PII: S0043-1354(98)00482-5

Wat. Res. Vol. 33, No. 11, pp. 25872592, 1999 # 1999 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/99/$ - see front matter

THE EFFECT OF WATER TREATMENT PROCESSES ON THE BIOLOGICAL STABILITY OF POTABLE WATER
M M J. Y. HU1*, Z. S. WANG2, W. J. NG1* and S. L. ONG1*
1 Civil Engineering Department, The National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260, Singapore and 2Environmental Engineering Department, Tsinghua University, Beijing 100084, People's Republic of China

(First received February 1998; accepted in revised form October 1998) AbstractThe AOC (assimilable organic carbon) method was used in this study to evaluate the biological stability of potable water. The potable water was drawn from a waterworks located in a petrochemical industrial area in China. Infrared spectra analysis was adopted in this study to examine the relationship between treatment process and organic compounds in water. By monitoring the AOC concentration in groundwater, potable water and the euent of each treatment process (biological pretreatment, ozonation, GAC adsorption), the following were noted: (1) a considerable AOC concentration could still be detected in potable water after advanced treatment processes, such as ozonation and activated carbon adsorption. Relatively poor biological stability was also noted in the potable water; (2) GAC was the most eective process with a total AOC removal eciency of more than 80%. The corresponding biotreatment removal eciency was only 45%. However, ozonation yielded a negative overall removal eciency of 119%; (3) while biological pre-treatment and GAC adsorption contributed towards a biologically stable water, ozonation yielded oxidation products which were biologically unstable. Ozonation, if used, should therefore be combined with the GAC or biological processes. Treatment processes (like ozonation) which increased the amount of organics in carbonyl group would likely lead to poor product water biological stability. # 1999 Elsevier Science Ltd. All rights reserved Key wordsAOC, groundwater, potable water, biological stability, GAC adsorption, ozonation, biological pre-treatment, carbonyl group

NOTATIONS

INTRODUCTION

AOC

assimilable organic carbon (mg acetateC/l) AOC-P17 AOC represented by strain P17 (mg acetate-C/l) AOC-NOX AOC represented by strain NOX (mg acetate-C/l) AOC-T total assimilable organic carbon (mg acetate-C/l) TOC total organic carbon (mg/l) DOC dissolved organic carbon (mg/l) AOC/TOC ratio of AOC to TOC AOC/DOC ratio of AOC to DOC Nmax-P17 maximum number of strain P17 Nmaxmaximum number of strain NOX NOX CFU colony formation unit GAC granular activated carbon

*Author to whom all correspondence should be addressed. [Fax: +65-7-791635; e-mail: cvehujy@nus.edu.sg].

Biological stability of drinking water has been gaining considerable attention in the elds of water treatment and water quality maintenance. Biologically stable drinking water is dened as one which would not cause reproduction of coliforms and heterotrophic bacteria. Bacterial regrowth is bacterial growth in drinking water after treatment, especially the growth of microorganisms within the distribution system. The link between biodegradable organics in drinking water and bacterial regrowth in potable water distribution systems has been noted by several researchers since 1980 (LeChevallier et al., 1987, 1991; Huck, 1990; Van der Kooij et al., 1982). Increases in organic content in a drinking water facilitate bacterial growth resulting in biological slimes. The latter may attach to the surfaces of the distribution pipes and water supply tanks and hence increase the energy costs for water transportation, pipe corrosion, and dissolution of iron and other metal ions into water (Bourbiget et al., 1982; Rittmann and Snnoeyink, 1984; LeChevallier, 1990). In order to assess the biological stability of water, an analytical method for determining the concentration of AOC has been developed (Van der

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Table 1. Typical groundwater characteristics Parameters Colour Ammonia-nitrogen Turbidity Phenols Oil and grease TOC Values <5 TCU <0.02 mg/l <1 FTU 0.002 mg/l 0.250.28 mg/l 7.013.6 mg/l

