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Effect of Suspended Solids On Wastewater
Effect of Suspended Solids On Wastewater
227-236, 1995
~ Pergamon 0043-1354(94)E0117-O ElsevierScienceLtd. Printedin Great Britain
Abstract--Effluents enriched with high suspended solids concentration were tested for disinfection with
chlorine dioxide. Following disinfection with various chlorine dioxide concentrations from 0 mg/l to
52.78 mg/1 and contact times from 2 up to 24 h, half of the experimental samples were crushed (by
Ultra-Turax) and tested for survival of indicator microorganisms. The crushing process revealed that a
certain fraction of indicator microorganisms were left intact as a result of chlorine dioxide disinfection.
This fraction was found to be able to regrow as was shown for all bacterial indicators, such as coliforms,
fecal coliforms, enterococci and heterotrophic count, despite high disinfectant concentrations. The study
results indicate that some microorganisms fraction entrapped into suspended floes can survive disinfection
with chlorine dioxide, depending also on indicator type, therefore their prior removal by coagulation,
sedimentation and filtration is a major prerequisite for successful disinfection.
227
228 NAVAN^RKIS et al.
Table I. Characteristics of raw and suspended solids enriched volume, and the reaction was stopped by the addition of
activated sludge effluent NTS. Then half of the experimental volume was crushed by
Concentration (ms/I) Ultra-Turax rapid mixer for 2min at 10,000rpm; (b) a
second experimental set under similar conditions was left to
Raw activated Enriched effluent stir for 24 h without NTS addition. At the end of 24 h half
Parameters sludge effluent suspension of the experimental volume was subjected to crushing
Total suspended solids mg/I 26.1 422.7 as above; (c) in the third experimental set the reaction was
Volatile suspended solids mg/I 22.7 346.1 stopped after 2 h contact time with NTS, and left under
Total COD mg/l 02 119.9 615.2 continuous stirring for 24 h, and indicator microorganisms
Soluble COD mg/I 02 98.3 96.7 were enumerated before and after crushing suspended
Nitrites NOf-N mg/I 0.0 0.0 solids; (d) and (e) were used as controls without any
NH4+ -N mg/l 43.9 44.33
Temperature ("C) 26 8.1 addition of chlorine dioxide for 2 and 24 h respectively. All
pH 8.0 8.1 experimental sets were anlaysed for microbiological indi-
cators.
Microbiological assays
suspended solids, taken directly from the activated sludge
reactor, were added to from an enriched effluent suspension Enumeration of bacteria in enriched effluent suspension,
(EES) of 422.7 mg/l total suspended solids. prior to and after disinfection, were performed for coil-
forms, fecal coliforms, enterococci and total count. Mul-
Chlorine dioxide production tiple-tube fermentation technique (MPN) was used for
Chlorine dioxide was produced from sodium chlorite enumeration of coliforms, fecal coliforms and enterococci
activated by 10% HCI solution (APHA, 1989). The chlorine (Standard Methods, 1989). Total heterotrophic count was
dioxide gas formed was driven off by air bubbling and then performed on plate count agar as already described (Stan-
absorbed into distilled water, cooled in an ice bath. dard Methods, 1989).
Coliphages as virus indicator were enumerated by MPN
Experimental procedure method (Kott, 1966) and verified on agar double layer
method with E. Scherichia coil CNt3 as host (E. Scherichia
The effect of chlorine dioxide was studied on survival of coli C, nalidixic resistant, from our collection) as already
indicator microorganisms distributed freely in the liquid, or described (Adams, 1959; Armon et al., 1988).
attached to the external surface and entrapped inside the
suspended solids.
