Relations between drinking water mutagenicity and water quality parameters

Chemos~here, Vol.17, No.i, P r i n t e d in G r e a t B r i t a i n

RELATIONS

BETWEEN

pp 189-202,

DRINKING

*T.

WATER

1988

0 0 4 5 - 6 5 3 5 / 8 8 $3.00 + .00 P e r g a m o n J o u r n a l s Ltd.

MUTAGENICITY

Vartiainen

AND

WATER

QUALITY

PARAMETERS

and A. L i i m a t a i n e n

N a t i o n a l P u b l i c H e a l t h Institute, D e p a r t m e n t of E n v i r o n m e n t a l H y g i e n e and Toxicology, Box 95, S F - 7 0 7 0 1 K u o p i o , FINLAND

P. K a u r a n e n U n i v e r s i t y of Kuopio, D e p a r t m e n t of C h e m i s t r y Box 6, S F - 7 0 2 0 0 Kuopio, F I N L A N D L. H i i s v i r t a National

Board

of Health,

Box 220,

SF-00531

Helsinki,

FINLAND

ABSTRACT

The f o r m a t i o n of m u t a g e n i c a c t i v i t y in d r i n k i n g w a t e r s c o n t a i n i n g various a m o u n t s of o r g a n i c m a t t e r was studied in Finland. It was found p o s s i b l e to model the m u t a g e n i c i t i e s of c h l o r i n a t e d d r i n k i n g w a t e r s as a f u n c t i o n of the total o r g a n i c c a r b o n (TOC), of the c h l o r i n e dose, and as a m i n o r factor, of the a m o u n t of ammonia. The e q u a t i o n was the sum of the two c h l o r i n a t i o n steps, e a c h of t h e m of the same form: [mutagenicity

in TA i00]=

A(l-e-kC),

where c=[TOC][CI2]. Here [TOC] is the c o n c e n t r a t i o n of total o r g a n i c carbon and [C12] the c h l o r i n e dose, in units of mg per liter; A and k are constants. The r e g r e s s i o n c o e f f i c i e n t R for the m e a s u r e d m u t a g e n i c i t i e s in TA i00 and the m o d e l l e d m u t a g e n i c i t i e s was 0.854 in 86 d r i n k i n g w a t e r samples. Ozone or chlorine dioxide preoxidation combined with chlorine p o s t d i s i n f e c t i o n r e s u l t e d in lower m u t a g e n i c i t i e s than if c h l o r i n e was used in b o t h steps. The m u t a g e n i c i t i e s were s l i g h t l y h i g h e r in w i n t e r than in summer. K e y words: d r i n k i n g water, mutagenicity, TOC, c h l o r a m i n e , c h l o r i n e dioxide, ozone.

189

Ames'

test,

TA

i00,

TA

98,

TA

97,

190

INTRODUCTION

In

our

water

previous

of

Kuopio,

Salmonella (2-11).

/microsome

This

humus

by

(THMs)

(19),

decreased Some

in

chlorinated of

TA

mutagenic which

was

(23),

was

compound The

first

are,

in

content

(27), water

and

the

surface

and

Africa

of

as well

them

of

of

been have

compounds

less

than

acids.

in

waters

was

the

The

2% of highly

the

correlations

were

as well

in C a n a d a

of

found

as

of

some

quality in

reported

found

in

they

the

raw

and

that

the

study

mutagenic

volatile

both c o n t a i n

concenthe

different

from

Canada

activity

organic high

to

Netherlands

contain

In the

South

between

the

correlation

waters

between

levels

and in F i n l a n d

no

waters; humus.

