Zebra mussel

mortality with chlorine

A kinetic model allows prediction
of the mortality of zebra mussels
as a function of chlorine

S
concentration, temperature,
and contact time.

John E. Van Benschoten, ince the introduction of the zebra

James N. Jensen, mussel (Dreissena polymorpha) into North America, an
Donald Harrington, extensive effort has been undertaken to identify meth-
ods to minimize or eliminate the impact of this organ-
and Daniel J. DeGirolamo ism . Th e poten tial for adverse effects from th e colo-
nization of the zebra mussel on engineered structures
h as becom e a con cern at m an y m u n icipal an d in du s-
trial facilities th at u se fresh water. Man y water treat-
m en t plan ts an d power plan ts th rou gh ou t th e Great
Lakes region h ave experien ced n egative effects from
m u ssel colon ization , in clu din g decreased h ydrau lic
capacity 1 an d fou lin g of trash bars, screen h ou ses,
steam condensers, heat exchangers, and service water
system s.2 Zebra m u ssel colon ization h as also resu lted
in in creased operation an d m ain ten an ce costs for
m an y m u n icipal an d in du strial water u sers.
Ch em ical con trol m eth ods u sin g oxidan ts an d
nonoxidizing biocides are
cu rren tly bein g u sed to
The rate of mortality of the zebra mussel in response to chlorine co n t r o l ze br a m u sse ls.
is described by a kinetic model that combines a statistical Com m on oxidan ts su ch
characterization of mussel mortality with a disinfection-type as ch lorin e, m on och lor-
modeling approach. Parameter estimates were made with nine am in e, ch lorin e dioxide,
sets of data from experiments conducted in Niagara River water. permanganate, and ozone
From the kinetic model, an operational diagram was constructed h ave been u sed for disin -
that describes the time to 95 percent mortality as a function of fe ct io n a n d bio fo u lin g
chlorine concentration and temperature. Either the model or the con trol an d are bein g in -
diagram can be used to assist utilities in planning chlorination vestigated for u se in con -
treatments for controlling zebra mussels. t r o llin g ze br a m u sse ls.
Ch lorin e is kn own to be

(C) 1995 American Water Works Association

MAY 1 9 9 5 101
 Experimental methods
TABLE 1 Summary of zebra mussel mortality data Toxicity tests w ere con -
Residual
du cted in con tin u ou s-flow
Chlorine reactors u sin g Niagara River
Temperature Concentration w ater. Details of th e stu dy
Mean ± Mean ± Fitted Parameters
Standard Standard m eth ods are reported else-
Deviation (n)* Deviation (n) µ s LT95 w h ere. 6 A su m m ary of th e
oC mg/L days days n’† r2 days ge n e r a l t e st p r o ce d u r e s is
1 .4 ± 1 .6 (3 5 ) 1 .0 ± 0 .5 (3 6 ) 3 5 .2 2 2 .6 10 0 .4 4 72 given in th is section .
1 .1 ± 1 .4 (3 2 ) 2 .1 ± 0 .1 (3 2 ) 1 5 .2 8 .0 2 10 0 .7 6 28 Stu dies w ere con du cted
0 .3 ± 0 .2 (2 1 ) 3 .0 ± 0 .1 (2 3 ) 1 3 .0 6 .8 5 11 0 .7 1 24
1 1 .5 ± 1 .7 (2 7 ) 0 .2 ± 0 .0 4 (1 8 ) 2 7 .7 9 .8 4 11 0 .9 5 44
a t t h e Er ie Co u n t y Wa t e r
1 1 .5 ± 1 .7 (2 7 ) 0 .5 ± 0 .0 3 (1 6 ) 2 2 .2 1 1 .8 11 0 .8 3 42 Au t h o r it y’s Va n d e Wa t e r
1 1 .5 ± 1 .7 (2 7 ) 1 .0 ± 0 .1 (1 8 ) 1 3 .1 5 .9 9 12 0 .9 4 23 t r e a t m e n t p la n t in To n a -
1 9 .7 ± 0 .6 7 (9 ) 0 .5 ± 0 .1 (9 ) 6 .1 3 1 .7 0 9 0 .9 8 8 .9
2 0 .1 ± 0 .1 (8 ) 1 .0 ± 0 .2 (1 7 ) 3 .6 6 0 .9 2 3 8 0 .9 7 5 .2
w a n d a , N.Y. Th is fa cilit y
2 3 .9 ± 0 .2 (7 ) 0 .9 2 ± 0 .0 6 (6 ) 5 .0 6 1 .3 0 6 0 .9 2 7 .2 receives its raw w ater from
* n = numbe r o f me as ure me nts
th e Niagara River. Th e Nia-
† n’ = numbe r o f data po ints in fitting pro c e dure ga r a Rive r h a s be e n co lo -
n ized by zebra m u ssels sin ce
a bo u t 1 9 9 0 . Te st r e a ct o r s
w ere co n t in u o u s- flo w
effective in con trollin g zebra m u ssels an d is bein g stirred-tan k reactors fabricated from clear acrylic.
u sed widely for th is pu rpose. Th e test reactors w ere 7.4-L capacity an d operated
Upon exposu re to ch lorin e or an oth er oxidan t, at a flow rate of approxim ately 1.0 L/ m in . Ch lorin e
m u ssels u su ally close th eir sh ells becau se th ey are was pumped from stock hypochlorite solutions to the
reported to be capable of detectin g as little as 0.04 test reactors th rou gh a tee in th e in flu en t lin e to
m g/ L total residu al oxidan t.3 Typically, closu re peri- th e reactors. Adu lt zebra m u ssels (> 10-m m sh ell
ods in crease with oxidan t con cen tration , alth ou gh len gth ) w ere con tain ed eith er in test vials m ade by
sh ort in tervals of valve movemen t are reported.3,4 At perforatin g 100-m L plastic bottles6 or in plastic m esh
con cen tration s of total residu al oxidan t > 0.5 m g/ L, baskets. 7 In eith er case, tracer stu dies w ere con -
m u ssels are reported to be closed n early
all th e tim e. 3 Du rin g ch lorin ation zebra
m u ssels typically exh ibit a lag period FIGURE 1 Observed zebra mussel mortality (symbols) and fitted
prior to th e on set of m ortality. In a syn - data (lines) using the normal cumulative normal
th esis of laboratory an d field stu dies of distribution function
th e u se of ch em ical oxidan ts for con -
trollin g zebra m u ssels, Van Ben sch oten
et al5 reported lag periods ran gin g from 100
two to eigh teen days.
With th e con tin u ed spread of th e
zebra m u ssel in Nor th Am erica, th e
m ost often asked qu estion s regardin g 80
con trol of zebra m u ssels con cern th e
dosage of ch lorin e th at sh ou ld be u sed
an d th e len gth of tim e ch lorin e m u st
Mortality—percent