The enriched effluent suspension was divided into a series RESULTS AND DISCUSSION
of I 1 Erlenmeyer flasks. Various doses of chlorine dioxide
were added to form the following initial concentrations: 0, Suspended solids together with soluble organic
28.54, 35.53, 44.20 and 52.58 rag/1. The flasks were mixed by compounds play a major role in disinfection
magnetic stirrers and sealed in the dark for periods of 2 h efficiency. As already shown by LeChevallier et al.
and 24 h contact time, at room temperature. At the end of (1988a, b), suspended solids protect microorganisms
contact time, aliquot of each disinfected sample was with- form the toxic effect of disinfectants. Various disin-
drawn from each flask and immediately transferred for fectants have to penetrate into suspended solids in
chemical analysis, to determine the residual CIO2, C10~- and
combined chlorine concentrations. To the remaining disin- order to inactivate the entrapped bacteria or viruses
fected effluents, granular sodium thiosulfate (NTS) was (LeChevallier et al., 1988b). The aim of this research
added, in order to stop the action of the residual disinfec- was to study the effect of suspended solids present in
tant. activated sludge effluent, on the chlorine dioxide
Chemical analyses disinfection efficiency. For this purpose activated
sludge effluent from Haifa Municipal Sewage Treat-
The chlorine dioxide stock solution always contains in
addition to chlorine dioxide, small amounts of chlorite ions ment Plant was enriched with supplementary sus-
and free chlorine. Their concentration prior and after the pended solids, by addition of mixed liquor from the
addition to the enriched effluent suspension (EES) were acitvated sludge reactor, to reach a final concen-
measured by amperometric titration using PAO, for deter- tration of 422.7mg/1. Various doses of chlorine
mination at pH 7.0 and above and thiosulfate for determi-
dioxide, such as 0, 28.54, 35.53, 44.20 and 52.78 mg/l
nation at pH 2.5 and below (Palin, 1974; Aieta and Roberts,
1981; Aieta et al., 1984; APHA, 1989). Table 2 shows the were added to the enriched effluent suspension (EES)
composition of chlorine dioxide stock solution used in the for 2 and 24h contact time. At the end of each
reported experiments. contact time, 100ml of the disinfected sample was
The chlorine dioxide, ClOy, combined chlorine and 1£C1, withdrawn from each flask and was chemically
the sum total of the oxygenated chlorine compounds and
chlorine residuals were determined immediately, at the end analysed to determine the residual CIO2, CIO2-,
of each contact time, as shown in Figs 1 and 2. The combined chlorine and ZCI = ECIO2 + CIO~ +
experimental procedures were as follows (Flow Chart 1): (a) HOC1 concentrations.
first set of effluent samples containing 422 mg/l activated Figures 1 and 2 show the residual concentrations
sludge suspended solids, were disinfected with chlorine
of CIO 2, C102-, combined chlorine and
dioxide for 2h contact time. Chlorine dioxide and its
accompanying chlorine compounds residuals were deter- ~£C1 = EC102 + C102- + HOCI as a function of ap-
mined immediately, in a sample, while in the remaining plied various doses of C102. The initial chlorine
dioxide doses applied in this study were much higher, The CIO 2 residual increased with an increasing C102
as compared to 8-9 mg/l chlorine dioxide required for dose and decreased with contact time.
effective disinfection of regular activated sludge efflu- In order to evaluate the disinfection efficiency of
ents (Narkis et aL, 1992), due to the presence of the chlorine dioxide on the entrapped indicator microor-
supplemented suspended solids. ganisms inside the suspended solids at the end of each
At all applied disinfectant doses, residual C102 was contact time, 0.3 g sodium thiosulfate was added, to
found after 2 h contact time, while after 24 h contact stop the disinfection process. The sample was then
time, the residual C10 2 was found only at doese of tested for "free and attached to the external surfaces
44.20 mg/l and above. For example, at a dose of of the suspended solids" (FATES) viable microor-
44.20mg/1 C102, a residual of 3.12mg/1 C102 was ganisms, before and after the suspended solids crush-
found after 2 h contact time and 0.11 mg/1 after 24 h. ing.
Mixed Liquor
~,w TSS = 396.6 mg/L
(e)
(c)
Flow chart 1. Flow diagram of enriched effluents suspension treated with constant chlorine dioxide dose
(28.54 mg/l), and assay procedure for indicator microorganisms enumeration. FATES, Free and attached
to the external surface indicators.
