansky and N. Narkis Table 1. Composition of mineral nutrients in the synthetic aqueous solutions, at pH 7.2 Constituent Concentration (NH4)2 SO4 MgSO4"VH20 Phosphate buffer CaCI2 FeCh.6H20 500 mg/L 200mg/L 30 m t / t 27.5 mg/L 0.5 mg/L

the organic contaminants removal efficiency and the final water quality are substantially improved (Perrotti and Rodman, 1974). The second mechanism is suggested by several authors (Ehrhardt and Rehm, 1985; Craveiro and Malina, 1991; Xiaojan et al., 1991). They reported on opposite results, which showed a gradual decrease in organic substances elimination, after several adsorption cycles in the presence of microorganisms. This phenomenon was explained as P A C surface saturation, which brought about reduction of organics removal efficiencies, indicating the absence of the bioregeneration phenomenon. Xiaojian et al. (1991) suggested that extra-cellular enzymatic reactions cannot take place within the sorbent's tiny micropores, since the enzyme's molecules are larger than the micropores' size. Thus, the improvement of wastewater purification is considered as a result of a simple combination of adsorption and biodegradation, without mutual enhancement. Both theories do not supply enough quantitative adsorption and biokinetic data in order to evaluate the P A C role in the removal of organics by PACT. The aims of this research were to study the mechanisms and physiological aspects of the simultaneous adsorption and biodegradation process for removal of phenol and aniline from aqueous solutions (Narkis and Orshansky, 1993a, b, 1995). EXPERIMENTAL
Materials

The following chemicals were used in this research: extra pure aniline, manufactured by Merck, Darmstadt, Germany; analytical grade phenol, manufactured by Riedel-de-Haen, Hanover, Germany; powdered activated carbon, product of BDH Chemicals Ltd, Poole, England; 4-aminoantipyrine, product of Janssen, Geel, Belgium; 2-naphthol-3.6 disulfonic acid disodium salt, product of Fluka Chemika, Switzerland.
Methods

Heterogeneous microbial culture, obtained from raw sewage, passed through adaptation during a 2-month period, to gradually increasing phenol or aniline concentrations in a continuous flow reactor, chemostat. The adaptation started with feeding media concentrations of 200 mg/L phenol or aniline, which was increased by 100 mg/L each week, up to 1000 mg/L. The feeding solution contained, besides phenol and aniline, nutrients in concentrations as will be further described. The volume of the reactor was 2.15L. Adsorption isotherms were determined separately for phenol and aniline in distilled water solutions, as well as in aqueous solutions containing mineral nutrients and inactivated microbialcells. For example, the compositionof mineral nutrients used in the case of 500 mg/L phenol studies is given in Table 1. The same nutrients were added to all the studied systems, in proportion to the organic substrate concentrations. The stock solution of the phosphate buffer was prepared according to the BOD test, as described in the Standard Methods for the Examination of Water and Wastewater (1992). The inactivation of the microbial biomass was carried out at 30 min of UV radiation of thin layers, 7-9 ram, of microbial suspensions dispersed in tap water. The concentration of the microbial