J. Y. Hu et al.
Table 2. Operating parameters for unit processes Treatment steps Bio-ceramic pre-treatment Ozonation (two stages) GAC adsorption Ozone disinfection Parameters and values ow rate: 3.0 l/h dose: 2.03.0 mg/l, detention time: 20 min/stage hydraulic loading: 5.6 m3/m2h, empty bed contact time: 14 min dose: 0.40.6 mg/l, detention time: 14 min

Kooij et al., 1982). Generally, a drinking water is dened as biologically stable when its AOC level is less than 1020 mg acetate-C/l without disinfection or less than 50100 mg acetate-C/l if it had been disinfected (LeChevallier et al., 1992, 1993). The AOC method is also employed to determine the inuence of water treatment technologies on water quality, especially on water biological stability in water distribution systems. This study focused on the AOC values of a groundwater and potable water and the eect various treatment processes had on the residual AOC and biological stability. In addition, infrared spectra analysis was carried out to explore the relationship between the AOC level and organic characteristics in the treated water.
MATERIALS AND METHODS

4 months. The bio-ceramic medium was loaded into a glass column with 5 cm diameter and 1.0 m height. The source water was fed through this column at a ow rate of 3 l/h. No aeration was needed because of the high dissolved oxygen concentration in the groundwater. Ozonation Ozonation was provided at a dosage of 23 mg/l. There were two stages in series with each stage at a hydraulic detention time of 20 min. When sampled on 29 March and 31 May, 1995, the dosages were then 2.4 and 2.0 mg/l, respectively. The distribution of ozone between the two stages was in the ratio of 6:4. Ozone was used again after the GAC adsorption but this was for disinfection. The ozone dosage was at 0.6 mg/l. GAC adsorption GAC adsorption was used to remove the organics remaining after ozonation. The hydraulic loading and empty bed contact time were 5.6 m3/m2h and 14 min, respectively. At the time when the study began, the GAC system had been in operation for 8 months and it was believed that there was some biological activity inside the GAC beds. AOC test Details of the AOC test had been presented by Zhang (1995). This method adopted the recommendations by Van der Kooij et al. (1982) and LeChevallier et al. (1993) for the purpose of rapid detection. Strain P17 and strain NOX had been used for AOC determinations in the following combinations: AOC(T) = AOC(P17) + AOC(NOX). Infrared spectra analysis and data handling Infrared spectra analysis was used to identify the characteristics of organics present in the various water samples. This was to explore the structural characteristics of these organics. The potassium bromide (KBr) disc method was adopted in this study. 0.1 ml of ether concentrate on the KBr crystal disc was prepared from each 4 l sample collected. The selective integral technique (Ning, 1989) was used to process each infrared spectra diagram. Four groups of organics were selected in the peak area integral and these were drawn from: oily matter such as alkanes, polycyclic aromatic hydrocarbons (aromatic ring and derivative of benzene cycle) and ozonation by-products with the carbonyl group.

Groundwater The groundwater samples were drawn from a petrochemical industry area for analysis in March and May, 1995. It had been reported that this water source had been polluted by petrochemicals previously (Hu et al., 1995). Some of the groundwater characteristics are listed in Table 1. Potable water Advanced treatment processes such as ozonation and GAC adsorption were adopted at a local waterworks to improve water quality. A schematic diagram of the treatment processes used in the plant is as shown in Fig. 1, in which a small-scale experiment is shown in dashed arrow. The operating parameters for each of the treatment steps are listed in Table 2. Bio-ceramic pre-treatment Bio-ceramic pre-treatment of source water was tested at the waterworks in March. The purpose of this small-scale experiment was to assess the feasibility of removing oily organics in the groundwater with a bio-ceramic column. The bio-ceramic is a support medium with a diameter between 25 mm. The medium with its biolm had been prepared in the laboratory before the experiment proper by contacting with synthetic oily water for almost

Fig. 1. A schematic of unit treatment processes in the treatment plant.