(25).

both

(ii)

al.

mutagenic

organochloride

but

raw

waters

and

of

co-workers

The

drinking

studied

was

content

adsorbable

Finnish

concentration

been

relationship

Netherlands,

et

organic,

water

have

(MX),

Holmbom

in F i n l a n d

drinking

and

the

observed.

from

chlorinated

waters

carbon

Kool to

by

single,

waters

A weak

(26).

in

drinking

organic

correlated

low

also

important

activity

in

a

most

waters

a

in the Ames'

these

and

humic

have (13)

as q u a n t i f i e d

mutagenic

mutagenicity

chlorination

drinking

waters

co-

generally

co-workers

TA i00 m u t a g e n i c i t y ,

present

the

total

parameters

waters

and

humus

properties

and

identified

chlorination

pulp

and

different

highest

treatment

Meier

many

total

and Canada,

was

raw

very

agents

and

mutagenic

the

South

in

aquatic

trihalomethanes

Guttman-Bass

and c a r c i n o g e n i c

20-22).

by

mutagenic

drinking

however,

pollution

The

in

isolated

Ames'

elsewhere

natural

of

by

acids

be

be

waters

activity

trations h umus

of

raw

activity

water

from

shown

of

the

to

to

the N e t h e r l a n d s ,

mutagenic

mainly

been

the

measurements

is

compounds,

from

in the c h l o r i n a t e d ,

mutagenic

has

drinking

in

of it.

formed

proved

shown

of

to s i m i l a r

high

3-chloro-4-(dichloromethyl)-5-hydroxy-2(SH)-furanone

recently was

chlorinated

very

report

of the total

isolated

correlation

treated

humic

of

be

chlorination

(12,

However,

7-8%

compound

parameters Africa,

of

to

produced

same

mutagenic

water

mutagenicity

MX

which

chlorinated

assay.

The

contrasting

known

activity

found

as c o m p a r e d

activity

with

was

apparently

to

drinking

for o n l y

98

(24).

only

solutions

mutagenicity

the

The

organic

accounted

is

according

compounds

mutagenic

(12-14).

the m u t a g e n i c

identified

(i),

mutagenicity

(15-18).

the

Finland,

test

chlorination

workers

series

studies

Eastern

and

compounds.

levels

of humic

matter. Disinfected

drinking

from e a c h other, different the

raw

mutagenic

waters

in

oxidated

waters

(28).

activity

Finland or

b)

of to

disinfected

follow

the

waters,

and d) to s e a r c h

tivities

waters,

made

of h u m u s - r i c h

due to the c o m p l e x i t y

seasonal

of d r i n k i n g

Our

aim

of humus

was

chlorinated compare in

the

of

for a m e t h o d using

to

investigate

drinking mutagenic

waterworks

variations

waters

a)

with

the

raw waters,

waters

to

activity

different

mutagenic

greatly

of humus

in

the

correlation

of

the

quality

of

drinking

of

of

c)

to

drinking

of the m u t a g e n i c

water parameters.

raw

waters,

disinfectants,

activities

for the e s t i m a t i o n

common

differ

and the d i v e r s i t y

ac-

191

EXPERIMENTAL

Materials Drinking genicity

in

icities once.

water one,

of

the

The

iron, and

from

three

raw

or

manganese,

from

the

termined

at

Unicarbo

Carbon

the

localities

all

(pH,

of

as

as

The

values,

the

total

Mekrij~rvi

Research

Analyzer,

according

(Table

pre-

and

and

Station

i).

for m u t a -

The

alkalinity)

postchlorine

carbon

technique

mutagen-

tested

at

ammonium,

least

nitrate, of

the

dosages

(TOC)

values

of

Joensuu)

(University

the

tested

were

colour,

organic

to

were

waterworks

conductivity,

well

waterworks.