suspensions were in the range of 30-40 mg cells/L. At the end of UV radiation, the complete microbial cells inactivation was confirmed by seeding them on solid Difco nutrient agar. Batch adsorption experiments were carried out, as described by Narkis and Ben-David (1985). To a series of 500 ml Erlenmeyer-flasks containing 250 mL of stock solutions of 1600 mg/L phenol or 1200 mg/L aniline in distilled water or in the nutrient solution, precisely weighted BDH powdered activated carbon doses, between 4 and 24 g/L, were added and were shaken in a shaker for 24 h at 25 + IC. A preliminary test showed that the adsorption equilibrium were reached after 6 h contact time. Therefore, in order to ensure that the adsorption systems reached equilibrium, the flasks were shaken for 24 h. At the end of this period, the solutions were filtered and the residual phenol or aniline concentration at equilibrium in the filtrate solutions were determined. Linearized Langmuir adsorption isotherms were obtained from which the limiting adsorption capacity Q, in mg adsorbed organic matter per gram PAC, b the constant related to the energy of adsorption, in L/mg, and the correlation coefficient r, were calculated. Biooxidation kinetic parameters were determined in batch reactors (Erlenmeyer flasks of 500 mL volume), mixed by a shaker, which contained 250 mL media of nutrient solution with an initial microbial biomass between 30 and 40 mg/L and various phenol or aniline concentrations, from 50 to 500 mg/L. In parallel, biodegradation kinetic studies were carried out by an "02 surrogate" technique (Gaudy et al., 1988) using Sapromat electrolytic respirometer. Standard deviation of oxygen uptake results were calculated to be +2.5%. Biokinetic constants calculations (Gaudy's approach) were carried out according to Gaudy et al. (1988) and Rozich and Gaudy (1992). A calibration curve of microbial suspension optical density at 2 = 560 nm as a function of dry cell mass concentration had been prepared and used for evaluation of the biomass increment rate. The simultaneous adsorption and biodegradation process respirometric studies were performed in Sapromat's batch reactors containing 250 mL solutions, with the following ingredients: phenol or aniline (500 mg/L), mineral nutrients, acclimated microbial biomass (30-40 mg/L) and various PAC concentrations between 0.74 and 3.68 g/L. One batch reactor did not contain PAC and served as a control. Phenol concentrations were determined by a 4-aminoantipyrine method and by COD (Standard Methods for the Examination of Water and Wastewater, 1992). Aniline concentration was determined by diazo coupling with 2-naphthol-3,6-disulfonic acid disodium salt (Korenman, 1975) and by direct UV absorption at 2 = 230 nm. Spectrophotometric measurements were carried out by using Milton Roy Spectronic 601. All the data are representative of repeated experiments. RESULTS AND DISCUSSION The aims of this research were to study the simultaneous adsorption and biodegradation process for the removal o f toxic organic compounds, phenol and aniline, from polluted waters. In the first stage of this research each process, adsorption and biodegra-

Characteristics of organics removal by PACT 10,

9 CJqe.. 0.3603 + 7.369 x 10`3 . C ( ~ - 1 3 5 . 7 engJO / . a ( --

393

700
600 4 0 0 m ~

b - 0.02o4 L/m0

7
~ 6~

" "

500 ~

a , " "
~ 300molL

"'t'=lH''''''~

3.

~fe,.~.~. , , ...... ; : 1-O0~-m=olL;;.; ; ; : ~:. :

lq
0 0 . . . . , . . . . i . . . . , . . . . . . . . . i . . . . , -

200

400

600

800

1000

1200

10

15 20 TIME (hrs.)

25

30

C PHENOL EQUILIBRIUM CONCENTRATION (rag/L)

Fig. 1. Linearized Langmuir adsorption isotherm of phenol in distilled water solution on powdered activated carbon,

Fig. 3. Oxygen uptake during biodegradation alone of various initial phenol concentrations in batch biological reactors.

2.0'
C,./qe - 7 . 4 7 6 x 10- 2 + 7.907. x

10-3.

( l o . 126.s mg/g

Adsorption alone
/ A d s o r p t i o n i s o t h e r m s o f p h e n o l a n d aniline o n P A C were s t u d i e d in distilled w a t e r a q u e o u s s o l u t i o n s , in the a b s e n c e a n d p r e s e n c e o f m i n e r a l n u t r i e n t s , a n d inactivated m i c r o b i a l cells. T h e linearized f o r m o f L a n g m u i r a d s o r p t i o n i s o t h e r m e q u a t i o n s w e r e o b t a i n e d , as s h o w n in Figs 1 a n d 2, f r o m w h i c h the limiting a d s o r p t i o n capacities Qo a n d the e n e r g y related L a n g m u i r c o n s t a n t s b were calculated a n d are s u m m a r i z e d in T a b l e 2. A c o m p a r i s o n o f these p a r a m e t e r s , for p h e n o l a n d aniline in distilled w a t e r s o l u t i o n s , s h o w e d a l m o s t

1.s. ~, o~ o o 0.s.

b-010S~L/m. -,

1.0.

