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~ t e r Re~ Vol 1-. No tl. pp. 16,o_9 16-~.

1~3 IJ043-1~54'~3S300-i) 00
Pr!nted in Great Britain Pcrgamor3 Pre,,~ Ltd

KINETIC M O D E L I N G OF U.V. DISINFECTION


OF WATER

BLAINE F. SEVERIN', MAKRAM T. SUIDANz and RICHARD S. ENGELBRECHTz


'Tennessee Eastman Co., Kingsport, TN 37662 and :Department of Civil Engineering,
University of Illinois at Urbana-Champaign. Urbana. IL 61801, U.S.A.

( Receiced Februarv 1983)

Abstract--The response of pure cultures of Escherichia coil Cand&hl parapsilosis, and bacterial virus f2
to ultraviolet light radiation was studied in a batch reactor and in a completely mixed, flow-through
annular reactor. Two kinetic models were tested as to their ability to scale between batch results and
flow-through reactor results. Using the respective best-fit kinetic parameters for each model from batch
data. the response of the organisms in the flow-through reactor could be predicted by using either
multi-target kinetics or series-event kinetics. The series-event model was judged to be superior to
multi-target kinetics because it better represents the known mechanism of u.v. inactivation than does
multi-target kinetics. Since two different models can be used to describe the data, the simple agreement
between experimental data and model predictions does not necessarily prove that either model is
mechanistically correct.

Key words--ultraviolet light, inactivation kinetics, reactor design, Escherichia toll. Cundida parapsih)sis,
bacterial virus f2, muhi-target kinetics, series-event kinetics, disinfection

NOMENCLATURE cable to reactor design have been developed and


tested. Haas and Sakellaropou[os (1979) proposed
A = absorbance at 254 nm in base,, cm -t models tbr disinfection in single lamp u.v. reactors
10 = intensity at surface of quartz tube, #W c m - : subjected to various mixing regimes. These models
/ = intensity at any point in the reactor, ,uW cm-" were based on a mixed second-order rate expression,
k = kinetic constant, cm-' i t W ~ s -~
first-order with respect to surviving organism density
m = intensity factor in annular reactor
M; = microorganisms having reached event level i and first-order with respect to u.v. intensity. Severin
n = threshold for inactivation in the series-event (1982) related the inactivation o f bacterial virus f2 in
model batch experiments and in experiments with a com-
n,. = number of critical sites in the multi-target model pletely mixed, flow-through reactor using a mixed
N, = density of organisms with i hits or density at
s e c o n d - o r d e r kinetic rate expression. However, it was
event level i, number cm-3
N t = initial density of organisms, number cm-3 impossible to relate batch and completely mixed,
Ns = density of surviving organisms, number cm -3 flow-through reactor results for E s c h e r i c h i a coli and
r = variable representing radial distance in com- C a n d i d a p a r a p s i l o s i s using mixed second-order inac-
pletely mixed flow-through reactor, cm
tivation kinetics. It was observed that these two
r~j= radius of quartz tube in completely mixed
flow-through reactor, cm organisms were initially resistant to u.v. in batch
t: = radius of completely mixed flow-through reactor, experiments. This observation was used to qual-
cm itatively explain the inability to relate batch and
r.v, = rate of formation of organisms with i hits on rate completely mixed, flow-through reactor kinetic data.
of formation of organisms at event level i, num-
The failure o f the simpler kinetic model led to the
ber cm - ~ s- L
t = contact time in batch reactor, s d e v e l o p m e n t and c o m p a r i s o n o f two kinetic models
r = theoretical contact time in completely mixed o f inactivation, multi-target kinetics and series-event
flow-through reactor, s. kinetics and the application o f these models to batch
and completely mixed, flow-through reactors.
INTRODUCTION
MULTI-TARGET MODEl.
Ultraviolet light (u.v.) has been p r o p o s e d as an
alternative to chlorine for the disinfection o f second- The initial resistance o f microorganisms to u.v.
ary treated municipal wastewater effluents. While inactivation has, in the past, been modeled with
many empirical observations have been m a d e on the multi-target kinetics. This model was first developed
u.v. process (Roeber and Hoot, 1975; Oliver and for types o f radiation other than u.v. and current
Carey, 1976; Scheible et al., 1979; J o h n s o n et al., observations on the mechanism o f u.v. inactivation
1979; Severin. 1980), few mechanistic models appli- do not generally support the model. However, it has