60
be added to effectively kill th e m u ssels.
For w aters in w h ich prech lorin ation
fo r ze b r a m u sse l co n t r o l r e su lt s in
in creased ch lorin ation by-produ ct for- 40
m ation , it is particu larly im portan t to
m in im ize th e u se of ch lorin e wh ile still
m ain ta in in g effe ctive con tr ol o f th e
zebra m u ssel. 20
This study
Th e specific objectives of th is stu dy Jenner and Janssen-Mommen
17

were to: (1) develop a kin etic m odel to Klerks and Fraleigh
16

qu an tify th e effects of ch lorin e dosage,

0
con tact tim e, an d tem peratu re on zebra
mussel mortality; (2) test the model using 0 10 20 30 40 50 60 70
experim en tal data; an d (3) apply th e
m odel to develop gu idelin es for im ple- Time—days
menting chlorination programs to control
zebra m u ssels.

(C) 1995 American Water Works Association

102 JOURNAL AWWA

du cted to verify u n in h ibited flow. Pu lse in pu ts of
m eth ylen e blu e dye w ere m ade to th e reactors an d
from th e resu ltin g con cen tration -versu s-tim e data
th e residen ce tim e distribu tion (E cu rve) w as cal-
cu lated an d com pared with a th eoretical com pletely
m ixed reactor. Th e experim en tal reactors closely
a p p r o x im a te d id e a l co m p le te ly m ix e d re a ct o r s.
Approxim ately 100 adu lt m u ssels were divided in to
sam ples of 10 m u ssels each an d w ere placed in th e
test reactors. Mu ssels w ere allow ed to acclim ate in
th e n on ch lorin ated test reactor for approxim ately
24 h . Du rin g th e experim en ts, su bsam ples w ere
with drawn periodically an d placed in u n ch lorin ated
w ater for 24–48 h , th en m ortality w as determ in ed.
On ly m in or differen ces in m ortality w ere n oted for
recovery periods > 24 h . 7 Sam ples w ere collected
at in tervals su ch th at a com plete m ortality cu rve
cou ld be determ in ed. Th u s, sam ple collection tim es
varied between experim en ts, depen din g on th e rate
of m u ssel m ortality. For th e m ortality assessm en t,
m u ssels th at exh ibited valve m ovem en t or filter
feedin g w ere scored as alive; gaped m u ssels th at
sh ow ed n o respon se to gen tle probin g w ere scored
as dead. Alth ou gh th e sh ells of som e m u ssels w ere
closed, m akin g m ortality determ in ation s am bigu -
ou s, con tin u ed observation of th ese m u ssels u su -
ally resu lted in a clear m ortality determ in ation
becau se live m u ssels even tu ally sh owed som e valve
m ovem en t or feedin g activity. Con trol reactors (n o
ch lorin e added) were operated in parallel with reac-
tors receivin g ch lorin e. Th e h igh est m ortality ob-
served from an y of th e con trol reactors in all th e
experim en ts w as approxim ately 15 percen t, an d in
m a n y ca se s n o m o rt a lit y w a s o bse rve d . Co n se-
qu en tly, m ortality data w ere n ot corrected for con -
trol m ortality. Residu al ch lorin e con cen tration s an d
w ater tem peratu res du rin g th e experim en ts are
sh ow n in Table 1.
An am perom etric ch lorin e an alyzer* was u sed to
m easu re th e total ch lorin e residu al in th e efflu en t
of each test reactor. Becau se th e am perom etric an a-
lyzer was sen sitive to ch an ges in tu rbidity, a colori-
m etric an alyzer† was u sed as an altern ative m eth od
to m easu re total ch lorin e residu al. For several exper-
(C) 1995 American Water Works Association
Zebra mussels im en ts, th e DPD m eth -
