~ 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

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

1669
I670 BLAINE F. 8EYERIN
still found general use ISmith and Hana~valt. 1969:
Harms, 1980) because of its simplicity of logic.
simplicit? of mathematics and ability to fit batch
data.
In this model, it is assumed that a particle contains
a finite number, n . of discrete critical targets, each of
which must be hit prior to full inactivation of the
particle. Since the number of targets is finite, the
probability of attaining a hit on the particle is
decreased as the reaction proceeds: i.e. since there are
fewer targets available as the reaction progresses, the
probability of attaining the next hit is decreased. A
particle may represent an organism with n,. targets or
a clump of organisms possessing a total of n c targets.
Due to the methods of enumeration used, however,
it is impossible to identify the difference in the
survival of a clump or an organism. Therefore, the
terms "'organisms" or "'particle" are used inter-
changeably in this presentation.
Application oJ multi-target kinetics to batch reactors
Batch u.v. inactivation data were collected in a
completely mixed, flat, thin-layer, closed-batch reac-
tor using water with high u.v. transmission. For such
a configuration, the u.v. intensity, I (/,~W cm 2), at all
points within the reactor may be assumed to be
uniform. Assuming that mixed second-order kinetics
describe the rate of inactivation of a critical target,
then probability, P(O), of a specific target surviving
attack is
P(0) = e -~"
and the probability of inactivating a specific target is
(1 - e -~") where k is a rate constant (cm-' I~W -~ s -~)
and t is the exposure time (s) to u.v. Assuming that
all targets are equivalent and that damage is ran-
domly distributed among the targets, then the proba-
bility of survival of a particle with n,. critical targets
is given by
N~
-- = 1 - (1 - e~") "'
Nt
where N, is the surviving organism density and N; is
the initial organism density.
Equation (2) may also be derived using a material
balance for a closed-batch reactor and the rate ex-
pression
r.,, = (n,. - i + t)klN,_ t - ( N , . - i)klN,
where r.,. is the rate of attaining the ith hit in a
particle and k represents the rate constant for at-
taining the last hit. The quantities ( n ~ - i + 1) and
(n,.- i) are probability factors applied to account for
the increased difficulty or specificity in hitting remain-
ing targets as the reaction proceeds. Equation (2) is
then obtained through sequential solution of equa-
tion (3) from i = 0 to i = n~ in the material balance
for a closed-batch reactor.
For a given value of kit, an increase in n~ results
in an increase in the surviving fraction of organisms.
et al.
To obtain values of nc and k from a set of data, the
intercept of a semi-log plot of surviving fraction vs t
gives n c. and the slope of the straight line segment is
- k l . However, since it is difficult to exactly deter-
mine the straight line portion of the curve from
experimental data, it is preferable to evaluate k and
n~ from a least-square fit of the data to equation (2).
Equation (2) is also applicable for describing u.v.
inactivation in plug-flow reactors with perfect cross-
flow mixing. In this instance, however, t is to be
replaced by z, the hydraulic detention time, and I is
to be replaced with the average intensity within the
reactor.
Application of the multi-target model to a mixed,
flow-through reactor o f annular design
A completely mixed, u.v. reactor of annular design
was employed to obtain continuous-flow inactivation
data. The light intensity in such a configuration is not
uniform. For modeling purposes, a radial approxi-
mation of an infinite line source was used to represent
the u.v. lamp where light is emitted radially from the
line and the intensity, L at a point at radial position
r, is given by the integrated form of Lambert's Law
(Jacob and Dranoff, 1966).
I = -l°r°
- e-2.303-i( . . . . . i (4)
r
where I0 is the intensity (uW) at the surface of the
quartz tube which separates the lamp from the water
in the reactor, r 0 (cm) is the outer radius of the quartz
(1)
tube, and A (cm-~) is the base 10 extinction coefficient
at 254 nm. A second, more complex model, the finite
length lamp model (Jacob and Dranoff, 1970) was
also investigated (Severin, 1982) and found not to
significantly alter the interpretation of inactivation
results.
The completely mixed, flow-through reactor model
is derived through the sequential solution of equation
(3) applied to the material balance for a completely
(2) mixed, flow-through reactor for i = 0 to i = n c which
yields the expression
~-~ imkloz
N, 1 (5)
NI t=l 1 + imkloz
where z is the hydraulic detention time in the reactor
and m is an intensity factor which represents the ratio
of the average intensity in the reactor to Io.