1669
I670 BLAINE F. 8EYERIN et al.

still found general use ISmith and Hana~valt. 1969: To obtain values of nc and k from a set of data, the
Harms, 1980) because of its simplicity of logic. intercept of a semi-log plot of surviving fraction vs t
simplicit? of mathematics and ability to fit batch gives n c. and the slope of the straight line segment is
data. - k l . However, since it is difficult to exactly deter-
In this model, it is assumed that a particle contains mine the straight line portion of the curve from
a finite number, n . of discrete critical targets, each of experimental data, it is preferable to evaluate k and
which must be hit prior to full inactivation of the n~ from a least-square fit of the data to equation (2).
particle. Since the number of targets is finite, the Equation (2) is also applicable for describing u.v.
probability of attaining a hit on the particle is inactivation in plug-flow reactors with perfect cross-
decreased as the reaction proceeds: i.e. since there are flow mixing. In this instance, however, t is to be
fewer targets available as the reaction progresses, the replaced by z, the hydraulic detention time, and I is
probability of attaining the next hit is decreased. A to be replaced with the average intensity within the
particle may represent an organism with n,. targets or reactor.
a clump of organisms possessing a total of n c targets.
Application of the multi-target model to a mixed,
Due to the methods of enumeration used, however,
flow-through reactor o f annular design
it is impossible to identify the difference in the
survival of a clump or an organism. Therefore, the A completely mixed, u.v. reactor of annular design
terms "'organisms" or "'particle" are used inter- was employed to obtain continuous-flow inactivation
changeably in this presentation. data. The light intensity in such a configuration is not
uniform. For modeling purposes, a radial approxi-
Application oJ multi-target kinetics to batch reactors mation of an infinite line source was used to represent
Batch u.v. inactivation data were collected in a the u.v. lamp where light is emitted radially from the
completely mixed, flat, thin-layer, closed-batch reac- line and the intensity, L at a point at radial position
tor using water with high u.v. transmission. For such r, is given by the integrated form of Lambert's Law
a configuration, the u.v. intensity, I (/,~W cm 2), at all (Jacob and Dranoff, 1966).
points within the reactor may be assumed to be
I = -l°r°
- e-2.303-i( . . . . . i (4)
uniform. Assuming that mixed second-order kinetics
r
describe the rate of inactivation of a critical target,
then probability, P(O), of a specific target surviving where I0 is the intensity (uW) at the surface of the
attack is quartz tube which separates the lamp from the water
in the reactor, r 0 (cm) is the outer radius of the quartz
P(0) = e -~" (1)
tube, and A (cm-~) is the base 10 extinction coefficient
and the probability of inactivating a specific target is at 254 nm. A second, more complex model, the finite
(1 - e -~") where k is a rate constant (cm-' I~W -~ s -~) length lamp model (Jacob and Dranoff, 1970) was
and t is the exposure time (s) to u.v. Assuming that also investigated (Severin, 1982) and found not to
all targets are equivalent and that damage is ran- significantly alter the interpretation of inactivation
domly distributed among the targets, then the proba- results.
bility of survival of a particle with n,. critical targets The completely mixed, flow-through reactor model
is given by is derived through the sequential solution of equation
(3) applied to the material balance for a completely
N~
-- = 1 - (1 - e~") "' (2) mixed, flow-through reactor for i = 0 to i = n c which
Nt yields the expression
where N, is the surviving organism density and N; is ~-~ imkloz
the initial organism density. N, 1 (5)
NI t=l 1 + imkloz
Equation (2) may also be derived using a material
balance for a closed-batch reactor and the rate ex- where z is the hydraulic detention time in the reactor
pression and m is an intensity factor which represents the ratio
of the average intensity in the reactor to Io.
r.,, = (n,. - i + t)klN,_ t - ( N , . - i)klN, (3)
2r0 [l - exp(--2.303A (? - ro))]
where r.,. is the rate of attaining the ith hit in a m = (6)
2.303 A (?2 _ r0 )
particle and k represents the rate constant for at-
taining the last hit. The quantities ( n ~ - i + 1) and The radius of the reactor is ? (cm). It is significant
(n,.- i) are probability factors applied to account for that m arises directly from the integration of the point
the increased difficulty or specificity in hitting remain- reaction rate over the entire reactor rather than from
ing targets as the reaction proceeds. Equation (2) is an a priori assumption that the average reaction rate
then obtained through sequential solution of equa- is properly defined by the average intensity.
tion (3) from i = 0 to i = n~ in the material balance
for a closed-batch reactor. SERIES-EVENT MODEL
For a given value of kit, an increase in n~ results
in an increase in the surviving fraction of organisms. A second approach to modeling u.v. inactivation is
Kinetic modeling of u.v. disinfection of water 1671