Biological stability of potable water

Table 3. Groundwater and potable water AOC concentrations Water sample Nmax-P17 (cfu/ml) March sampling (groundwater) May sampling (groundwater) March samplinga (potable water) March samplingb (potable water) May samplinga (potable water) May samplingb (potable water)
a b

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P17 AOC(P17) (mg acetate-C/l) 654 387 940 1122 254 283 Nmax-NOX (cfu/ml) 3.2 105 1.0 106 5.7 105 8.5 105 1.3 105 2.7 105

NOX AOC(NOX) (mg acetate-C/l) 27 84 48 71 11 23

AOC (P17+NOX) (mg acetate-C/l)

2.7 106 1.6 106 3.9 106 4.6 106 1.0 106 1.2 106

681 471 988 1193 265 306

Sampled at a minimum distance (right after the water treatment plant). Sampled at a maximum distance (about 6 km away from the water treatment plant). P17, Pseudomonas uorescens strain; NOX, Spirillum species strain. RESULTS AND DISCUSSIONS

The results of the AOC determinations for groundwater and potable water samples are summarised in Table 3. The AOC/TOC values of water samples collected in this study are shown in Table 4. The AOC results of the eects of water treatment processes on the biological stability of potable water are shown in Table 5 and Fig. 2 (AOC value right after ozone disinfection was omitted because of some errors in the sampling and not shown here). The result of infrared spectra analysis is shown in Fig. 3. The range of wave numbers was selected with reference to Ning (1989). The characteristics of the organic compounds are indicated by the peak areas of the organics and their relative ratios in Table 6. Biological stability of groundwater and potable water AOC values in the March and May groundwater samples were 681 and 471 mg acetate-C/l, respectively. These values were much higher than the values reported in the literature of 0.110 mg acetate-C/l for uncontaminated groundwater (Rittmann and Snnoeyink, 1984). Surface water AOC levels have been noted to be as high as 20611 mg acetateC/l (Table 7) and in some rivers receiving wastewater discharges levels as high as 663 mg acetate-C/l (Gibbs et al., 1993). The results obtained in this

study indicate that the AOC concentrations in March were similar to values from rivers receiving wastewater discharges. It was probable that the biologically unstable groundwater character was linked to the petrochemical industry in the vicinity. The groundwater samples from the two sampling periods were quite dierent in terms of AOC values and composition. This may be noted from the AOC-P17 and AOC-NOX values (Table 3). This was true too of TOC values (Table 4). The higher AOC concentration in March corresponded with the dry season and hence lower groundwater levels. Such seasonal uctuations have been reported before, with the largest uctuations generally occurring in spring and the least in winter (Huck et al., 1991). Table 3 showed that, AOC levels in the potable water samples were well over 100 mg acetate-C/l. The study suggested that even with advanced water treatment processes, AOC levels in the potable water investigated could remain suciently high for bacterial regrowth to occur in the distribution system. AOC levels in March were even higher than inuent AOC levels although this was not so in May. This phenomenon may be associated with groundwater characteristics. From the AOC values of groundwater and drinking water obtained, it may be noted that the AOCP17 levels were generally much higher than the

Table 4. AOC/TOC ratios in groundwater, potable water and the euents of the various treatment processes Sample March sampling (groundwater) May sampling (groundwater) March sampling (potable water)b March sampling (potable water)c May sampling (potable water)b May sampling (potable water)c Bio-ceramic euent Ozonation euent GAC adsorption euent Production plant Aa Production plant Ba Production plant Ca
a b

TOC (mg/l) 13.6 7.0 10.8 9.4 9.0 7.0 7.0 11.4 10.1 3.3 1.9 3.6

AOCT (mg acetate-C/l) 681 471 988 1193 265 306 380 1492 271 49 15 62

AOCT/TOC (%) 5.0 6.6 9.1 12.7 2.9 4.4 5.4 13.1 2.7 1.5 0.8 1.7

Reported by Van der Kooij (1989), and presented as DOC or AOCT/DOC. Sampled at a minimum distance (right after the water treatment plant). c Sampled at a maximum distance (about 6 km away from the water treatment plant).