(3)
2r0 [l - exp(--2.303A (? - ro))]
m = (6)
2.303 A (?2 _ r0 )
The radius of the reactor is ? (cm). It is significant
that m arises directly from the integration of the point
reaction rate over the entire reactor rather than from
an a priori assumption that the average reaction rate
is properly defined by the average intensity.
SERIES-EVENT MODEL
A second approach to modeling u.v. inactivation is
 Kinetic modeling of u.v. disinfection of water
with series-event kinetics. An event is assumed to be
a unit of damage. Events occur in a stepwise fashion
and each step is assumed to be an integer function.
The rate at which an organism passes from one event
level to the next is first-order with respect to u.v.
intensity and independent of the event level occupied
by the organism. As long as an organism is exposed
to u.v. it continues to collect damage. However. a
threshold exists, whereby, organisms which have
reached an event level greater than the threshold are
inactivated, and all those which are below this level
survive. The threshold may vary depending on the
culturing conditions used. both prior to and after
irradiation: however for a given set of conditions, the
threshold level is constant. The above is expressed
as a series chemical reaction based upon single
organisms.
Mo2~ M,!£...M, ~ - L . . . M , _ ~ 3 k L M,3~t . . .
where k is the mixed, second-order reaction rate
constant (cm-' # W -~ s-~), l is the local point light
intensity (pWcm--'), M, is an organism which has
reached event level i, and n is the threshold level of
the organism.
Application o f the series-event model to batch reactors
For a batch reactor operated under the conditions
described earlier, the rate at which organisms pass
through event level i, r v,, (number cm -3 s -t) is given
by
r.~., = k i N i _ i -- k l N i .
Equation (8) is then incorporated into a material
balance for a batch reactor, and the resulting equa-
tion is solved sequentially from i = 0 to i = n - 1.
The general expression for the time-varying density
of organisms at any level i, N~, (number cm -3) is
given by
N, = N t ( k l t )i -~t,
- -
i.'
e (9)
where N, is the initial density of organisms prior to
exposure to u.v. light, and t is the exposure time (s)
to u.v. The density of surviving organisms N~, i.e.
those which have reached level n - 1 or less, is given
by
,,-I e -~t' ~+l (k[t)i
,v,= K ,v,.= N, ~ ,7
i=O i=0
Wei and Chang (1975) used an expression similar
to equation (10) to describe the inactivation of
clumps of organisms with chlorine. The n u m b e r of
organisms per clump that they observed was finite
and varied from 1 to 18. The use of equation (10) to
describe the data of Wei and Chang (1975), however,
is inappropriate since it embodies the assumption
that the occurrence of an event in a viable organism
is independent of the occurrence of previous events.
1671
When an event occurs in a d u m p . it is possible that
this event occurs in an organism which is alread? past
the threshold level, theretbre making the event useless
in terms of inactivating the clump. The experimental
system studied by Wei and Chang is more representa-
tive of multi-target kinetics. Equation (10) ~ould be
valid tbr describing the inactivation of clumps of
single-event organisms, providing the clump size was
infinitely large and the inactivation of only a few
organisms in a clump was adequate to inactivate the
entire clump. This, however, is not the case.
Equation (10) is also appropriate ['or describing the
inactivation efficiency of a plug-flow u.v. disinfection
process. In this instance, however, t is to be replaced
with the hydraulic detention time. r, and I is to be
replaced with the u.v. intensity averaged over the
cross-sectional area perpendicular to the flow.
Application o f the series-event model to el mLved,
(7) flow-thro,~gh reactor o J a n n u l a r design
The local rate at which organisms pass through
event level i, r~, is given by equation (81. where
equation (4) is substituted tbr I.
rA, =
kl°r°. e -_, ~o~r~..... ~(N, . I "%)" (I I)
r
Equation (11) is then incorporated into a material
balance for a completely mixed, flow-through reac-
tor, and the resulting equation is solved sequentially
from i = 0 to i = n - 1. The resulting general expres-
sion tbr the density of organisms that have reached
event level i, N~, is given by
(mkloz )7
(8) N, (1 + m k l o r y NI (12)
and the density of surviving organisms in the effluent,
N,, is then given by
,-i ,- i (mklor),
N,= ,=0
Z ,v,= X,=y_0
= (l+mk/0r) '~l'
{13)
Equation (13) can be rewritten in a closed form as
N~ l - [('F
1+ (13)
Equation (13) can be used to predict the performance
of any completely mixed, flow-through reactor: how-
ever, for general applications the quantity m l o should
be replaced by the average intensity within the reac-
tor.