colonize on artificial
od 8 was u sed to m easu re
structures as easily
as on living ones
total ch lorin e residu al.
and have become
a concern for many Analysis of
utilities. mortality data
Cu m u lative m ortal-
ity-versu s-tim e plots are
o ft e n sigm o id a l 9 a n d
som etim es are an alyzed by m eth ods based
on th e cu m u lative n orm al distribu tion (e.g.,
probit an alysis). Fraction m ortality, expressed
as a cu m u lative n orm al distribu tion , is de-
fin ed as:
t
(1/ s 2p) e e – {[t–µ ]
2
/ 2s2 } dt
0
Th e cu m u lative distribu tion is defin ed by tw o
param eters, µ an d s. Alth ou gh m eth ods su ch as pro-
bit an alysis attem pt to lin earize m ortality data an d
th en fit th e two popu lation param eters, in th is stu dy
µ an d s were fit directly to m ortality data u sin g th e
cumulative normal distribution function (normdist) in
the spreadsheet EXCEL. The Solver function then was
u sed to m in im ize th e error su m of squ ares between
observed an d fitted data. Aside from sim plicity, an
advan tage of th is m eth od over probit an alysis is th at
0 and 100 percent mortality data can be used in the fit-
ting procedure because no transformations of the raw
data are requ ired. Th e tim e to 50 percen t m ortality
(i.e., LT50 ) is equ al to µ . Tim es to 95 percen t m ortal-
ity (i.e., LT95 ) were calcu lated based on th e fitted val-
ues of µ and s. Fitted values of µ and s were observed
to be correlated an d cou ld be described by Eq 2:
s = a µb (2)
in wh ich a an d b are em pirical con stan ts.
Kinetic modeling
Alth ou gh fittin g experim en tal data to a cu m u la-
tive normal distribution provides a convenient means
of ch aracterizin g m ortality data, it provides little
in sigh t to factors affectin g zebra m u ssel m ortality
(e.g., con cen tration an d tem peratu re). It h as been
sh own previou sly 5 th at disin fection m odels m ay be
useful in describing zebra mussel mortality. However,
plots of ln N/N0 versu s tim e u su ally are n ot lin ear
an d often exh ibit an in itial lag or sh ou lderin g ph e-
n om en on (N an d N0 are th e n u m ber of m u ssels su r-
vivin g at an y tim e an d th e in itial n u m ber of m u s-
se ls, r e sp e ct ive ly) . Th is p h e n o m e n o n h a s be e n
observed in th e m ortality of m icrobial clu m ps10 an d
m u lticellu lar organ ism s.11
Alth ou gh sim ple kin etic m odels can n ot describe
com plete zebra m u ssel m ortality cu rves, Van Ben -
schoten et al5 showed that logarithmic plots of oxidant
con cen tration versu s th e tim e to 50 percen t m ortal-
*Model 1870 Residu al An alyzer/ Mon itor, Capital Con trols Co., Col-
m ar, Pa.
†Model DR/ 700, Hach Co., Lovelan d, Colo.
MAY 1 9 9 5 103
 ity were lin ear in accordan ce with a sim -
FIGURE 2 Logarithmic plot of chlorine concentration versus LT50 p le d isin fe ct io n m o d e lin g a p p r o a ch .
for mortality data in three temperature ranges Accordin g to th e Ch ick–Watson law:

dN/ dt = – k C n N (3)
10.0
in wh ich N is th e n u m ber of m u ssels, k =
rate con stan t ([m g/ L] -1 day -1 ), C = ch lo-
rin e con cen tration (m g/ L), an d n = con -
stan t. In tegratin g Eq 3 betw een lim its
Chlorine Concentration—mg/L Cl2

from N0 to N at tim es t = 0 to t, respec-

tively, yields:

o
0.3–1.4 C ln N/N0 = – k C n t (4)
1.0
The time to 50 percent mortality (LT50 ) is
calcu lated by rearran gem en t of Eq 4:

o LT50 = 0.693/ k C n (5)