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Table 5. AOC concentrations in the euents of treatment processes

Sample Groundwater Bio-ceramic euent Ozonation euent GAC adsorption euent

AOC(P17) (mg acetate-C/l) 654 371 1439 271

AOC(NOX) (mg acetate-C/l) 27 9 53 0

AOC(P17+NOX) (mg acetate-C/l) 681 380 1492 271

AOC(NOX)/AOC(P17+NOX) (%) 4.0 2.5 3.6 0.0

AOC-NOX levels. The AOC-NOX concentration in water was less than 4% of the total AOC, while AOC-P17 concentration made up more than 90% of the total AOC. This suggested compounds like alcohols, hydrocarboxylic acids and carbohydrates, which were easily utilized by the P17 strain, could be major contributors to the AOC, but carboxylic acids constituted only a minor fraction of the AOC. Potable water at dierent sampling locations showed a dierence in AOC levels. An increase in AOC concentrations was noted with AOC levels in March increasing more sharply in the distribution system compared to May. The AOC level (6 km from the treatment plant) in March was 1193 mg acetate-C/l (Table 3). The reasons could be that residual ozone had continued oxidation of residual organics in the distribution system. This postulate was supported by the detection of residual ozone at the furthest point of the distribution system (0.14 mg O3/l) due to the relatively short residence time. AOC concentration after treatment by various unit processes and AOC removal eciency From Table 5 it could be seen that the AOC level in the groundwater was reduced from 681 mg acetate-C/l to 380 mg acetate-C/l after the bio-ceramic pre-treatment. This nding was in agreement with other reports that biological ltration in water treatment was capable of reducing AOC concentrations (Van der Kooij, 1992; Huck et al., 1994) and reduced the bacterial regrowth potential in distribution systems. The AOC removal eciencies by bio-ceramic were 44.2, 43.3 and 65.3% in terms of AOC-T, AOC-P17 and AOC-NOX, respectively (Fig. 2). AOC-P17 would still be the major AOC re-

sidual. These suggested that compounds such as oxalic acids could be expected to be more easily biodegraded than compounds represented by strain P17. The bio-ceramic euent AOC/TOC (5.4%) was almost the same as the groundwater's (5.0%) (Table 4). This suggested that bio-ceramic pre-treatment had reduced the TOC and AOC in almost equal proportions. On the contrary, AOC in water from the twostage ozone oxidation system increased to 1492 mg acetate-C/l. Ozonation resulted in a negative overall removal in terms of total AOC (119.1%). This nding was consistent with reports in the literature (Narkis and Schneider-Rotel, 1980; Van der Kooij et al., 1989; LeChevallier et al., 1992). However, the magnitude of the increases observed in the latter studies was much lower than what was experienced in this study. The magnitude of increase was related to the ratio between ozone dosage and DOC concentration. Furthermore the nature of the organic materials present could also be expected to inuence the amount of AOC produced during ozonation (Van der Kooij, 1990). Ozonated water had a AOC/TOC value of 13.1% which was very much higher than groundwater's. This high AOC/TOC and the sharp increase in AOC after ozonation conrmed that ozonation tended to yield a product water with poor biological stability. While a sharp increase in AOC level after ozonation was noted, this study revealed that the increase was due primarily to AOC-P17 concentration instead of AOC-NOX. This observation was consistent with the ndings reported by Van der Kooij et al. (1989) but dierent from observations reported by Huck et al. (1991), in which the

Fig. 2. Removal eciency of AOC by unit treatment processes.