" (1o)
EQUIPMENT AND PROCEDURES
Continuous flow disinfection data were developed
using a completely mixed, single lamp, annular reac-
tor (Fig. 1). This reactor was made from a 14.0cm
diameter (i.d.) Plexiglass column, 27cm in height.
The volume of the reactor, excluding the volume of
the quartz tube, was 4010 cm< A 2.54-cm diameter
(o.d.) quartz tube housed a General Electric Vohare
u.v.-LUX gl0T5½ low pressure mercury vapor lamp,
6"'-
~Q
T reactor was confirmed by showing that no gradients
Our et I OD v lorno
CD uClrt Z
CD
CD
OD OIO
:F,7.0c
•~ I--- r " 1 2 7 c m
Fig. 1. Completely mixed, flow-through u.v. reactor.
powered by a Universl M ~ . Co. (Patterson, N J)
Thermomatic-X fluorescent lamp d.c. ballast. Volt-
age (140 V) was supplied by a Variac voltage regu-
lator (General Radio Company, Concord, MA). The
inside wall of the reactor was painted lamp black to
minimize reflection. The incident light intensity at the
surface of the quartz tube (34,000bzWcm--') was
measured using the potassium ferrioxalate chemical
actinometry test (Calvert and Pitts, 1966). Complete
mixing in the reactor was achieved by the use of two
impeller systems placed on opposite sides of the
reactor. Each impeller shaft contained five, equally
spaced, three-bladed impellers. The shafts were
driven by Fisher Scientific (Chicago, IL) Dyna-mix
motors rated at 6000 rpm and operated at 85""/o of
capacity. The reactor was operated under a slight
head to eliminate free face vortexing. Flows could be
adjusted to provide retention times between 20 and
260 s.
Water used in the experiments with the flow-
through reactor was prepared in a 200 1. reservoir by
adding I I. of stock phosphate buffer solution (24 g
KH_,POa and 6 g N a O H per 1. stock) and appropriate
amounts of organism culture and u.v. light attenu-
ating agent to 200 1. DI water. The buffer maintained
the pH between 6.5 and 7.0. Organism densities in the
test water varied between 2 x 105 and 1 x 10~ colony
forming units (cful or plaque forming units (pfu) per
ml. The u.v. attenuating agent was para-
hydroxybenzoic acid (PHBA), which has a narrow
absorbance peak around 244 nm. P H B A was used to
simulate natural tannic acid components present in
wastewater. Quantities up to 500 ml of a stock P H B A
solution (10 g I -~) added to 200 1. DI water provided
a range of absorbances at 254 nm, ,4, between 0.04
and 2.2 c m - ~. The absorbance of the test water was
measured on an A C T A III Spectrophotometer (Beck-
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
of surviving organisms existed within the reactor
(Severin, 1982).
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
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
6 3 c m above the surface of the water. A shutter
arrangement was used to control exposure time. a
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-
rioxalate chemical actinometry test.
Test water used in the batch reactor was prepared
by adding 2.5 ml of stock phosphate buffer solution
and 500 ml DI water to the reactor. This solution was
then sterilized for 5 min with u.v. prior to the addi-
tion of organisms. The organism densities ranged
from 2 x l0 s to 1 x 106cfu or pfu ml -~ test water.
The pH of the water was between 6.5-7.0, and the
temperature of the water was 20 4- 1.0:C. No PHBA
was added to the water, and in all tests the u.v.
absorbance was below 0.04 cm-*. At this level, the
average intensity through the water column was
approx. 95~(, of the input energy flux at the water
surface.