230 NAVANARKISet al.
The EES's coliforms reduction by disinfection with observations (Narkis et al., 1992). After 2 h contact
various doses of chlorine dioxide, before and after time, coliphages were completely inactivated at CIO 2
crushing, is shown in Fig. 3. After 2 h contact time doses of 35.53 and above. Suspended solids crushing
[Fig. 3(a)], a 4-5 log reduction in coliforms numbers resulted in coliphages release or regrowth of E. coli
was observed at all C102 doses examined. Neverthe- host survivors (Fig. 4) of 1-2 orders of magnitude
less after the suspended solids crushing, 1-2 logs of [Fig. 6(a)]. After contact time os 24 h, coliphages were
coliforms numbers were recovered from the EES. At completely inactivated at all C102 doses [Fig. 6(b)]. A
24 h contact time of EES with various doses of C102, small number of bacteriophages survived after 24 h at
a smaller reduction of total coliforms was observed 28.54mg/I C102 due to insufficient disinfectant re-
[Fig. 3(b)]. These results were expected due to a sidual. After 2 h contact time of chlorine dioxide,
decrease in active C10: concentration as a function of sodium thiosulfate was added, and the suspension left
contact time, affecting disinfection efficiency. Higher to stay for 24 h in the absence of the disinfectant.
coliform numbers found in this experimental set, Complete reduction in bacteriophage numbers was
can also indicate possible regrowth of the surviving observed [Fig. 6(c)]. Even the crushed fraction did not
fraction after 24 h contact time. The EES crushed reveal any surviving bacteriophages despite the pres-
fraction was equal or higher in surviving coliform ence of possible E. coli hosts as shown in Fig. 4.
numbers at all 0 0 2 doses. The lowest coliform Heterotrophic bacteria (as total count) was ex-
reduction was obtained after 2 h of C102 contact pected to be more resistant to chlorine dioxide disin-
time, a reaction ended by sodium thiosulfate ad- fection. As shown in Fig. 7, after 2 h contact time the
dition, and left for an additional time of 24 h before heterotrophic count was reduced by 4-6 orders of
assay [Fig. 3(c)]. Under these conditions the coliforms magnitude, depending on chlorine dioxide concen-
were reduced by only 1-2 order of magnitude without tration. Crushing the suspension revealed hetero-
any difference between the crushed and uncrushed trophic bacteria I-2 orders of magnitude entrapped
fraction. inside the suspended solids [Fig. 7(a)]. After 24 h
A similar behaviour was observed with fecal coli- contact time, increasing doses of C102 showed
forms, expected to be equally affected by C102 increasing inactivation of total count [Fig. 7(b)].
(Fig. 4). Indeed, fecal coliforms reduction was almost Crushing the suspended solids proved again that
identical to total coliforms after 2 h contact time at heterotrophic bacteria is entrapped inside the sus-
all C102 doses [Fig. 4(a)]. A more efficient reduction pended solids and were much less affected at 28.54
in fecal coliforms was achieved after 24 h contact and 35.53 mg/1 C102.
time, with similar regrowth pattern as total coliforms Addition of sodium thiosulfate after 2 h contact
[Fig. 4(b)]. As expected the crushed fraction showed with chlorine dioxide and the suspension let to stay
higher fecal coliforms number. The 2 h contact time for additional 24 h, showed that chlorine dioxide did
and count at 24 h time interval, did not show any not affect the total count of the free, attached and
difference between the two physical treatments, only entrapped heterotrophic bacteria [Fig. 5(c)]. The re-
regrowth of the indicators, following disinfection growth of the heterotrophic population was close to
termination [Fig. 4(c)]. the initial numbers at the start of the experiment,
A remarkable reduction was achieved with entero- showing an excellent recovery potential. The hetero-
cocci (Fig. 5). After 2 h of chlorine dioxide contact trophic count was similar with slightly higher num-
time, enterococci were reduced by five logs starting bers for the crushed fraction at 28.54mg/1 and
with 28.54 mg/1 chlorine dioxide and completely inac- 52.78 mg/l [Fig. 5(c)].