Biological stability of potable water

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Fig. 3. Infrared spectra of euents from treatment processes.

increase in AOC following ozonation was associated primarily with AOC-NOX. AOC levels could be expected to be low following granular activated carbon treatment (Van der Kooij et al., 1989; Huck et al., 1991) because ozonation would lead to easier adsorption or degradation of the by-products by the subsequent unit processes. Filtration through granular activated carbon resulted in removal eciencies of 81.2, 100 and 81.8% in terms of AOC-P17, AOC-NOX and AOCT, respectively. The higher removal eciency of AOC-NOX suggested that this component was more easily adsorbed than the AOC-P17. These results showed that GAC adsorption and biodegradation were eective at AOC control. Similar observations had been reported by other researchers (Van der Kooij, 1990; Huck et al., 1994). With GAC ltration after ozonation, the AOC level in the euent was substantially reduced to 271 mg acetate-C/l. However, the treated euent was still unable to meet the desired criterion of 100 mg acetate-C/l for biologically stable water

(Brandfrond et al., 1994). The reason for the relatively high AOC even after GAC treatment in this study would be related to the relatively high AOC concentration in the ozonated euent. In contrast, GAC euent AOC/TOC (2.7%) was much smaller than the corresponding value in the ozonated euent. This low AOC/TOC value suggested that GAC treatment was very ecient in improving the biological stability of its treated euent. It would be worth while pointing out that the acceptable AOC/DOC ratios in the euent of three production plants were around 0.81.7%. The higher AOC/TOC in the produced water observed in this study indicated the relatively poor biological stability of drinking water. Organic characteristics in the euent of various treatment processes Table 6 summarised the characteristics of organic compounds obtained from the infrared spectra analysis. The organic compounds present in the groundwater remained largely unchanged after the

Table 6. The peaks areas of samples from infrared spectra analysis Samples 16231563 (I)a Groundwater (March) Bio-ceramic euent Ozonation euent GAC adsorption euent
a b

Wave number (cm1) (organics) 775720 (II)b 1.1 1.1 1.9 0.8 18201654 (III)c 14.3 14.4 32.2 11.9 29972835 (IV)d 10.5 8.7 16.7 8.8

Ratios of organics (III)/(I + II + IV)e 1.2 1.4 1.6 1.2

0.4 0.5 1.1 0.6

(I) represents skeleton of aromatic ring. (II) represents mono-substitution derivative of benzene cycle. c (III) represents carbonyl group. d (IV) represents alkane. e (I + II + IV) represent the total amount of oily matter; (III)/(I + II + IV) represents the ratio of carbonyl group to oily matter.

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Table 7. AOC concentration in several surface watersa

Water type Lake River with opening storage Meuse river with opening storage North Saskatchewan river
a

AOC(P17) (mg acetate-C/l) 47 31 97 20611(P17+NOX)

The Netherlands, for pure bacteria supply and to Miss Suqi Zhang for analyses of samples.
REFERENCES

Reported by Huck (1990) and Van der Kooij (1990).

bio-ceramic pre-treatment process except for the alkanes group (IV) which was signicantly reduced. The four groups of organics increased after ozonation. The increase in the carbonyl group was probably the largest contributor to the sharp increase in AOC in the ozonated water. The GAC treatment showed reductions in all 4 kinds of organics and hence the low AOC. Furthermore, the ratio of (III)/ (I + II + IV) of 1.2, which was similar to the corresponding ratio of groundwater, suggested that GAC had the ability to remove organics with a carbonyl group in water for water biological stability improvement.
CONCLUSIONS

The following conclusions can be drawn from the present investigation. 1. It was noted that the product water from advanced water treatment processes employing ozonation and activated carbon adsorption may still have an AOC concentration of more than 265 mg/l which is considered high with respect to potable water standard. 2. Ozonation could signicantly increase biodegradable organic compounds and yield a negative overall AOC removal eciency of 119.1%. This suggested ozonation by-products could favour formation of AOC. These by-products were mostly detected as AOC-P17 and were mainly organics with the carbonyl group. 3. Biological pre-treatment could help to minimise bacterial regrowth in distribution systems by removing about 45% of AOC. 4. GAC ltration proved to be most eective at removing AOC with a high removal eciency of more than 80%. 5. Treatment processes (like ozonation) which increased the amount of organics in carbonyl group would likely lead to a product water with poor biological stability. Ozonation therefore, should be combined with the GAC or biological processes to minimize the AOC formation potential.