A pure culture of Candida parapsilosis, isolated by
Engelbrecht et al. (1974), was maintained on refrig-
erated slants of yeast malt agar (YMA), prepared by
adding 3 g yeast extract, 3 g malt, 5 g peptone, 10 g
dextrose and 12g agar to 1 l. DI water. Inactivation
tests were performed on 20-24 h cultures of C. para-
psilosis grown in yeast malt broth ( Y M A without
agar) on a shaking water bath at 27 :C. The yeast was
enumerated using pour plates of Y M A . incubated for
3 days at 27:C.
A pure culture of E. toll, initially isolated From a
secondary wastewater effluent, was maintained on
refrigerated nutrient agar slants. Fresh cultures of E.
coli were grown at 37~C on a shaker water bath in
nutrient broth with 100 ppm by volume of "Tween
80" (Polyoxyethylene Sorbitan M o n o Oxylate; ICN
Pharmaceuticals, Inc., Cleveland, OH). a non-ionic
surfactant, added as an anticlumping agent. Cultures
grown for 20--24 h were used in the inactivation tests.
E. coli was enumerated using 20-24 h nutrient agar
pour plates incubated at 35°C.
Initial cultures of bacterial virus f2 and host or-
ganism E. coli K-13 were obtained from Vincent
Oliveri, The Johns Hopkins University, Baltimore,
MD. Bacterial virus f2 was cultured and enumerated
using a modification of the method described by Loeb
and Zinder (1961). Host cultures of E. coli K-13 were
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
shaking water bath. Stock virus suspensions were
prepared by the addition of the virus (0.1 infectively
ratio of virus to bacteria) to pregrown cultures of E.
coil K-13, having a density of approx. 3 x 10'~ bacte-
ria ml-L Alter lysis of the infected culture for 8-12 h
at 37~C on a shaking water bath, cell debris was
removed by centrifugation at 2500rpm for 15 min
(Sorval model GLC-2 lab centrifuge type HL-4 rotor
head, Sorval Inc., Newtown, CT). The supernatant
liquor, containing the virus stock, was maintained in
5 ml aliquots at 4~C. Virus density was determined
using an agar overlay method. TYE agar (10 g agar
I-~ TYE broth) plates and fresh cultures of host
bacteria were prepared in advance of testing. Just
prior to use, I ml of a sterile stock solution of calcium
chloride (22 g 1-~) was added to each 20 ml of host
bacteria culture. Three drops of the bacteria culture,
to provide a lawn of host cells, and 0.1 ml of a proper
dilution of virus suspension were then added to 3 ml
of melted TYE agar. This mixture was then poured
over a hardened agar plate. Plaques were counted
after 8-24 h incubation at 35~C.
RESULTS
Analysis with multi-target kinetics
Batch inactivation data are presented in Fig. 2. The
solid lines represent the least-square, best-fit of the
experimental data to equation (2). The best-fit values
of k and n, are presented in Table 1. The sum of
squares of deviation were calculated as the sum of the
squares of the differences between the natural loga-
rithms of the surviving fraction and the model solu-
tion. The search for the best-fit parameters was
initiated by assuming an integer values of n., then
determining the corresponding value of k which gave
the least sum of squares of deviation. Other integer
values of n,. were subsequently tested until a global
m i n i m u m was found. Both E. coli (201 hit) and C.
parapsilosis (1871 hit) appear initially resistant to u.v.
while bacterial virus f2 (single hit) is not. The obser-
vation that bacterial virus f2 is a single hit organism
is consistent with other observations with viruses with
single stranded nucleic acid (Harms, 1980).
Twenty-one experiments were performed using the
completely mixed, flow-through reactor; 6 with E.
toll, 9 with bacterial virus f2, and 6 with C. para-
psilosis. Experiments were performed by applying test
water to the reactor at various flow rates in order to
achieve contact times between 20 and 260 s. Each
experiment was performed using a water with
different u.v. absorbance. The range of absorbances
tested was from less than 0.02 to as high as 2.2 cm -~.
To test the applicability of the multi-target model
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-
diction [equation (5)] using the kine{ic parameters
from Table 1. Figure 3 shows the data for E. coli,
bacterial virus f2 and C. parapsilosis collected in
experiments using waters with no u.v. attenuating
agent added. The absorbances in these experiments
were 0.009, 0.003 and 0.020 cm -~, respectively. Solid
lines represent the predictions using the multi-target
model; generally good predictions are obtained.