with series-event kinetics. An event is assumed to be When an event occurs in a d u m p . it is possible that
a unit of damage. Events occur in a stepwise fashion this event occurs in an organism which is alread? past
and each step is assumed to be an integer function. the threshold level, theretbre making the event useless
The rate at which an organism passes from one event in terms of inactivating the clump. The experimental
level to the next is first-order with respect to u.v. system studied by Wei and Chang is more representa-
intensity and independent of the event level occupied tive of multi-target kinetics. Equation (10) ~ould be
by the organism. As long as an organism is exposed valid tbr describing the inactivation of clumps of
to u.v. it continues to collect damage. However. a single-event organisms, providing the clump size was
threshold exists, whereby, organisms which have infinitely large and the inactivation of only a few
reached an event level greater than the threshold are organisms in a clump was adequate to inactivate the
inactivated, and all those which are below this level entire clump. This, however, is not the case.
survive. The threshold may vary depending on the Equation (10) is also appropriate ['or describing the
culturing conditions used. both prior to and after inactivation efficiency of a plug-flow u.v. disinfection
irradiation: however for a given set of conditions, the process. In this instance, however, t is to be replaced
threshold level is constant. The above is expressed with the hydraulic detention time. r, and I is to be
as a series chemical reaction based upon single replaced with the u.v. intensity averaged over the
organisms. cross-sectional area perpendicular to the flow.

Application o f the series-event model to el mLved,


Mo2~ M,!£...M, ~ - L . . . M , _ ~ 3 k L M,3~t . . . (7) flow-thro,~gh reactor o J a n n u l a r design
The local rate at which organisms pass through
where k is the mixed, second-order reaction rate
event level i, r~, is given by equation (81. where
constant (cm-' # W -~ s-~), l is the local point light equation (4) is substituted tbr I.
intensity (pWcm--'), M, is an organism which has
reached event level i, and n is the threshold level of rA, =
kl°r°. e -_, ~o~r~..... ~(N, . I "%)" (I I)
r
the organism.
Equation (11) is then incorporated into a material
Application o f the series-event model to batch reactors balance for a completely mixed, flow-through reac-
tor, and the resulting equation is solved sequentially
For a batch reactor operated under the conditions
from i = 0 to i = n - 1. The resulting general expres-
described earlier, the rate at which organisms pass
sion tbr the density of organisms that have reached
through event level i, r v,, (number cm -3 s -t) is given
event level i, N~, is given by
by
(mkloz )7
r.~., = k i N i _ i -- k l N i . (8) N, (1 + m k l o r y NI (12)
Equation (8) is then incorporated into a material
and the density of surviving organisms in the effluent,
balance for a batch reactor, and the resulting equa-
N,, is then given by
tion is solved sequentially from i = 0 to i = n - 1.
The general expression for the time-varying density ,-i ,- i (mklor),
of organisms at any level i, N~, (number cm -3) is N,= ,=0
Z ,v,= X,=y_0
= (l+mk/0r) '~l'
{13)
given by
Equation (13) can be rewritten in a closed form as
N, = N t ( k l t )i -~t,
- -
i.'
e (9)
N~ l - [('F
1+ (13)