20–24 C

o
11.5 C
No t e t h a t a lo ga r it h m ic p lo t o f Eq 5
sh ou ld be lin ear with a slope = –n.
Assu m in g th e effect of tem peratu re
can be described by th e Arrh en iu s equ a-
0.1 tion , Eq 5 can be rewritten as:
1 10 100
LT50 = k’ exp {Ea/R [(1/ 273.15)
LT50—days
+ T – 1/ 293.15]} C–n (6)

in wh ich k’ = 0.693/ k20 , k20 = rate con -

stant at 20 oC, Ea = activation energy (kcal
m ol-1 ), R = gas con stan t (1.987 ˘ 10 –3
FIGURE 3 Fitted versus observed mortality values kcal K-1 mol-1), and T = temperature (oC).
To u se Eq 6 to describe m ortality at an y
tim e, it was h ypoth esized th at valu es of
80
µ obtain ed in th e an alysis of m ortality
LT50 data cou ld be fit to Eq 6 becau se LT50 =
µ . Th e co n st a n t s k’, E a , a n d n w e r e
LT95
adju sted to m in im ize th e su m of squ ares
60
betw een observed an d calcu lated LT50
valu es. From Eq 6, µ can be predicted
based on tem peratu re an d ch lorin e con -
Fitted Mortality—days

centration. Eq 2 then can be used to pre-

dict s. With estim ated valu es of µ an d
40 s, tim es to 95 percen t m ortality (i.e.,
LT95) were predicted using Eq 1 and com-
pared with experim en tal data.

Results
20 Analysis of mortality data. Zebra
m u ssel m ortality data fit to th e cu m u la-
tive n orm al distribu tion for th ree data
sets are sh own in Figu re 1. As LT50 val-
u es in crease, th e cu rves flatten , su ggest-
0 in g th at for zebra m u ssel m ortality data,
0 20 40 60 80 a possible relation sh ip between µ an d s
Observed Mortality—days m ay exist. Th e cu m u lative distribu tion
Fitted LT50 values calculated using Eq 6; fitted LT95 values based on ten ds to overestim ate m ortality at low
Eqs 2 and 6; line is fitted = observed m ortality levels, especially at larger LT50
valu es, bu t appears to accu rately m atch
th e m ortality cu rves at h igh er m ortality.

(C) 1995 American Water Works Association

104 JOURNAL AWWA
From a practical standpoint, errors at low
mortality are of little significance because FIGURE 4 Correlation between s and µ for mussel mortality data
estimating total treatment time (i.e., time
to a h igh level of m ortality) is of m ost
in terest. 40
Experiment. Tem peratu re an d ch lo-
rin e su m m ary statistics are sh ow n in
Table 1. Variability in temperature some-
times was considerable. For example, the 30
study with a mean temperature of 11.5 oC

Standard Deviation—days
was conducted during a period when the
Niagara River decreased in tem peratu re
from 14 to 9 o C, resu ltin g in a relatively
large stan dard deviation of 1.7 o C. All 20
experiments from this study reflect ambi-
en t tem peratu res in th e Niagara River.
Ch lorin e residu al statistics sh ow m oder-
ate variability with relative standard devi-
10
ation s (RSD/ m ean ) gen erally 20 percen t
or less. Variation s in ch lorin e con cen tra-
tion s reflect th e com bin ed variability in
chlorine feed equipment, analytical error,
an d variation s in raw -w ater flow an d 0
qu ality (e.g., ch lorin e dem an d). Also 0 10 20 30 40
sh own in Table 1 are th e resu lts of fit-
tin g th e m ortality data to th e cu m u la- LT50—days
1.3
tive n orm al distribu tion . Th e r 2 valu es Line is σ = 0.2 µ
are gen erally good except for experi-
m en ts con du cted at tem peratu res < 5 o C.
In th ese experim en ts, com plete m ortal-
ity did n ot occu r, even th ou gh th e experim en ts were dan ce with th e Ch ick–Watson law (see Eq 5). Th e
con du cted for >30 days. Alth ou gh th e experim en tal slopes of th e regression lin es are < –1 (–1.03 to –2.0),
resu lts from th is stu dy were u n replicated, addition al in dicatin g n < 1 for a Ch ick–Watson -type disin fec-
stu dies h ave sh own th at variability in zebra m u ssel tion m odel.
m ortality cu rves is greatest at in term ediate m ortality Kinetic modeling. A plot of fitted valu es of LT50
an d lower at both low an d h igh m ortality.12 Becau se u sin g Eq 6 versu s observed data for all n in e data sets
th e cold tem peratu re stu dies ach ieved on ly in term e- is sh own in Figu re 3. Th e solid lin e in Figu re 3 sh ows
diate m ortality levels, th e h igh er variability in th esea 1:1 correspon den ce between fitted an d observed
data. Th e data fit is good (r2
= 0.89) with a standard error