More importantly, the batch data (Fig. 2) showed
that bacterial virus f2 is more resistant than C.
Analysis with series-event kinetics
Figure 5 shows the fit of the batch results as
analyzed with series-event kinetics. The solid lines
are the least square, best fit of the data to the
batch series-event model [equation (10)]. Kinetic par-
ameters were interpreted in a manner similar to that
described for multi-target analysis. The least square
best fit values of k and n are presented in Table 2. E.
coli shows an event level of 9, C. parapsilosis has an
event level of 15 and bacterial virus f2 is a single-
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.
Equation (13) indicates that the survival fraction,
Ns/N ~, is a function only of the dimensionless groups
mklor and n. It may be expected, therefore, that all
the data collected in the tests with the completely
mixed, flow-through reactor can be condensed onto
a single graph of three plots of Ns/N t vs mklor; one
plot for each organism since each organism exhibits
a different value of n. Figure 6 is a plot of fraction
survival vs mklor for all the flow-through reactor data
as analyzed using the series-event model, The solid
lines are the predicted results using equation (10) and
the best-fit value of n calculated from the batch data.
The points represent the observed fraction survivals
plotted vs mklor where m, I0 and ~ are experimentally
determined and k is the best-fit value from the batch
data. Excellent conformity between observed data
and the model solution is seen. The degree of scatter
is not uncommon for disinfection studies. In all three
cases, the correlation (r 2) of the data to the predic-
tions was in excess of 0.955. It is important to note
that series-event kinetics also predicts the inversion of
response of f2 virus and C. parapsilosis observed in
the two reactor situations.
Both multi-target and series-event kinetics have
been found useful in fitting batch u.v. inactivation.
The rate expressions for both models are easily
extended to completely mixed, flow-through reactor
configurations, and the kinetic parameters found
from batch data can be used successfully to predict
the efficiency of flow-through reactors. Outwardly
therefore, there appears to be little justification for
the preference of one model over the other. This leads
to the interesting point that two mechanistic models
cannot both be correct. Obviously, the ability of a
model to fit and predict experimental performance
does not lend absolute proof to the correctness of the
mechanism.
The major difference in the two models is the
mathematical preception of the targets or events. The
logic of the multi-target model necessitates that the
number of targets be finite and discrete, such that the
probability of attaining successive hits within an
organism is reduced as the number of available
targets is depleted. The number of critical targets, nc,
is the total extent to which an organism or particle
may be damaged since only nc targets exist. Whether
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
-°
"~ 001
o.oo J i [
0 I I, 0 I0
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
of the mathematics. The probability o.f events occur-
ring in the series-event model, however, is not re-
duced as the reaction proceeds due to the assumption
of the infinite availability of sites. In this regard, the
threshold value, n, is not under the same constraint
as n,., i.e. the threshold values is not the number of
available sites. It represents the number of sites which
must be destroyed before inactivation occurs. More
sites than the threshold number may be destroyed
throughout the course of the reaction. This allows for
a more flexible interpretation of the threshold than is
possible for the critical target number.
It is important to consider these observations in
relation to the known mechanisms of u.v. inac-
tivation. The major biochemical reaction in u.v.
irradiated organisms is thought to be the formation
of cyclobutane dimers between intrastrand pyrim-
idine in nuclei acids (Smith and Hamawalt, 1969;
Harms, 1980). Therefore, a large number of sites are
potentially available for reaction. However, there is
no evidence that certain specific sites are required to
be destroyed prior to inactivation (Harms, 1980).
Both these observations are more in line with the
series-event model than with the multi-target model.
The more flexible nature of the threshold value
over the critical target number lends itself to a test of
the two models. Many organisms have the ability to
repair u.v. inflicted damage. Culture conditions, both
prior to and after u.v. exposure, also can affect
sensitivity. One such repair mechanism is photo-
reactivation, in which exposure to near u.v. light
(340-380 nm) stimulates constitute enzymes to seek
and split thymine dimers. Presume that two organism
cultures are treated equivalently except for exposure
to near u.v. after initial exposure to u.v. at 254 nm.
"..
= o'-,% _
. vjo',<...