Acknowledgements This research was supported in part by a grant from the National Nature Science Fund, China. Sincere thanks go to Dr Van der Kooij, The Netherlands Water Works Testing and Research Institute,

Bourbiget M. M., Dodin A. and L'Herritier R. (1982) Limiting bacterial aftergrowth in distribution systems by removing biodegradable organics. AWWA Ann. Conf., Miami, FL. Brandfrond S. M., Palmer C. J. and Olson B. H. (1994) Assimilable organic carbon concentrations in Southern California surface and groundwater. Water Res. 28(2), 427. Gibbs R. A., Scutt J. E. and Croll B. T. (1993) AOC concentrations and bacterial numbers in a water distribution system. Water Sci. Technol. 27(34), 159. Hu J. Y., Zhang S. Q. and Wang Z. S. (1995) The eect of treatment processes on drinking water biological stability. Proceedings of the International Symposium on Water Treatment Technology, Beijing, China. Huck P. M. (1990) Measurement of biodegradation organic matter and bacterial growth potential in drinking water. J. AWWA 82(7), 78. Huck P. M., Fedorak P. M. and Anderson W. B. (1991) Formation and removal of assimilable organic carbon during biological treatment. J. AWWA 83(12), 69. Huck P. M., Zhang S. L. and Price M. L. (1994) BOD removal during biological treatment: a rst-order model. J. AWWA 86(6), 61. LeChevallier M. W., Babcock T. M. and Lee R. G. (1987) Examination and characterisation of distribution system biolms. Appl. Environ. Microbiol. 53(12), 2714. LeChevallier M. W. (1990) Coliform regrowth in drinking water: a review. J. AWWA 82(11), 74. LeChevallier M. W., Schulz W. and Lee R. G. (1991) Bacterial nutrients in drinking water. Appl. Environ. Microbiol. 57(3), 857. LeChevallier M. W., Becker W. C., Schorr P. and Lee R. G. (1992) Evaluating the performance of biological active rapid lters. J. AWWA 84(4), 137. LeChevallier M. W., Shaw N. E., Kaplan L. A. and Bott T. L. (1993) Development of a rapid AOC method for water. Appl. Environ. Microbiol. 59(5), 1526. Ning Y. C. (1989) The Structure Identication of Organic Chemicals and Organic Spectroscopy. Tsinghua University, Beijing. Narkis N. and Schneider-Rotel M. (1980) Evaluation of ozone induced biodegradability of wastewater of a drinking water distribution system. Water Res. 14(8), 929. Rittmann B. E. and Snnoeyink V. L. (1984) Achieving biologically stable drinking water. J. AWWA 76(10), 106. Van der Kooij D., Visser A. and Hijnen W. A. M. (1982) Determining the concentration of easily assimilable organic carbon in drinking water. J. AWWA 74(10), 540. Van der Kooij D., Hijnen W. A. M. and Kruithof J. C. (1989) The eects of ozonation, biological ltration and distribution on the concentration of easily assimilable organic carbon (AOC) in drinking water. Ozone Sci. Eng. 11, 297. Van der Kooij D. (1990) Assimilable organic carbon (AOC) in drinking water. In Drinking Water Microbiology: Progress and Recent Development, ed. G. A. McFeters. Springer-Verlog, New York. Van der Kooij D. (1992) Assimilable organic carbon as an indicator of bacterial regrowth. J. AWWA 84(2), 57. Zhang S. Q. (1995) Methods and signicance of AOC. Proceeding of the 4th Conference on Advanced Treatment for Drinking Water, Banbu, China.