T
of 3.6 days. Th e fitted con -
stan ts w ere k’ = 4.63 (k =
he effect of temperature on zebra mussel 0.15 [m g/ L] -1 day -1 ), E a =
mortality in the presence of chlorine 16.5 kcal/ m ol, an d n = 0.71.
The relationship between
is significant. th e popu lation param eters
µ (LT50 ) an d s is sh own in
Figu re 4. Th ere is an obvi-
experim en ts resu lted in a poorer fit of th e m odel to ou s positive correlation betw een th ese param eters
the data. Also shown in Table 1 are the LT95 values for for th e zebra m u ssel m ortality data. Th e solid lin e in
each of th e experim en ts calcu lated u sin g th e fitted Figure 4 was fit using Eq 2 with fitted values of a = 0.2
valu es of µ an d s an d Eq 1. an d b = 1.3. LT95 valu es were predicted u sin g th e fit-
Effects of tem peratu re an d ch lorin e con cen tra- ted con stan ts from Eqs 2 an d 6 an d were com pared
tion on LT50 valu es are sh own in Figu re 2 in wh ich w ith m easu red data (Figu re 3). Th e kin etic m odel
data collected at similar temperatures have been com- appears to describe th e experim en tal data reason ably
bin ed. Th e separation of th e regression lin es for th e well (r2 = 0.82, stan dard error = 9.1 days).
temperature ranges shown and the negative slopes for
each of th e regression lin es in dicate th at mu ssel mor- Discussion
tality depen ds stron gly on tem peratu re an d also on Th e effectiven ess of ch lorin e in con trollin g zebra
ch lorin e con cen tration . At each tem peratu re, th e m u ssels is a fu n ction of ch lorin e con cen tration , tem -
log–log plots of the data are reasonably linear in accor- pe r atu re , a n d co n ta ct tim e . A kin e tic m o d e lin g

(C) 1995 American Water Works Association

MAY 1 9 9 5 105
 approach was developed that allows pre-
FIGURE 5 Predicted versus observed LT50 values using Eq 6 for diction of zebra m u ssel m ortality as a
data from Table 2 fu n ction of th ese variables. Th e kin etic
m odel is based on both th e cu m u lative
n orm al distribu tion to fit m ortality data
70 a n d a d isin fe ct io n k in e t ic m o d e lin g
approach as a means of incorporating the
16
Klerks and Fraleigh (free Cl2)
effects of concentration and temperature.
60 16
Klerks and Fraleigh (total Cl2) Becau se of th e lag tim e observed w ith
Jenner and Janssen-Mommen
17
zebra m u ssel m ortality, a sim ple kin etic
18
50
Martin et al
7
m odel su ch as th e Ch ick–Watson law
University at Buffalo (0.75–2 mm) cannot accurately describe mortality data.
LT50 Predicted—days

7
University at Buffalo (2.5–5 mm)
Altern atives to th e Ch ick–Watson law
40 h ave been proposed to accou n t for a lag
(or tailin g) in m ortality data. For exam -
ple, Hom ’s m odel13 is sh own in Eq 7:
30

ln N/N0 = – k C n t m (7)
20
Th e valu e of m determ in es if th e m odel
describes a lag (m > 1) or tailin g off (m <
10 1) in m ortality data. Alth ou gh th e Hom
model can be used to fit mortality data at
0
a given con cen tration an d tem peratu re,
0 10 20 30 40 50 60 70
it was found that values of m were a func-
tion of con cen tration an d tem peratu re
LT50 —days
for th e zebra m u ssel m ortality data. Th at
is, th is m odelin g approach cou ld n ot
describe all th e data with on e set of con -
stan ts, even w h en expressin g th e rate
con stan t by th e Arrh en iu s law.
FIGURE 6 Operational diagram for the time to 95 percent mortality Th e ability of th e proposed m odel to
as a function of temperature and total residual chlorine describe the lag observed in mussel mor-
concentration tality is accou n ted for by th e popu lation
param eter s, wh ich was described as a
fu n ction of µ . Becau se µ was a fu n ction
100 of concentration and temperature, s also
varied as a fu n ction of th ese param eters.
Aside from th e fact th at th e system atic
variation of s with µ provides a con ve-
80
n ien t m ean s of ch aracterizin g m u ssel
m ortality data, it is also of som e opera-
tion al sign ifican ce. For exam ple, an y
Predicted LT95—days