Finland

seasons

the

KMnO 4

chloride,

waters

in

different

from

parameters

drinking

obtained

39

four

waters

control

nitrite, waters

samples

developed

raw were

were

de-

using

by

a

Salonen

(29). In

April

waters

1985,

were

determination column

The

and

types

was

of

classify

into

No

In

treatment

type

filtration,

to

J,

the

followed

iron by

presented The

of

their

in T a b l e

study,

treatment

of

The

mills

from

mean

the

drinking

waters doses

of

waters.

mg/l and were

to

of

from

D

and

1.7~1.2,

alum

used

In

as

coagulation

In

flotation),

sand

from

C to

process

con-

types

or

sand

as em-

raw water

preceding

acidic

to

used was

types

chlorine.

in

was

clarification,

treatment

preoxidants

from in

D

tree

neutral

pH,

filtration,

pH

and postdisinfectants

At

to

0.80

1.0~0.5,

the

of

the

same

numbers

E type

time,

of

during

the

waterworks

the

amount

waterworks

of

using

course changed

chlorine different

changed. by

J is

5.2

and

the

8.8

activity

were was

drinking

1.4~0.2

and

mg/l

waters. in

the

drinking

from

mg/l

zero

its of

expulp

in it.

in

and

for

effluent

found

0.048 from

reason of

7.55

in raw waters

range

in

the

amounts

waters

of a m m o n i a the

case:

high

mutagenic in raw

to

mg/l and

a special

was

6.44

values

water

to t h e w a t e r w o r k s

several

the

the high

from

The mean

zero

type.

reason,

pH were

pH was

in d r i n k i n g

packed

possible

water

was

the

with

or

reported

E waterworks

raw water

range

were

a consequence,

processes

values

a

hydroxide

chlorine. C,

preoxidation

different

ground sodium

water

with

In t y p e

of

with

The

technique.

it w a s

coagulation,

disinfection

The

A,

with

ground

disinfection

(sedimentation

this

type

waterworks,

In t y p e

alum

consisted

designated

the

in the

The

0.053

treatment

of

space

drinking

Finland.

equipped

head

of

of

of the waters

of t h e

i):

(THMs)

Center

I.

process For

waterworks

clusion

as

the

adjustment

possible

results

and

decreased.

types

process

disinfection.

mutagenicity

this

was

and

and

using

recharged

and

coagulation,

clarification

adjustment, are

and

Research

chromatograph

as r a w w a t e r .

filtration

treatment

by

pH

consisted

used

trihalomethanes

quality

(Table

only

artificially

was

gas

processes

types or

process

direct

a

detector

and the

adjustment

water

of

cases

B,

pH

surface

eight

of

Technical

by

treatment

treatment

and

sisted

The

performed

to the

ployed.

J,

in

the waterworks

them

water.

the

concentrations

an e l e c t r o n - c a p t u r e

According

raw

the

analyzed

5.9

waters

to 8.8 in

in r a w w a t e r s

and

to

0.58

mg/l

The

mean

prechlorine

waterworks

of

in r a w

types

E,

192

F,

and

J,

respectively,

1.3!0.9 , 1.0!0.5, waterworks

of

and

The

correlation

for

92

Table

drinking

of

water-

postchlorine

0.7!0.2,

in

doses

1.9!0.1, and

different

coefficient

were

1,4!0.3,

J,

types

1.0+0.9,

and

0.6+0.6,

1.9!0.3

respectively.

The

of

shown

R of K M n O 4 v a l u e s

waters

to T O C

are

mg/l

TOC

of

Table

2.

in

concentrations

in the

values

was

0.954

samples.

treatment

processes

in the w a t e r w o r k s

Predisin-

Precipi-

Post-

fectant

tation

disin-

agents

fectant

works

Ground

the

B,C,D,E,F,G,H,I,

waters

raw water

I. W a t e r

Type

0.7i0.3,

type

raw

and

at

Number

different

times.

of waterworks

April

Nov.

July

Oct.

March

1985

1985

1986

1986

1987

3

2

3

3

9

C12

2

1

2

2

2

none

C12

4

3

4

3

0

waters

A

none

Artificially B

none

recharged none

ground

water

none or

Surface

none

I

waters

C

none

D

none

I/I+II

C12

5

1

8

8

0

E

C12

I/I+II

C12

7

7

4

4

0 0

F

CIO 2

I/I+II

C12

2

1

2

2

G

ozone

I

NH2CI

2

1

2

2

0

H

none

I

NH2CI

1

1

1

1

0

I

KMnO 4

I

C12

0

1

1

1

0

J

C12

I

C12

1

1

1

1

0

numbers

27

19

28

27

organics

was

or

none total

I = A 1 2 ( S O 4 )3 II=

ii

F e 2 ( S O 4 )3

Isolation The

of mutagenic

concentration

8 resin,

using

flow

rate

tate.