0.0 0 . . . . 50 . . . . . .100 . . . . . 150 . . . .

200

similar limiting adsorption capacity values, and __ substantially different energies of adsorption. The Fig. 2. Linearized Langmuir adsorption isotherm of aniline aniline b value was found to be five times higher than in distilled water solution on powdered activated carbon, for phenol. The presence of the mineral nutrients and
C ANILINE EQUILIBRIUM CONCENTRATION (mgtL)

dation, was studied separately. In the second stage simultaneous adsorption and biodegradation was investigated,

inactivated microbial cells increased the adsorption capacities of PAC and considerably reduced the energy of adsorption. However, the energy of adsorption for aniline in saline solution still remained twice as high as for phenol.

Table 2. Effect of aqueous solution compositions on PAC adsorption characteristics of aniline and phenol in a single and bi-solute systems Langmuir linearized isotherm equations C 1 C qc bQ "~ Qo Media Distilled water Phenol Aniline Distilled water + mineral nutrients Phenol Aniline Sorbate (g/L) r

Qo
m~ gorganics PAC 135.7 126.6 166.3 126.1 150.3 131.8 156.9 137.1

b
(L/mg) 0.0204 0.1057 0.0121 0.0249 0.0111 0.0470 0.0098 0.0200

Correlation coetficient 0.999 0.996 0.995 0.997 0.998 0.997 0.998 0.996

C/q~ = 0.3603 + 7.3690 10-3C C/q, = 7.476 10 2 + 7.9019 x 10-3C

10-3C 10-3C 10-3C 10-~C 10-3C 10-3C

C/q, = 0.5003 + 6.0117 C/q~ = 0.3187 + 7.9319 Distilled water + inactivated microbial cells Phenol C/q, = 0.5996 + 6.6527 Aniline C/q~ = 0.1613 + 7.5863 Distilled water + mineral nutrients + inactivated microbial cells Phenol C/q, = 0.6480 + 6.3732 Aniline C/q, = 0,3673 + 7.2917 x

394

F. Orshansky and N. Narkis

1000" 900

800

~"

700"

y-15.900+1.5930C

-.

. "~ 4 0 0 ]
Z

S00mglL ~
-

=====================

_1_0_0_re_g_/ 100molL L
. .

:~ ~.,
Z

>.
. . . . . .

300"
200"
100.

o
100 0 0 10 20

8
70 0 0 . . . . , , , -

30

40

50

60

TIME (hrs.)
Fig. 4. Oxygen uptake during biodegradation alone of various initial aniline concentrations in batch biological reactors.

100 200 300 400 500 600 INITIAL ANILINE CONCENTRATION (m01L)

Fig. 6. Oxygen uptake as a function of initial aniline concentration.

Biotreatment alone

For aniline: O5 ....... ~ = 15.900 + 1.593C; r = 0.997 (2)

In the study of the biological treatment alone, the oxygen consumption during the biooxidation of various initial concentrations of aqueous phenol and aniline solutions were determined in Sapromat respirometer. The oxygen uptake, as a function of time and initial organic substrate concentration are shown in Figs 3 and 4. The initial substrate concentration affected the amount of oxygen consumed and the time for complete oxygen uptake. Complete biooxidation for aniline took a longer time than for phenol at the same initial concentrations. The asymptotic values of oxygen uptake were recorded when complete biooxidation took place. A linear relationship was found between the asymptotic values of the oxygen uptake and the initial phenol and aniline substrates concentration, as shown in Figs 5 and 6 and equations (1) and (2). For phenol: 02 ...... ~ = -2.5695 + 1.3457C; r = 0.999 (1)

where C is the initial substrate concentration in the liquid phase. Oxygen uptake and biomass increment results were used for kinetic parameters calculations, as summarized in Table 3. The biokineticparameters, Y a n d p . ~ were determined from the biomass increment, while BODr,p and R, the respirometric biomass equivalent, were calculated from the respirometric data. A relationship between the values of the biokinetic parameter Y, determined from the biomass increment observed, and those calculated from respirometric data, BODr++p and R can be expressed by equation (3). Yphenol BODrespanmne Raniline x Yaniline BODr,o ph0.o~ Rpho,o~ (3)