60
strategies that involve low mortality rates
(e.g., low con cen tration or tem peratu re
con dition s) w ill also resu lt in larger s
valu es, an d con sequ en tly ch lorin e addi-
40 tion and monitoring should be exten ded
for lon ger periods to en su re th at a satis-
2.0 1.0 0.5 0.25 factory m ortality level is ach ieved.
Th e effect of tem peratu re on zebra
20 mussel mortality in the presence of chlo-
rin e is sign ifican t. Th e activation en ergy
of 16.5 kcal/ m ol calcu lated in th is work
is at th e u pper en d of activation en er-
0 gies reported for m icroorgan ism s su ch
0 5 10 15 20 25 as Escherichia coli an d polioviru s, wh ich
o
Temperature— C ran ge from 6 to 20 kcal/ m ol. 14,15 Bio-
Values at lines indicate milligrams per litre of total residual chlorine logical reaction s often u n dergo a dou -
blin g in th e rate with a 10 o C in crease in
tem peratu re. Usin g th e Arrh en iu s equ a-

(C) 1995 American Water Works Association

106 JOURNAL AWWA
 TABLE 2 Mussel mortality data used for model prediction

Chlorine LT50 LT50

Temperature Concentration Observed Predicted
oC mg/L days days Comments Source

1 1 .1 0 .0 8 / 0 .3 2 5 3 .7 68/ 25 Te mpe rature and Cl2 c o nc e ntratio n Kle rks and Frale igh1 6
1 1 .1 0 .2 6 / 0 .6 2 3 1 .9 29/ 16 are me an value s , 1 4 –1 6 -mm
1 1 .1 1 .3 5 / 1 .7 4 1 6 .3 9 .1 / 7 .6 mus s e ls , Cl2 c o nc e ntratio n and
8 .1 3 .1 7 / 4 .3 1 2 4 .4 6 .7 / 5 .4 LT5 0 value s are fo r fre e / to tal Cl2
8 .1 7 .5 9 / 9 .0 2 1 9 .5 3 .6 / 3 .2
1 2 –1 5 0 .2 5 2 3 .4 2 3 .6 Expe rime ntal me tho ds no t re po rte d Je nne r and Jans s e n-Mo mme n 1 7
1 2 –1 5 0 .5 1 4 .1 1 4 .4
1 2 –1 5 1 .0 8 .5 8 .8
12 1 15 1 0 .2 3 –7 -mm mus s e ls , o bs e rve d LT5 0 Martin e t al1 8
12 2 .5 10 5 .3 value s appro ximate
12 5 6 3 .2
12 8 4 2 .3
9 .6 1 .0 1 4 .1 1 2 .9 0 .7 5 –2 -mm mus s e ls State Unive rs ity o f Ne w Yo rk
9 .6 1 .0 2 5 .7 1 2 .9 2 .5 –5 -mm mus s e ls at Buffalo , unpublis he d data 7

tion , a dou blin g of th e rate con stan t for a ch an ge in
tem peratu re from 10 to 20 o C correspon ds to an acti-
vation en ergy of 11.4 kcal/ m ol. For an activation
en ergy of 16.5 kcal/ m ol, n early a th reefold in crease
in the rate would be observed with a 10 o C increase in
tem peratu re (10 to 20 o C).
To test th e gen erality of th e m odel, several data
sets from th e literatu re were com piled an d u sed for
m odel testin g. A su m m ary of th ese data is given in
Table 2. Observed an d predicted LT50 valu es from
Table 2 are plotted in Figu re 5. Alth ou gh th e m odel
was developed u sin g total ch lorin e residu al con cen -
trations, the data of Klerks and Fraleigh 16 show much
better agreem en t with th e m odel prediction wh en
observed data. Somewhat surprisingly, predicted LT50
valu es are less th an observed. Becau se m etabolic
rates for sm aller organ ism s u su ally are m ore rapid
th an for larger an im als, larger predicted LT50 valu es
th an observed m igh t h ave been expected. For adu lt
m u ssels, it h as been sh ow n th at m u ssel m ortality
was sim ilar for th e followin g size ran ges: 6–12 m m ,
14–18 m m , an d 19–24 m m .7
Th e proposed kin etic m odel was u sed to produ ce
an operation al diagram for con trollin g zebra m u ssels
(Figu re 6) in wh ich tim es to 95 percen t m ortality are
sh own as a fu n ction of water tem peratu re an d ch lo-
rine dosage. The strong effect of temperature is appar-
en t. From an operation al perspective, it appears th at
ch lorin ation < 10 o C m ay