where N, is the initial density of organisms prior to


Equation (13) can be used to predict the performance
exposure to u.v. light, and t is the exposure time (s)
of any completely mixed, flow-through reactor: how-
to u.v. The density of surviving organisms N~, i.e.
ever, for general applications the quantity m l o should
those which have reached level n - 1 or less, is given
be replaced by the average intensity within the reac-
by
tor.
,,-I e -~t' ~+l (k[t)i
,v,= K ,v,.= N, ~ ,7 " (1o)
i=O i=0
EQUIPMENT AND PROCEDURES
Wei and Chang (1975) used an expression similar
to equation (10) to describe the inactivation of Continuous flow disinfection data were developed
clumps of organisms with chlorine. The n u m b e r of using a completely mixed, single lamp, annular reac-
organisms per clump that they observed was finite tor (Fig. 1). This reactor was made from a 14.0cm
and varied from 1 to 18. The use of equation (10) to diameter (i.d.) Plexiglass column, 27cm in height.
describe the data of Wei and Chang (1975), however, The volume of the reactor, excluding the volume of
is inappropriate since it embodies the assumption the quartz tube, was 4010 cm< A 2.54-cm diameter
that the occurrence of an event in a viable organism (o.d.) quartz tube housed a General Electric Vohare
is independent of the occurrence of previous events. u.v.-LUX gl0T5½ low pressure mercury vapor lamp,
6"'- BLAINE F. SEVERIN e£ a l

man, Ind.. London. England}. P H B A in this range


of concentrations was not toxic to the micro-
organisms. The temperature of the test water was
2 0 + 1.0C. Complete mixing in the flow-through

~Q
T reactor was confirmed by showing that no gradients
Our et I OD v lorno of surviving organisms existed within the reactor
(Severin, 1982).
CD uClrt Z tube
Batch disinfection data were generated using a
fiat-tray reactor with a 254cm water depth and a
total volume of 500 ml. The u.v. source was a General
CD Electric G15T8 lamp mounted in a parabolic, stain-
less steel reflector, and utilizing a Sylvania FS-2
Glostat Ballast at line voltage. The lamp was placed
CD 6 3 c m above the surface of the water. A shutter
arrangement was used to control exposure time. a
OD OIO magnetic stirrer provided mixing in the reactor. The
u.v. intensity at the surface of the water was mea-
sured to be 4 5 0 # W c m - - ' using the potassium fer-
:F,7.0c
rioxalate chemical actinometry test.
•~ I--- r " 1 2 7 c m Test water used in the batch reactor was prepared
by adding 2.5 ml of stock phosphate buffer solution
Fig. 1. Completely mixed, flow-through u.v. reactor.
and 500 ml DI water to the reactor. This solution was
then sterilized for 5 min with u.v. prior to the addi-
powered by a Universl M ~ . Co. (Patterson, N J) tion of organisms. The organism densities ranged
Thermomatic-X fluorescent lamp d.c. ballast. Volt- from 2 x l0 s to 1 x 106cfu or pfu ml -~ test water.
age (140 V) was supplied by a Variac voltage regu- The pH of the water was between 6.5-7.0, and the
lator (General Radio Company, Concord, MA). The temperature of the water was 20 4- 1.0:C. No PHBA
inside wall of the reactor was painted lamp black to was added to the water, and in all tests the u.v.
minimize reflection. The incident light intensity at the absorbance was below 0.04 cm-*. At this level, the
surface of the quartz tube (34,000bzWcm--') was average intensity through the water column was
measured using the potassium ferrioxalate chemical approx. 95~(, of the input energy flux at the water
actinometry test (Calvert and Pitts, 1966). Complete surface.
mixing in the reactor was achieved by the use of two A pure culture of Candida parapsilosis, isolated by
impeller systems placed on opposite sides of the Engelbrecht et al. (1974), was maintained on refrig-
reactor. Each impeller shaft contained five, equally erated slants of yeast malt agar (YMA), prepared by
spaced, three-bladed impellers. The shafts were adding 3 g yeast extract, 3 g malt, 5 g peptone, 10 g
driven by Fisher Scientific (Chicago, IL) Dyna-mix dextrose and 12g agar to 1 l. DI water. Inactivation
motors rated at 6000 rpm and operated at 85""/o of tests were performed on 20-24 h cultures of C. para-
capacity. The reactor was operated under a slight psilosis grown in yeast malt broth ( Y M A without
head to eliminate free face vortexing. Flows could be agar) on a shaking water bath at 27 :C. The yeast was
adjusted to provide retention times between 20 and enumerated using pour plates of Y M A . incubated for
260 s. 3 days at 27:C.
Water used in the experiments with the flow- A pure culture of E. toll, initially isolated From a
through reactor was prepared in a 200 1. reservoir by secondary wastewater effluent, was maintained on
adding I I. of stock phosphate buffer solution (24 g refrigerated nutrient agar slants. Fresh cultures of E.
KH_,POa and 6 g N a O H per 1. stock) and appropriate coli were grown at 37~C on a shaker water bath in
amounts of organism culture and u.v. light attenu- nutrient broth with 100 ppm by volume of "Tween
ating agent to 200 1. DI water. The buffer maintained 80" (Polyoxyethylene Sorbitan M o n o Oxylate; ICN
the pH between 6.5 and 7.0. Organism densities in the Pharmaceuticals, Inc., Cleveland, OH). a non-ionic
test water varied between 2 x 105 and 1 x 10~ colony surfactant, added as an anticlumping agent. Cultures
forming units (cful or plaque forming units (pfu) per grown for 20--24 h were used in the inactivation tests.
ml. The u.v. attenuating agent was para- E. coli was enumerated using 20-24 h nutrient agar
hydroxybenzoic acid (PHBA), which has a narrow pour plates incubated at 35°C.
absorbance peak around 244 nm. P H B A was used to Initial cultures of bacterial virus f2 and host or-
simulate natural tannic acid components present in ganism E. coli K-13 were obtained from Vincent
wastewater. Quantities up to 500 ml of a stock P H B A Oliveri, The Johns Hopkins University, Baltimore,
solution (10 g I -~) added to 200 1. DI water provided MD. Bacterial virus f2 was cultured and enumerated
a range of absorbances at 254 nm, ,4, between 0.04 using a modification of the method described by Loeb
and 2.2 c m - ~. The absorbance of the test water was and Zinder (1961). Host cultures of E. coli K-13 were
measured on an A C T A III Spectrophotometer (Beck- grown in TYE broth (tryptone 10 g 1-~, yeast extract
Kinetic modeling of u.~. disinfection of ~ater 1673