By substituting the experimental results from Table 3 into the right part of equation (3), the following relationship was found, as shown in equation (4). 0.659 1.59 0.389 x ~ = 2.00 (4)

80o
"

y..2.SSOS+1.34src
r-0.999

7006oo-

g I~1 ~"
,,~ >~ O

500-

The calculated value 2.00 is in complete agreement with the ratio of Ra,m.0 to Rph~.o], obtained from the experimental results of this research, which equals 2.00. These data prove that respirometric technique is
Table 3. Kinetic parameters determined in biological treatment alone of phenol and aniline Parameter ,u,~, K~ y BOD~p .... Unit h -] mg/L m~ biomass formed mg substrate removed Phenol 0.458 60.7 0.659 Aniline 0.228 49.0 0.389

300200. 100. 0

100

200

300

400

500

INITIAL PHENOL CONCENTRATION (m01L)

Fig. 5. Oxygen uptake as a function of initial phenol concentration,

R.~

m~ 02 uptake mg substrate removed mg O~ uptake mg biomassformed

1.34 2.25

1.59 4.50

Characteristics of organics removal by PACT

. PAC C0NC. (g/L)

395

d
ID ~00

o
'
~ll

"t
500

- * - , +2.21 '
2.1IS

J - ~ l

'-" z

l'/'IdtZ"
A71".4;'.~

o
~74

t~

2oo

:I< "
,z

"h',/
i5 2'0 2'5 30

I
35
4'0 45

100
0

2.9s
S,68

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

10

15
TIME

20 (hrs.)

25

30

35

TIME (hrs.)

Fig. "i. Oxygen uptake by microbial culture during simultaneous adsorption and biodegradation of 500 mg/L phenol in batch reactors containing various PAC concentrations. Reactor volume 250 mL.

Fig. 9. Oxygen uptake by microbial culture during simultaneous adsorption and biodegradation of 500mg/L aniline in batch reactors containing various PAC concentrations. Reactor volume 250 mL.

a reliable method which can be used for PACT evaluation,

Simultaneous adsorption and biotreatment Simultaneous adsorption and biodegradation of phenol and aniline was studied in a series of batch respirometric experiments. In the absence of microbial cells and substrates, the total oxygen uptake of PAC alone in distilled water was in the range of 6.0-17.0mgO2/L, depending on PAC concentration, which was relatively low. Phenol. Figure 7 shows the oxygen uptake as a function of time during simultaneous adsorption and
i..
--I 70' 0.00 PACIL

biodegradation of constant initial phenol concentration, of 500 mg/L, and various concentrations of PAC, from 0.00 to 3.68 g/L. In the absence of PAC the asymptotic oxygen uptake occurred after 30 h. PAC addition enhanced the respiration rate. The higher the PAC concentration the shorter the time required for getting an asymptotic oxygen uptake, and the sharper the slope of increased oxygen uptake curves. The oxygen uptake rates were calculated in intervals of l h each, during phenol biooxidation in simultaneous adsorption and biodegradation process+ for 500 mg/L phenol aqueous solution and various
A

A
70.t 0.740 PACIL

Ot

~ . e .o .

60-4 +
50 50

1.470

PAC/t

4o
~
"= O~

~ 4o 1
m 20
~ .... , .... , .... , .... , .... i .... , .... 5 10 15 20 25 30 35 4~ 10

../
-

20.
10 ' 0 0

\
5

"
N O "J

~ ,o 3o
os 20
1 " 0" - : ; " 5 . . . . 1 0 ' .... 15 ' .... 20 ' .... 25 ' ....30 ' .... '5

n ! 0 . . . . 5, . . . . 1 0 , . . . .1 5 , .... 20 , .... 25 ,....1 3~ 0 ....