tivated above this concentration [Fig. 5(a)]. The It is known that suspended solids in solution have
crushed fraction conferred some enterococci numbers a protective role in microorganism inactivation by
at all chlorine dioxide doses. Enterococci reduction disinfectants. As shown by others (LeChevallier et al.,
after 24 h contact time showed a similar inactivation 1988a, b), suspended solids play a role as a surface to
behaviour, reaching complete inactivation at which microorganisms may adhere. In addition it
44.20 mg/l C102. In this experiment, crushed fraction should be mentioned that suspended solids are not a
was only higher at 35.53 to 44.2mg/1 [Fig. 5(b)]. rigid matrix, but a sponge-like matrix, in which
Addition of sodium thiosulfate, after chlorine dioxide liquids can penetrate. In such matrixes bacteria are
2 h contact time and then let to stay for 24 h, resulted adsorbed on surface or entrapped inside.
in higher numbers of surviving enterococci, either On one hand this entrapment offers a better protec-
released or regrown [Fig. 5(c)]. The crushed fraction tion to microorganisms against disinfectants, and on
showed slightly higher numbers at 28.54mg/1 to the other hand the sponge-like structure of the flocs
52.78 mg/1 of C102 doses. enable disinfectant penetration. Crushing the sus-
In general, bacteriophages are more susceptible to pended solids revealed either the surviving fraction of
to chlorine dioxide inactivation compared to chlor- the microorganisms, or the regrown one. Studying
ine, which is ineffective against viruses (Narkis et al., various indicator microorganisms reaction towards
1992). In addition bacteriophages do not regrow chlorine dioxide disinfectant showed that each indi-
following inactivation by chlorine dioxide. The re- cator group was affected differently, except for the
sults shown in Fig. 6 corroborate these previous related coliforms and fecal coliforms. Among the
Pme L"! (ClO2) ) mg L"1 (C102) 24 h contact time
~! 2 h coMact time
- I 2 h contact time, and crush - ] 24 h contact time, and crush
lx10z lx10s
Oh(co~r~) (contr.)
10x10r I0x107
;2.78 28.54 mg I- "1
;2.71 )8.54 mg L"1
c-
fOx107 txlo8
IOxlO7 xl0 8
~)
i2.78 r mg L"1
IOxlO7 lx10e
1 0 X 1 0 7 ~ ~ 10X107
1~107 1~107
Fig. 4. Fecal coliforms survival after disinfectionof enriched effluentsuspension (EES) by various doses of chlorine dioxide with and without tlocs crushing. (a) After 2 h contact
time; (b) after 24 h contact time; (c) after 2 h contact time, Na-thiosulfate addition, and let to stay for 24 h.
0 mgL"1(el02) [ ] 2 h contacttime 0 mgL"1 (C!02) [] 24 h contact time
[ ] 2 h contacttime, and crash [] 24 h contact time, and crush
Ix107 "'; 0 h (control) lX107 .'1 0 h (control)
44.2 rngL"1 (Sl) 35.53 mgL"1 44.2 mgL"1 (b) 35.53 mgL "1
%,
",% 0
,.~
.. IxI07
52.78mgL "I \ ' " / ~ . N ~ L "1
/
1
\ 1. l
'4
1)(107 lX10 7
Fig. 5. Enterococci survixal after disinfection of enriched effluent suspension (EES) by various doses of chlorine dioxide with and without flocs crushing. (a) After 2 h
contact time; (b) after 24 h contact time: (c) after 2 h contact time, Na-thiosulfate addition, and let to stay for 24 h.
0 mgL "1 (C102) [ ] 2 h contact time 0 mgL"1 (C102)
[ ] 24 h contacttime
lx107 [ ] 2 h contact time, and crush 24 h contacttime, and
lx107 [] crush
/I" ..~ oh(co.~)
f ",
f'/" L\ "',\\ /// "%,~\
lxlOr , , ~ i \ , ~ " ' ~ lxlOr lx107~ , ~ . lx10'
~ /
lX107 Ix107
"x -, 7
\ /
'\ c~
, /
t4.2 mgL"1 (I) 35.53 mgL"1 14.2 mgL "1 Oh) 35.53 mgL "1
! m
lx10a lx10 a
"-ig. 7. Heterotrophic bacteria survival after disinfection of enriched effluent suspension (EES) by various doses of chlorine dioxide with and without floes crushing. (a) After 2 h contact
time; (b) after 24 h contact time; (c) after 2 h contact time, Na-thiosulfate addition, and let to stay for 24 h.