IO

OI

• A A ,5 rl c =1

"O 000~

00001

°/ "\
ooooo~ I I I I
0 50 I00 r SO 200
Contact time (s)
Fig. 2. Batch inactivation data: analysis with multi-target kinetics. O I E . co~i: 0 - - C . parapsilosis:
~ - - f 2 virus.

l g l ~, and sodium chloride 8 g 1-~ at 3 7 C on a solid lines represent the least-square, best-fit of the
shaking water bath. Stock virus suspensions were experimental data to equation (2). The best-fit values
prepared by the addition of the virus (0.1 infectively of k and n, are presented in Table 1. The sum of
ratio of virus to bacteria) to pregrown cultures of E. squares of deviation were calculated as the sum of the
coil K-13, having a density of approx. 3 x 10'~ bacte- squares of the differences between the natural loga-
ria ml-L Alter lysis of the infected culture for 8-12 h rithms of the surviving fraction and the model solu-
at 37~C on a shaking water bath, cell debris was tion. The search for the best-fit parameters was
removed by centrifugation at 2500rpm for 15 min initiated by assuming an integer values of n., then
(Sorval model GLC-2 lab centrifuge type HL-4 rotor determining the corresponding value of k which gave
head, Sorval Inc., Newtown, CT). The supernatant the least sum of squares of deviation. Other integer
liquor, containing the virus stock, was maintained in values of n,. were subsequently tested until a global
5 ml aliquots at 4~C. Virus density was determined m i n i m u m was found. Both E. coli (201 hit) and C.
using an agar overlay method. TYE agar (10 g agar parapsilosis (1871 hit) appear initially resistant to u.v.
I-~ TYE broth) plates and fresh cultures of host while bacterial virus f2 (single hit) is not. The obser-
bacteria were prepared in advance of testing. Just vation that bacterial virus f2 is a single hit organism
prior to use, I ml of a sterile stock solution of calcium is consistent with other observations with viruses with
chloride (22 g 1-~) was added to each 20 ml of host single stranded nucleic acid (Harms, 1980).
bacteria culture. Three drops of the bacteria culture, Twenty-one experiments were performed using the
to provide a lawn of host cells, and 0.1 ml of a proper completely mixed, flow-through reactor; 6 with E.
dilution of virus suspension were then added to 3 ml toll, 9 with bacterial virus f2, and 6 with C. para-
of melted TYE agar. This mixture was then poured psilosis. Experiments were performed by applying test
over a hardened agar plate. Plaques were counted water to the reactor at various flow rates in order to
after 8-24 h incubation at 35~C. achieve contact times between 20 and 260 s. Each
experiment was performed using a water with
RESULTS different u.v. absorbance. The range of absorbances
tested was from less than 0.02 to as high as 2.2 cm -~.
Analysis with multi-target kinetics To test the applicability of the multi-target model
Batch inactivation data are presented in Fig. 2. The for the completely mixed, flow-through reactor, ex-