TIME

(hrs.)

TIME

(hrs.)

TIME

(hrs.)

~":
~:~ 70" 2.210 PACIL

~ao
"] 70' 2.950 PACIL

= . ,
70"1 3.680 PAC/L

~SO-

'
a

. =
20.
10 e4 0 --, .... = .... , .... , .... i .... , ....

!
s
lo is

50.

SO

/\
~
.... , .... , .... , .... , .... +.~..., ....

30. 20.
10' 0' ....

~
" M

201
20
10 O/

=0

ms 3 0

as

1o

IS

2 0 ms a o (hrs.)

~o

is

=0

ms ~,o a s

TIME

(hrs.)

TIME

TIME

(hrs.)

Fig. 8. Oxygen uptake rates, for each 1 h interval, during simultaneous adsorption and biodegradation of 500 mg/L phenol single solute solution and various PAC concentrations in batch reactors.

396

F. Orshansky and N. Narkis

Table 4. Simultaneousadsorptionand biodegradationtreatment of phenol and anilineaqueous solutions. Data determinedin Sapromat Respirometerbatch reactorsin the presenceof variousPAC concentrations.Initialconcentration:phenol 500.00mg/L, aniline504.00mg/L. Reaction time: phenol 30 h, aniline42 h PAC Oxygen consumed Biooxidized Residual concentrations Calculated residuals Conc. by biooxidation substrate in liquid phase adsorbed on PAC Phenol Aniline Phenol Aniline Phenol Aniline Phenol Aniline g/L mgO~/L mgO2/L mg/L mg/L mg/L mg/L m g / g P A C mg/gPAC 0.0000 567 794 489.30 502.80 10.70 1.02 --0.7368 642 672 479.10 425.80 0.10 <0.03 28.37 104.80 1.4740 629 630 469.40 399.21 0.15 < 0.04 20.76 72.50 2.2108 612 594 456.72 376.10 0.15 < 0.03 19.58 57.40 2.9476 611 562 455.97 355.61 0.12 < 0.01 14.94 50.00 3.6844 616 548 459.70 343.50 0.05 < 0.02 10.94 43.30

PAC concentrations as shown in Fig. 8. Maximum oxygen uptake rates were found in the presence of PAC after different time periods elapsed from the beginning of the process. The higher the PAC concentration, the shorter the time needed for achieving the maximum oxygen uptake rate, up to a dose of 2.95 g PAC/L. A higher PAC dose, 3.68 g/L, did not change the time needed to reach a maximum oxygen uptake rate but shortened the time required for complete oxygen uptake. In the absence of PAC no maximum oxygen uptake was observed. In the presence of 2.21 g PAC/L, two small peaks were observed. Further investigations (Narkis and Orshansky, 1996) showed that only at this PAC concentration the biomass was equally distributed between the liquid phase and PAC surface, indicating that the substrate biodegradation took place at the same rate in both phases, at different periods of the process, Aniline. Different behaviour was observed in simultaneous adsorption and biodegradation of aniline 500 mg/L aqueous solution and various PAC concentrations, as shown in Fig. 9. In the case of aniline, in the linear part of the curves, similar slopes or rates were found in the absence and presence of various PAC concentrations, A lag phase of 12 h was observed in the presence of all PAC concentrations, while in the absence of PAC, no lag phase was found. The asymptotic oxygen uptake value in the absence of PAC was significantly higher than in the presence of PAC. As the PAC concentration increased, the asymptotic oxygen uptake value became lower. All these facts indicate that PAC presence had no effect on aniline biooxidation enhancement in simultaneous adsorption and biodegradation treatment. In the case of aniline PAC presence reduced the microbial respiration in this process, as compared to biotreatment