R
not be practical because the
tim e requ ired at ch lorin e
dosage # 1 m g/ L will be >
aw-water quality characteristics may be 20 days. In term s of total
ch lo r in e u se , t h e fit t e d
important in affecting mussel mortality. valu e of n = 0.73 im plies
th at w ith low er ch lorin e
co n ce n t r a t io n s t h e t o t a l
am ou n t of ch lorin e n eeded
free residu al ch lorin e data are u sed. On e reason for is less. Similar observations have been made by Klerks
th is differen ce m ay be th at th e ratio of free to total an d Fraleigh ,16 Jen n er an d Jan ssen -Mom m en ,3 an d
ch lorin e in th e experim en ts reported by Klerks an d Van Ben sch oten et al. 5 Alth ou gh lower con cen tra-
Fraleigh is less th an observed in Niagara River water. tion s redu ce th e total am ou n t of ch lorin e n eeded,
For exam ple, at a dose of 0.5 m g/ L, Klerks an d the longer mortality times and correspondingly larger
Fraleigh 16 report a free-to-total-ch lorin e ratio of 0.25 s valu es m ay create addition al operation al problem s
co m p a r e d w it h r a t io s o f 0 .8 4 ( 0 –5 o C) a n d 0 .7 in term s of equ ipm en t operation an d m on itorin g
(10–25 o C) for data collected u sin g Niagara River requ irem en ts.
water at a total chlorine residual of approximately 0.5
m g/ L.12 Th e data of Jen n er an d Jan ssen -Mom m en 17 Conclusions
sh ow excellen t agreem en t with m odel prediction s. Th e followin g con clu sion s m ay be m ade from th e
How ever, details of th eir experim en ts, in clu din g resu lts of th is stu dy:
m u ssel size an d raw-water ch aracteristics, were n ot • The degree of zebra mussel mortality from chlo-
reported. Alth ou gh th e kin etic m odel was based on rin e is a fu n ction of con tact tim e, ch lorin e con cen -
adult mussel (> 10 mm) mortality data, model results tration, and temperature. The dependence of the rate
for the juvenile mussel mortality data of Martin et al18 on ch lorin e appears to be less th an first order in total
an d u n pu blish ed data collected at th e Un iversity at residu al ch lorin e con cen tration . Th e rate con stan t
Bu ffa lo a r e in r e la t ive ly go o d a gr e e m e n t w it h describin g zebra m u ssel m ortality from ch lorin e is a