Table 1. Kinetic parameters for multi-target model from batch data


k x 10~ Regression
n (cm-"#W -I s -I) coefficient (r")
E. coli 201 0.893 0.958
C. parapsilosis 1871 0.433 0.953
f2 virus 1 0.0724 0.986
I674 BLAINE F. SEVERINet al.

I.O --
parapsilosis. However. the response in the
flow-through reactor is opposite of this and C. para-
psilosis appears more resistant than bacterial virus f2.
First-order kinetics are not able to predict this in-
version in response (Severin, 1982), while Fig. 3
0.1 shows that the multi-target kinetic mode[ does predict
the inversion.
Equation (5) shows that the survival fraction,
8 Ns/NI, is a function of the two dimensionless groups
mklor and n<. All the data from the completely mixed,
o
I..L 0.01
flow-through reactor can, therefore, be condensed
onto a single graph (Fig. 4) of three plots of Ns/N t vs
mklor, one plot for each organism. The solid lines are
predictions calculated using equation (5) and the
best-fit values of n< from the batch data. The points
presented are the observed fraction survivals plotted
0.00~ I I I I 1
0 50 i00 150 200 250 vs the corresponding values of mklor where m, Io and
r are experimental observations and k is the best-fit
Theoretical contact time ( s )
kinetic constant from the batch data. Excellent con-
Fig. 3. Prediction of inactivation in the completely mixed, formity is seen between observed data and the model
flow-through reactors in waters with low u.v. absorbance solution. The degree of scatter is not uncommon for
using multi-target kinetics. ©--E. coli, A =0.009cm-~;
O--C. parapsilosis, A =0.02cm-I; A - - f 2 virus, A = disinfection studies. In all three cases, the correlation
0.003 cm-'; - - predicted from batch parameters. (r-') of the data to the predictions was in excess of
0.97.

perimental results were compared to the model pre- Analysis with series-event kinetics
diction [equation (5)] using the kine{ic parameters Figure 5 shows the fit of the batch results as
from Table 1. Figure 3 shows the data for E. coli, analyzed with series-event kinetics. The solid lines
bacterial virus f2 and C. parapsilosis collected in are the least square, best fit of the data to the
experiments using waters with no u.v. attenuating batch series-event model [equation (10)]. Kinetic par-
agent added. The absorbances in these experiments ameters were interpreted in a manner similar to that
were 0.009, 0.003 and 0.020 cm -~, respectively. Solid described for multi-target analysis. The least square
lines represent the predictions using the multi-target best fit values of k and n are presented in Table 2. E.
model; generally good predictions are obtained. coli shows an event level of 9, C. parapsilosis has an
More importantly, the batch data (Fig. 2) showed event level of 15 and bacterial virus f2 is a single-
that bacterial virus f2 is more resistant than C. event organism. An interesting feature of both the

IO

° %-,(,,
A G °'O.
._~ ,,, " ~ 0.~20. n c = 1871

O.OI

o.oo ~ I I I I
o.t Lo )o ~oo Jooo Eo,ooo

KI o r

Fig. 4. Prediction of completely mixed, flow-through reactor results over a wide range of contact times
and u.v. absorbance using multi-target kinetics. ©--E. coli: O--C. parapsilosis: ~ - - f 2 virus: - -
predicted from batch parameters.
Kinetic modeling of u.v. disinfection of water 1675