from the respirometric batch reactors after 30 h in the case of phenol and after 42 h in the case of aniline. This time coincides with the beginning of the asymptotic oxygen uptake phase, as shown in Figs 7 and 9. The residual organics concentrations in the liquid phase were determined by chemical analysis, after filtration of the samples through a millipore filter. Table 4 summarizes the residual concentrations of phenol and aniline, which was analytically determined in the liquid phase, the amount of oxygen consumed, as determined by Sapromat respirometer and the calculated biooxidized and adsorbed substrate. By using the respirometric BOD results, from the biotreatment experiments summarized in Table 3 and the oxygen consumed during simultaneous adsorption and biodegradation from Table 4, the amounts of biooxidized substrates could be calculated, as summarized in Table 4. By subtracting the amounts of the biooxidized substrates from their initial concentrations, the residual phenol and aniline adsorbed on PAC were evaluated and given in Table 4. Both aniline and phenol are biodegradable in the absence of PAC. In order to achieve 97.86% phenol biodegradation, 30 h were required and 42 h for 99.76% removal of aniline. In the presence of PAC, ,
200"

is0

El ~ - ~ , A..Ino [ ] ~ g p , c Phenol mg4"mlx~llkl~ut ra ,,,o,g pAe ~ !t /k I ~

100 I

Mechanisms of simultaneous adsorption and biodegradation process. Simultaneous adsorption and biodegradation treatment of phenol and aniline aqueous solutions, carried out in Sapromat respirometer batch reactors, were compared. The same PAC doses were added to the phenol and aniline aqueous solutions with similar 500 mg/L initial concerttrations, The samples of the treated waters were taken out

~"

"

__~
o.74 ~.47 2.2~

IL t
2.os .e8

PAC CONCENTRATION (g/L)

Fig. 10. Calculated residual non-biodegraded phenol and aniline remained adsorbed on the PAC surface, after 30 h for phenol and 42 h for aniline, in simultaneous adsorption and biodegradafion treatment, as a function of PAC concentrations.

Characteristics of organics removal by PACT between 0.74g/L and 3.68 g/L, very low organic materials residuals were found in the liquid phase, between 0.05 and 0.15mg/L phenol and less than 0.01 to 0.04 mg/L aniline. Almost all the residual non-biodegraded phenol and aniline remained adsorbed on the PAC surface. The amount of the adsorbed organics is given in Table 4, and in Fig. 10. Figure 10 shows the residual phenol and aniline as a function of PAC doses, which remained on the PAC in the mixed liquor, expressed as mg/L and as mg adsorbed phenol or aniline per gram powdered activated carbon. The amount of non-biodegraded aniline was much higher than of phenol. The percentage of the non-biooxidized phenol remained adsorbed on PAC, was in the range of 4-9% and of 15-32% for aniline, as a function of PAC concentration, The remaining aniline was strongly adsorbed on the PAC surface, not being available for biodegradation. This fact is in a good agreement with the higher energy of adsorption of aniline than of phenol, as determined from the adsorption isotherms. When the adsorbed non-biodegraded organics were expressed in mg/L mixed liquor, the higher the PAC concentration, the larger the residual organics concentration. When the residuals were expressed as mg organics per gram PAC, as the PAC concentrations were higher, the amounts of remained organics became lower. The respirometric experiments results, as well as the residual phenol and aniline in the liquid phase, determined by chemical analysis, and the calculated non-biodegraded residuals adsorbed on the PAC, enabled the comparison of the behaviour of phenol and aniline in the simultaneous adsorption and biodegradation systems. In the case of phenol, PAC addition enhanced the biooxidation processes as compared to biotreatment alone. This fact can confirm the approach in which activated carbon enhances enzymatic reactions in ~-o
pAc conc.