A

recently

of

0.67

bed

using

dissolved at p H

volumes

per

description

of

2

(conc.

minute, the

done

HCI),

elution

with

extraction

by

adsorption

resin 300

volume ml

procedure

of was

of

o n XAD 50 ml,

ethyl

ace-

published

testing was

tester

Sodium

assayed strains

azide

mutagens

and

by TA

the i00,

plate TA

incorporation

98,

and

TA

97

method

without

(NaN 3 ) and methylmethanesulphonate

4-nitro-o-phenylenediamine control

the

of water

(30).

Mutagenicity

vation.

of

4 liters

detailed

Mutaqenicity

(31)

compounds

the

(4-NPD) solvent

for

(DMSO)

TA

98

and

TA

as a n e g a t i v e

(MMS)

97

were

of A m e s metabolic for

used

control.

TA

et al. actii00

and

as p o s i t i v e

193

The

samples

formed liter

in of

linear curve

were

water

to

The

sample,

regression due

linear

diluted

duplicate.

portion

i.e.

(least

the

in

the

the

to

obtain

of

curve

was

slope

square)

toxicity

of

DMSO

mutagenicity

of

the

method.

In

sample,

the

the

4-5

doses.

calculated dose the

Each

as

net

response

case

slope

of

was

test

was

per-

revertants curve

using

flattening determined

per the

of

the

from

the

(32).

T a b l e 2. T h e T O C c o n c e n t r a t i o n s of t h e r a w a n d d r i n k i n g w a t e r s of the d i f f e r ent types of waterworks (the m e a n v a l u e s , t h e s t a n d a r d d e v i a t i o n s (sd), and the n u m b e r s (N) w h i c h i n d i c a t e the t o t a l n u m b e r s o f t e s t s in d i f f e r e n t t y p e s of w a t e r w o r k s ) . Type

of

raw waters

drinking

waters

waterworks

mean

Ground

sd

mean

sd

2.38

0.99

20

9

waters

A

2.75

Artificially

1.03

recharged

B

ground

waters

9.05

6.88

3.85

1.71

C

7.47

2.32

6.21

2.01

14

D

11.2

2.16

5.96

1.39

25

E

12.0

3.14

6.40

1.15

22

Surface

waters

F

9.85

3.54

5.18

0.52

7

G

8.27

i. Ii

3.89

0.62

3

H

27.9

2.92

9.39

0.66

4

I

11.9

0.07

5.63

0.37

3

J

i0.i

1.19

6.62

1.07

4

RESULTS

In

Finland,

waterworks recharged last

ground

cent

number

of

of

because

The

1985.

ten years.

per

of

surface

in

the

Pt/l.

Drinking water

as

in of

permanganate

waters

has

spite

using

Finland

recommendations

distributed

In

drinking

permitted

studied

of

water

of

the

surface use

is

level

is

for

in

to

this

by the waterworks

water

15

raw

water

water

about

amount

35%

is o n e surface 2)

of

to

mg

represented

in Finland.

to

in

KMn04/I,

for

The

more

or than

about

a

the

45%

water, total

in

was

4

the

number

humus

content

Central

Europe.

performed

impurities

about

recharging

of t h e

water.

by

artificially

surface

tenth

compared

cases

used

and

by artificial

(Table

is

work

from

in most

supplies

the

ground

great

organic

consumption, apply

of

made

mainly

high

water

55%

natural

increased

of g r o u n d

municipalities

waters

maximum

The

together

share

total.

last

disinfection

measured

water The

DISCUSSION

represented

proportion

the waterworks

the

surface

The

water

The

AND

with

chlorine.