~ O.OOr

00001

o,oooot I I
50 I00 150 200

Contact time s)

Fig. 5. Batch inactivation data: analysis with series-event kinetics. O--E. coli; C. parapsilosis; A--f2
bacterial virus.

series-event model and the multi-target model is that DISCUSSION

ifn or nc is unity, then both models simplify to mixed,


second-order kinetics. Both multi-target and series-event kinetics have
Equation (13) indicates that the survival fraction, been found useful in fitting batch u.v. inactivation.
Ns/N ~, is a function only of the dimensionless groups The rate expressions for both models are easily
mklor and n. It may be expected, therefore, that all extended to completely mixed, flow-through reactor
the data collected in the tests with the completely configurations, and the kinetic parameters found
mixed, flow-through reactor can be condensed onto from batch data can be used successfully to predict
a single graph of three plots of Ns/N t vs mklor; one the efficiency of flow-through reactors. Outwardly
plot for each organism since each organism exhibits therefore, there appears to be little justification for
a different value of n. Figure 6 is a plot of fraction the preference of one model over the other. This leads
survival vs mklor for all the flow-through reactor data to the interesting point that two mechanistic models
as analyzed using the series-event model, The solid cannot both be correct. Obviously, the ability of a
lines are the predicted results using equation (10) and model to fit and predict experimental performance
the best-fit value of n calculated from the batch data. does not lend absolute proof to the correctness of the
The points represent the observed fraction survivals mechanism.
plotted vs mklor where m, I0 and ~ are experimentally The major difference in the two models is the
determined and k is the best-fit value from the batch mathematical preception of the targets or events. The
data. Excellent conformity between observed data logic of the multi-target model necessitates that the
and the model solution is seen. The degree of scatter number of targets be finite and discrete, such that the
is not uncommon for disinfection studies. In all three probability of attaining successive hits within an
cases, the correlation (r 2) of the data to the predic- organism is reduced as the number of available
tions was in excess of 0.955. It is important to note targets is depleted. The number of critical targets, nc,
that series-event kinetics also predicts the inversion of is the total extent to which an organism or particle
response of f2 virus and C. parapsilosis observed in may be damaged since only nc targets exist. Whether
the two reactor situations. or not this is acceptable for a particular biological

Table 2. Kinetic parameters for series-event model from batch data


k x I0J Regression
n (cm2#W -I s -I) coefficient(r'-)
E. coli 9 1.538 0.967
C. parapsilosis 15 0.891 0.965
f2 virus 1 0.0724 0.986
676 BL~dXE F. SEVER[N et al.

,0

"..
-° = o'-,% _
. vjo',<...

"~ 001 • n=15

A r]:9 O0

r] =

o.oo J i [ I
0 I I, 0 I0 I00 I000 I0,000

KI ° T

Fig. 6. Prediction of inactivation in the completely mixed, flow-through reactor over a wide range of
contact time and u.v. absorbance using series-event kinetics. Q)--E. coil: Q - - C . parapsilosis: A--F2
bacterial virus; - - predicted from batch parameters.