397

1 ~
Z

1.s.
~

g/L 704 0.

a w ~ o ~ o

1.0' ~ \
~[ ~ a 0.s ~.,

-.---o--- 1.47 --"'4"-" 2.21

x 2.95 ---0--- 3.m

x.Z7777Z

,ion,
W A V E L E N G T H trim)

" ~ ' ~ " ~ ~ 0.0 ................... ~ ~ ................... , ~....... ~=:..7.-.7 .......... 19o 21o 2ao 250 2to 2go alO aao Fig. 12. UV spectra of soluble organics remaining after 42 h of simultaneous adsorption and biodegradation and after biotreatment alone of aniline single solute aqueous solutions. Cell length 1 cm. PACT (Kalinske, 1972; Perrotti and Rodman, 1974; Speitel e t al., 1989). In the case of aniline, on one hand, PAC addition reduced the microbial respiration, while on the other hand, very low residual aniline concentrations were found in the treated water. Hence, a significant part of the aniline was adsorbed and remained non-biooxidized. Therefore, the aniline removal by PACT can be considered as a simple combination of adsorption and biodegradation, without mutual enhancement. This fact is in agreement with the suggestions of Xiaojian e t al. (1991).
Treated water quality

407 -_1

' 30. ~, 2o

!
~ ~

a O o

<.J 15, = 10.

w " s o. 0

PACC O N C E N T R A T I O N (g/L)

0.74

1.47

2 . 2 1 2.95

3.68

Fig. 11. Soluble COD determined in the filtered liquid after 30 h of simultaneous adsorption and biodegradation of phenol as a function of various PAC concentrations,

The simultaneous adsorption and biodegradation process, proved to be a suitable treatment in order to achieve high quality effluents, with better removals of phenol and aniline than by biotreatment alone, as confirmed by the results presented in Figs 11 and 12. The soluble COD, determined in the filtered liquid, after 30 h of simultaneous adsorption and biodegradation of phenol, with various PAC concentrations, is shown in Fig. 11. As the PAC concentrations became higher, the residual COD became lower. For comparison, the soluble COD of 37.7 mg O~/L, which was found after 30 h in the bioreactor in the absence of PAC, was also given. The biologically treated liquid contained 10.7 mg/L residual phenol, determined by chemical analysis (Table 4), as compared with 0.15 mg/L residual phenol, after simultaneous adsorption and biodegradation process. In the case of aniline, the residual soluble organics were followed by UV spectra determination, at wavelengths from 190 to 330 nm. Figure 12 shows the UV spectra of the soluble organics remaining after 42 h of simultaneous adsorption and biodegradation of aniline aqueous solutions, as compared to biotreatment alone. The same curve was obtained for all the UV optical densities, determined in the filtered liquid from the simultaneous adsorption and

398

F. Orshansky and N. Narkis

Acknowledgements--The research was supported by The

biodegradation, with various PAC concentrations. The UV optical density after biotreatment alone was higher than in the presence of PAC. These results, as well as the COD results, proved that final water of higher quality can be obtained in simultaneous adsorption and biodegradation of phenol or aniline solutions, than in biological treatment alone. SUMMARY Simultaneous adsorption and biodegradation treatment of phenol and aniline in synthetic aqueous solutions proved to remove efficiently these toxic organics. Higher final water quality was achieved by the simultaneous adsorption and biodegradation process, rather than by biological treatment alone, The presence of PAC in the biological treatment of phenol enhanced the biooxidation and microbial respiration, while in the case of aniline, they were reduced. Aniline was found to be more resistant towards biodegradation in the absence and presence of PAC. Starting with relatively high concentrations of phenol and aniline solutions of 500 rag/L, very low residuals, like 0.15mg/L phenol and less than 0.04 mg/L aniline, were found in the liquid phase from the simultaneous adsorption and biodegradation process. On the other hand, the percentage of non-biodegraded phenol, 4-9%, and aniline, 1532%, remained adsorbed on the PAC surface. The high energy of adsorption of aniline affected the biooxidation of the adsorbed aniline, Two different mechanisms for organics removal, by simultaneous adsorption and biodegradation, are suggested. In the case of phenol, PAC addition .enhanced the microbial respiration and biooxidation, In the case of aniline, PAC presence reduced the microbial respiration, since a significant amount of non-biodegraded aniline remained strongly adsorbed on the PAC and was not available for biodegradation. Although final high quality of the filtered water was achieved, in the case of aniline, simultaneous adsorption and biodegradation treatment is a simple combination of adsorption and biodegradation, with no mutual enhancement. This treatment can produce high quality effluents after PAC separation, The experimental approach to simultaneous adsorption and biodegradation process by using adsorption isotherms and respirometric characterization was proved to be suitable for the PACT technology study and prediction of the expected results. It is suggested that the energy of adsorption may provide an indication as to which organic pollutants might conveniently be removed by simultaneous adsorption and biodegradation treatment.