• n=15
A r]:9 O0
r] =
I
I00 I000 I0,000
KI ° T
The act of photoreactivation can be viewed as in-
creasing the survival of the reactivated culture by
increasing the total damage the organisms can sustain
prior to inactivation. This is equivalent to increasing
the threshold value in the series-event model. How-
ever, the kinetic constant, k, should still remain the
same for the two cultures.
Stevens (1980) studied the photoreactivation of E.
coli using the same culture and same batch reactor
equipment used in this study. In his experiments, a
culture of E. coli was irradiated with inactivating
light. Samples were collected after various exposure
times of up to 80 s. Each sample was then divided
into two portions; one was exposed to photo-
reactivating light for 1 h while the second was kept in
the dark for l h prior to plating. These data are
presented in Fig. 7. Both sets of data can be repre-
sented with the series-event model by a kinetic con-
stant of 0.88 x l0 -3 cm-' # W -~ s -t and threshold
values of 5 for the non-reactivated E. coli and 8 for
photoreactivated E. coil with regression coefficients
(r 2) exceeding 0.993. The data of Stevens (1980) may
also be analyzed using multi-target kinetics, in which
case, the n u m b e r of critical targets is 19 for non-
reactivated E. coli and 507 for photoreactivated E.
coil However, in multi-target kinetics, it is assumed
that there is a finite number of critical sites and that
inactivation occurs upon the destruction of the last
site. In the example given, therefore, the logic of the
multi-target model is violated since it is impossible to
have 507 sites, as observed in the photoreactivation
data, while only 19 existed in the analysis oF the
non-reactivation data.
One final difference between series-event and multi-
target kinetics is the types of problems which each is
theoretically better adapted to solve. The series-event
 Kinetic modeling of u.v. disinfection of v~ater
rO
ool
"6
>
~a 0 001
g resistance of bacterial virus t"2 and C. parapilosis
ooool
U-
00(X)OI
O000001
0 20 40 60
Contact time (s)
Fig. 7. Photoreactivation of E. coh in batch reztctors (after
Ste,,ens, 1980). C)--No photorcactivation: O--with photo-
reactivation.
model is better adapted to study the threshold efl'ect
on single organisms. The multi-target model is better
adapted for studying the effects of clumping of
organisms, in which each organism acts as a single
target in a clump of many targets.
CONCLUSION
(I) The multi-target model of inactivation has
been applied to closed-batch u.v. inactivation results
with E. toll, C. parapsilosis, and bacterial virus f2.
The logic of the model has been extended to a
completely mixed, flow-through reactor of annular
design. Model kinetic parameters obtained from the
batch data were applied to the equation for the
completely mixed, flow-through reactor system. Ex-
cellent predictions were obtained for flow-through
reactor data collected over a wide range of contact
times and in waters with a wide range of u.v. absorb-
ances. While the model is not entirely consistent with
the information available on the mechanism of u.v.
inactivation, it is important that the mathematics can
be used in a predictive mode with different reactor
configurations.
(2) The series-event model of u.v. inactivation has
been presented and equations developed for closed
batch and completely mixed, flow-through reactors of
annular design. Kinetic parameters developed from
batch data in clean water were used to predict the
response of the three test organisms in the
flow-through reactor operated over a wide range of
contact times and using a wide range of water quality
1677
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
simple second-order inactivation kinetics were not
adequate to relate the inactivation of E. co[i and C.
parapsilosis in batch and in a completely mixed,
flow-through reactor. In fact, an inversion in the
occurred in the t~vo reactor systems. This inversion
occurs because of the initial resistance of C. para-
psilosis and the manner in which this resistance
impacts completely mixed flow-through reactor re-
sults. Simple second-order kinetics were unable to
predict this inversion while multi-target kinetics and
series-event kinetics were able to predict this in-
version.
I (4) The analysis presented here show that two
80
kinetic models with dissimilar logic can be developed
to fit batch data, and be extended to predict results
in a completely mixed flow-through reactor. There-
fore, agreement between experimental data and
model calculation does not provide proof that a
model is mechanistically correct. The important step
in scaling between reactor configurations appears to
be the ability to mathematically describe the initial
resistance of organisms, which ultimately dominates
completely mixed flow-through reactor kinetics.
Acknowledgement--The authors would like to thank
William W. Graessley, Senior Scientific Advisor, Exxon
Research & Engineering Co., Linden, NJ for valuable
discussion.
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