(C) 1995 American Water Works Association

MAY 1 9 9 5 107
stron g fu n ction of tem peratu re, with an estim ated
activation en ergy of 16.5 kcal/ m ol. Th is correspon ds
to abou t a th reefold in crease in th e rate for a ch an ge
in tem peratu re from 10 to 20 o C.
• Th e m odelin g approach u sed to describe m or-
tality data com bin ed a statistical approach u sin g th e
n orm al cu m u lative distribu tion with a kin etic m od-
elin g approach . Th e m odel was applied to n in e data
sets w ith a ran ge in tem peratu res from 0.3 to 24 o C
an d ch lorin e con cen tration s from 0.25 to 3 m g/ L.
Application of th e m odel to in depen den t m u ssel
m ortality data in dicates th at raw-water qu ality ch ar-
acteristics m ay be im portan t in affectin g m u ssel
m ortality.
• Usin g th e kin etic m odel, an operation al dia-
gram w as con stru cted an d is proposed as a u sefu l
tool for design in g con trol program s for adu lt zebra
m u ssels u sin g ch lorin e.
Acknowledgment
Th is work was fu n ded in part by th e Erie Cou n ty
Wa t e r Au t h o r it y, w h o se su p p o r t is gr a t e fu lly
ackn owledged.
References
1. LEPAGE, W.L. Th e Im pact of Dreissena polymorpha
on Waterworks Operation s at Mon roe, Mich i-
gan . Zebra Mussels: Biology, Impacts, and Controls
(T.F. Nalepa an d D.W. Sch loesser, editors). Lewis
Pu bl., Boca Raton , Fla. (1993).
2. KOVALAK, W.P. ET AL. In festation of Power Plan t
Water System s by th e Zebra Mu ssel (Dreissena
polymorpha). Zebra Mussels: Biology, Impacts, and
Controls (T.F. Nalepa an d D.W. Sch loesser, edi-
tors). Lewis Pu bl., Boca Raton , Fla. (1993).
3. J ENNER, H.A. & J ANSSEN-M OMMEN, J.P.M. Mon i-
torin g an d Con trol of Dreissena polymorpha an d
Other Macrofouling Bivalves in the Netherlands.
Zebra Mussels: Biology, Impacts, and Controls (T.F.
Nalepa and D.W. Schloesser, editors). Lewis Publ.,
Boca Raton , Fla. (1993).
4. KRAMER, J.M.; J ENNER, H.A.; & DE ZWART, D. Th e
Valve Movem en t Respon se of Mu ssels: A Tool
in Bio lo gica l M o n it o r in g. Hydrobiologia ,
188/ 189:433 (1989).
5. VAN BENSCHOTEN, J.E. ET AL. Chemical Oxidants for
Con trollin g Mu ssels: A Syn th esis of Laboratory
an d Field Stu dies. Zebra Mussels: Biology, Impacts,
and Controls (T.F. Nalepa an d D.W. Sch loesser,
editors). Lewis Pu bl., Boca Raton , Fla. (1993).
6. D E G IROLAM O , D.J.; J ENSEN , J.N.; & VAN B EN -
SCHOTEN, J.E. Inactivation of Adult Zebra Mussels
by Ch lorin e. 1991 AWWA An n . Con f., Ph iladel-
ph ia, Pa.
7. DEGIROLAMO , D.J. In activation of Adu lt Zebra
Mu ssels by Ch lorin ation . Master’s th esis, State
Un iv. of New York at Bu ffalo, Dept. of Civil
En grg., Bu ffalo, N.Y. (1992).
8. Standard Methods for the Examination of Water and
Wastewater. APHA, AWWA, an d WPCF, Wash -
in gton , D.C. (17th ed., 1989).
(C) 1995 American Water Works Association
108 JOURNAL AWWA
9. COSSINS, A.R. & BOWLER, K. Temperature Biology of
Animals. Ch apm an an d Hall (1987).
10. W EI, J.H. & CHANG, S.L. A Mu lti-Poisson Distri-
bu tion Model for Treatin g Disin fection Data. Dis-
infection: Water and Wastewater (J.D. Johnson, edi-
tor). An n Arbor Sci. Pu bl., An n Arbor, Mich .
(1975).
11. J.M. Mon tgom ery Con su ltin g En gin eers. Water
Treatment Principles and Design . Wiley In tersci.,
New York (1985).
12. VAN BENSCHOTEN, J.E. ET AL. Optimizing the Use of
Chemical Oxidants for Control of the Zebra Mus-
sel (Dreissena polymorpha). Fin al Rept. Niagara
Moh awk Power Corp., Syracu se, N.Y. (1992).
13. HOM, L.W. Kinetics of Chlorine Disinfection in an
Ecosystem. Jour. San. Engrg. Div.—ASCE, 98:1:183
(1972).
14. FAIR, G.M. ET AL. Th e Beh avior of Ch lorin e as a
Water Disinfectant. Jour. AWWA , 40:1051 (1948).
15. HAAS, C.N. Disin fection . Water Quality and Treat-
ment (F.W. Pon tiu s, editor). McGraw-Hill, New
York (1990).
16. KLERKS, P.L. & FRALEIGH, P.C. Con trollin g Adu lt
Ze br a M u sse ls Wit h Ox id a n t s. Jou r. AW WA ,
83:12:91 (Dec. 1991).
17. J ENNER, H.A. & J ANSSEN-M OMMEN, J.P.M. Ch lo-
rin e Min im ization in Macrofou lin g Con trol in
th e Neth erlan ds. Water Chlorination: Chemistry,
Environmental Impact, and Health Effects, Vol. 5.
(R.L. Jolley et al, editors). Lew is Pu bl., Boca
Raton , Fla. (1984).
18. M ARTIN, I.D. ET AL. Acu te Toxicity an d Pu lse-
dosed Delayed Mortality at 12 an d 22 o C With
Sodiu m Hypoch lorite, Bu lab 6002 an d Hydro-
gen Peroxide on the Biofouling Mollusc, Dreissena
polymorpha. Mackie & Assoc. Water Systems Ana-
lysts, Gu elph , On t. (1991).
SELLECK, R.E. ET AL. Kin etics of Bacterial Deactivation
With Ch lorin e. ASCE (JEED), EE6, 1197 (Dec.
1978).
About the authors: John E. Van
Benschoten is an associate professor
in the Department of Civil Engi-
neering of the State University of
New York at Buffalo, Buffalo, NY
14260, where he has been active in
zebra mussel research since 1990.
Van Ben sch oten is a gradu ate of
Union College, Schenectady, N.Y. (BS) and the University
of Massachusetts at Amherst (MS and PhD). A member of
AWWA, ASCE, and the International Association on Water
Quality, he was the recipient of an AWWA Best Paper
Award in 1994. James N. Jensen is also an associate pro-
fessor in the Department of Civil Engineering at the State
University of New York at Buffalo. At the time of the
research described in this article, Donald Harrington was
a graduate student at the State University of New York at
Buffalo. Daniel J. DeGirolamo is a project engineer with
O’Brien & Gere Engineers, 5000 Brittonfield Pkwy., P.O.
Box 4873, Syracuse, NY 13221.