Ministry of Science and Arts, The Program for Immigrant Absorption and the Center for Absorption in Science, The Ministry of Immigrant Absorption, State of Israel. The grants from both Ministries are gratefully acknowledged.

REFERENCES

Craveiro F. A. and Malina J. F., Jr (1991) Anaerobic degradation of phenol and bioregeneration of granular activated carbon. J. Hazard. Wat. 28, 189-190. Ehrhardt H. M. and Rehm H. J. (1985) Phenol degradation by microorganisms adsorbed on activated carbon. Appl. Microbiol. Biotech. 21, 32-35. Gaudy A. F., Ekambaram A. and Rozich A. F. (1988) A respirometric method for biokinetic characterization of toxic wastes. Proc. lnd. Waste Conf. 43rd, 35-44. Hutton D. G. and Robertaccio F. L. (1975) Wastewater Treatment. USA du Pont de Nemours, E. I. and Co., US. 3904518 750909, US 702846 700114, 9 pp. Kalinske A. A. (1972) Enhancement of biological oxidation of organic waste using activated carbon in microbial suspension. Wat. Sewage Wks 199, 62. Korenman I. M. (1975) Photometric Analysis (Russ.), Chimija, 417. Narkis N. and Ben-David B. (1985) Adsorption of non-ionic surfactants on activated carbon and mineral clay. Wat. Res. 19(17), 815-824. Narkis N. and Orshansky F. (1993a) Upgrading of biodegradation processes for the removal of toxic organics from polluted waters by addition of activated carbon. Annual Report, submitted to the Ministry of Scienceand Arts (March). Narkis N. and Orshansky F. (1993b) Upgrading of biodegradation processes for the removal of toxic organics from polluted waters by addition of activated carbon. Annual Report, submitted to the Ministry of Science and Arts (December). Narkis N. and Orshansky F. (1995) Upgrading of biodegradation processes for the removal of toxic organics from polluted waters by addition of activated carbon. Annual Report, submitted to the Ministry of Science and Arts (March). Narkis N. and Orshansky F. (1996) Upgrading of biodegradation processes for the removal of toxic organics from polluted waters by addition of activated carbon. Annual Report, submitted to the Ministry of Scienceand Arts (June). Perrotti A. E. and Rodman C. A. (1974) Factors involved with biological regeneration of activated carbon. Water Am. Inst. Chem. Engr. Syrup. Set. 144, 316-325. Rozich A. F. and Gaudy A. F., Jr (1992). Design and
Operation of Activated Sludge Processes Using Respirometry Lewis Publishers, Boca Raton, pp. 5-24.

Speitel G. E., Jr, Lu C.-J., Zhu X. J. and Turakhia M. H. (1989) Biodegradation and adsorption of a bisolute mixture GAC columns. J. Wat. Poll. Control Fed. 61, 221-229. Standard Methods for the Examination of Water and Wastewater (1992) Am. Public Health Assoc., Am. Wat. Wks Assoc. and Wat. Pollut. Control Fed., 18thedn. Xiaojian Z., Zhansheng W. and Xiasheng G. (1991) Simple combination of biodegradation and carbon adsorption-the mechanism of the biological activated carbon process. Wat. Res. 25(2), 165-172.