236 NAVANARKISet al.
bacterial indicators, enterococci (fecal streptococci) Aieta E. M. and Roberts P. V. (1981) Chlorine dioxide:
were the most susceptible to chlorine dioxide inacti- chemistry, generation and residual analysis. In: Chemistry
in Water Reuse (Edited by Cooper W. J., Vol. 1, Chap.
vation, followed by coliforms and fecal coliforms and 20. Ann Arbor Science Publ. U.S.A.
heterotrophic bacteria. Bacteriophages were also Aieta E. M., Roberts P. V. and Hernandez H. (1984)
drastically affected by chlorine dioxide as already Determination of chlorine dioxide chlorine, chlorite and
reported (Narkis et al., 1992), and were not able to chlorate in water. J A W W A , Res. Technol. 76, 64-69.
APHA (1989) Standard Methods for the Examination of
recover in order to infect their potential host, which Water and Wastewater, 17th edition. American Public
partially recovered after 22 h without chlorine diox- Health Association, Washington, D. C.
ide [Figs 3(c) and 4(c)]. Armon R., Arella M. and Payment P. (1988) A highly
efficient second-step concentration technique for bacterio-
CONCLUSIONS phages and enteric viruses using ammonium sulfate and
Tween 80. Can. J. Microbiol. 34, 651-655.
Chlorine dioxide disinfection efficiency of enriched Israel Ministry of Health (1979) "Criteria for Treatment
Processes for Wastewater Reused in irrigation" 2rid sug-
effluent suspension depends on: gestion.
(1) Disinfectant penetration into floc particle as Kott Y. (1966) Estimation of low numbers of Eseherichia
confirmed by bacteriophage inactivation. eoli bacteriophage by use of the Most Probable Number
(2) The resistance of the various indicator micro- method. Appl. Microbiol. 14, 141-143.
organisms to chlorine dioxide. LeChevallier M. W., Cawthon C. D. and Lee R. G. (1988a)
Factors promoting survival of bacteria in chlorinated
Monitoring disinfection efficiency by enumerating water supplies. Appl. Environ. Microbiol. 54, 649-654.
free microorganisms seems to be an over simplifica- LeChevallier M. W., Cawthon C. D. and Lee R. G. (1988b)
tion of the real situation. In experiments with chlorine Inactivation of biofilm bacteria. Appl. Environ. Microbiol.
dioxide for 2 h contact time, the decrease in bacterial 54, 2492-2499.
Narkis N. and Kott Y. (1992) Comparison between chlorine
indicators was significantly higher, however the ex- dioxide and chlorine for use as a disinfectant of waste-
periment which was continued for an additional 24 h water effluents. Wat. Sci. Technol. 26, 1483-1492.
resulted in bacterial indicator regrowth (Figs 3, 4, 5 Narkis N., Offer R., Linenberg E. and Betzer N. (1990) The
and 7). The regrowth occurred as a result of two use of chlorine dioxide in disinfection of wastewater. In
factors: (i) resistant indicator microorganisms en- Water Chlorination, Chemistry, Environmental Impact
and Health Effect (Edited by Jolly R. E.) Vol. 6. Chap. 73,
trapped into suspended solids which survived the pp. 955-966. Lewis publ.
disinfection, and (ii) oxidation of complex organics to Narkis N., Kott Y., Katz A., Orshansky F., Friedland Y.,
lower molecular weight organics, which in turn are Betzer N., Offer R. and Melamed E. (1992) Effluents'
metabolically more accessible to the surviving bac- disinfection by combinations of chlorine dioxide and
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and Ecosystem Stability, Jerusalem, June 21-26, 1992.
cators surviving fraction and even regrowth following Palin A. T. (1974) Analytical control of water disinfection
the cessation of disinfectant activity by sodium thio- wit reference to differential DPD methods for chlorine,
sulfate. Bacteriophage efficient inactivation by chlor- chlorine dioxide, bromine, iodine and ozone. Inst. Water
ine dioxide in suspended solids supports the use of Eng. 28, 139-154.
State of California (1978) Water Reclamation Criteria. Cali-
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In summary the actual study results indicate that resulting from the interactions of chlorine dioxide with
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WHO Euro Report and Studies No. 42. Regional Office
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