problem is not the question. Rather, it is a constraint The act of photoreactivation can be viewed as in-
of the mathematics. The probability o.f events occur- creasing the survival of the reactivated culture by
ring in the series-event model, however, is not re- increasing the total damage the organisms can sustain
duced as the reaction proceeds due to the assumption prior to inactivation. This is equivalent to increasing
of the infinite availability of sites. In this regard, the the threshold value in the series-event model. How-
threshold value, n, is not under the same constraint ever, the kinetic constant, k, should still remain the
as n,., i.e. the threshold values is not the number of same for the two cultures.
available sites. It represents the number of sites which Stevens (1980) studied the photoreactivation of E.
must be destroyed before inactivation occurs. More coli using the same culture and same batch reactor
sites than the threshold number may be destroyed equipment used in this study. In his experiments, a
throughout the course of the reaction. This allows for culture of E. coli was irradiated with inactivating
a more flexible interpretation of the threshold than is light. Samples were collected after various exposure
possible for the critical target number. times of up to 80 s. Each sample was then divided
It is important to consider these observations in into two portions; one was exposed to photo-
relation to the known mechanisms of u.v. inac- reactivating light for 1 h while the second was kept in
tivation. The major biochemical reaction in u.v. the dark for l h prior to plating. These data are
irradiated organisms is thought to be the formation presented in Fig. 7. Both sets of data can be repre-
of cyclobutane dimers between intrastrand pyrim- sented with the series-event model by a kinetic con-
idine in nuclei acids (Smith and Hamawalt, 1969; stant of 0.88 x l0 -3 cm-' # W -~ s -t and threshold
Harms, 1980). Therefore, a large number of sites are values of 5 for the non-reactivated E. coli and 8 for
potentially available for reaction. However, there is photoreactivated E. coil with regression coefficients
no evidence that certain specific sites are required to (r 2) exceeding 0.993. The data of Stevens (1980) may
be destroyed prior to inactivation (Harms, 1980). also be analyzed using multi-target kinetics, in which
Both these observations are more in line with the case, the n u m b e r of critical targets is 19 for non-
series-event model than with the multi-target model. reactivated E. coli and 507 for photoreactivated E.
The more flexible nature of the threshold value coil However, in multi-target kinetics, it is assumed
over the critical target number lends itself to a test of that there is a finite number of critical sites and that
the two models. Many organisms have the ability to inactivation occurs upon the destruction of the last
repair u.v. inflicted damage. Culture conditions, both site. In the example given, therefore, the logic of the
prior to and after u.v. exposure, also can affect multi-target model is violated since it is impossible to
sensitivity. One such repair mechanism is photo- have 507 sites, as observed in the photoreactivation
reactivation, in which exposure to near u.v. light data, while only 19 existed in the analysis oF the
(340-380 nm) stimulates constitute enzymes to seek non-reactivation data.
and split thymine dimers. Presume that two organism One final difference between series-event and multi-
cultures are treated equivalently except for exposure target kinetics is the types of problems which each is
to near u.v. after initial exposure to u.v. at 254 nm. theoretically better adapted to solve. The series-event
Kinetic modeling of u.v. disinfection of v~ater 1677

rO as measured by u.v. absorbance of 254 nm. Excellent


predictions were obtained. In a comparison to the
multi-target model, the series-event model was tbund
to be superior because it better represents funda-
mental knowledge of the mechanism of u.v. inac-
tivation.
(3) It was shown previously (Severim 1982) that
ool
simple second-order inactivation kinetics were not
"6
>
adequate to relate the inactivation of E. co[i and C.
parapsilosis in batch and in a completely mixed,
~a 0 001 flow-through reactor. In fact, an inversion in the
g resistance of bacterial virus t"2 and C. parapilosis
occurred in the t~vo reactor systems. This inversion
ooool occurs because of the initial resistance of C. para-
U-
psilosis and the manner in which this resistance
impacts completely mixed flow-through reactor re-
sults. Simple second-order kinetics were unable to
00(X)OI
predict this inversion while multi-target kinetics and
series-event kinetics were able to predict this in-
version.
O000001 I (4) The analysis presented here show that two
0 20 40 60 80
kinetic models with dissimilar logic can be developed
Contact time (s) to fit batch data, and be extended to predict results
Fig. 7. Photoreactivation of E. coh in batch reztctors (after in a completely mixed flow-through reactor. There-
Ste,,ens, 1980). C)--No photorcactivation: O--with photo- fore, agreement between experimental data and
reactivation. model calculation does not provide proof that a
model is mechanistically correct. The important step
in scaling between reactor configurations appears to
model is better adapted to study the threshold efl'ect be the ability to mathematically describe the initial
on single organisms. The multi-target model is better resistance of organisms, which ultimately dominates
adapted for studying the effects of clumping of completely mixed flow-through reactor kinetics.
organisms, in which each organism acts as a single
target in a clump of many targets. Acknowledgement--The authors would like to thank
William W. Graessley, Senior Scientific Advisor, Exxon
Research & Engineering Co., Linden, NJ for valuable
CONCLUSION discussion.

(I) The multi-target model of inactivation has


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