drinking as

water,

colour,

200 half

15 mg

inhabitants. of

all

the

194

T able 3. The m e a n m u t a g e n i c a c t i v i t i e s and TA 97 w i t h o u t e n z y m a t i c activation. to Table i. Type

of

TA i00

of d r i n k i n g w a t e r s in TA i00, TA 98, Type of w a t e r w o r k s from A to J refers

TA 98

TA 97

waterworks

Mean

Ground

Range

Mean

Range

Mean

Range

<50

<50-130

150

<100-540

<50-420

490

<100-1700

waters

A


<100-450

Artificially

recharged

B

700

Surface

ground

20

waters

<100-1700

90

9

waters

C

1400

<100-2800

300

<50-1800

960

<100-2800

D

2300

800-6000

340

< 50 - 1 4 0 0

1300

<100-6400

14 22

E

3650

650-7400

480

<50-1600

1700

<100-6800

22

F

1110

830-1700

G

590

70

<50-250

690

<100-1400

7

480-650

i00

<50-240

320

100-460

3

H

5600

4200-7940

480

370-550

1350

960-1900

4

I

3070

2540-3340

190

130-230

1240

680-1850

3

J

7750

3560-14000

1090

210-3000

3930

1010-7700

4

The

level

ties

of

used

were

of m u t a g e n i c

drinking above

of

drinking

B)

as

as

than

waters

(Table

The

highest

on

levels two

ground

amount

values

are used

Most

of the

however,

raw w a t e r

in

in

TA

(Fig.l),

KMnO

i00

values

in

raw

in

waters from

in

comparable,

because

of

C and D)

were

were

also

dependent water.

were

sur-

(type E).

activities

countries

were

surface

(types

drinking

(type

G)

from

waters

in F i n l a n d other

waters

processed

drinking

and

activities

chlorinated

waters

but h i g h

strains

(type

the m u t a g e n i c i t i e s water

reported

directly

to

copper,

waters

to

TA i00,

of d r i n k i n g

those

and d r i n k i n g

activities

activity

than

activi-

the

ground waters

and w i t h p o s t c h l o r i n a t i o n

in s t r a i n

matter

zinc,

raw

lower drinking

all

The

from one to (2-11).

the

The

different

concentration.

of o r g a n i c

calcium,

centrations) mutagenic

than

recharged

of

mutagenic

in

The m u t a g e n i c

and p o s t c h l o r i n a t e d

matter

A)

drinking

still

In all strains,

activities

for s a m p l e

Correlations

magnesium,

found

organic

higher

not,

of pre-

strains.

of m u t a g e n i c

methods

artificially

but

The

(type

postchlorinated

prechlorination

were

of

magnitudes

from

waters.

waters

in a few cases.

mutagenicities

of that

values

in d r i n k i n g ground

only

waters,

The

in the o t h e r

the

limit

processed

3).

half

of

preozonated,

without

about

found

in

in

face w a t e r s

activity made

detection

waters

well

higher

were

waters

in

or

in

drinking

TOC

values

(R=0.495,

mutagenic

water

quality

aluminum, drinking waters.

of d r i n k i n g

parameters

fluoride, waters Linear

(correlation

p
activities

did

not

manganese,

or nitrous correlate

correlations

coefficient

and c o l o u r

(iron,

nitric,

waters.

of

R=0.478,

(R=0.465,

to

conthe

mutagenic p<0.001)

p
were

195

8000-

6OOO

% >

m •

44:)OO •

i

-e e

•

•

2000 •

m O

•

mmLQm mmm

•

•

•

•

•

•

m m m m

-.

. m m

•

mm

~"-

..

•

m| --~

~

!

~-

i

,

,

l

6

,

i

w

J

I0

w

!

i

14 toO/!

TOC

F i g u r e i. T h e c o r r e l a t i o n b e t w e e n activities in T A i00 of d r i n k i n g 0.478.

found.

The

matter with

mutagenic

and

chlorine

increasing

drinking TOC,

KMnO4,

It w a s

and

of

the

cluded If

drinking

chlorine

oxidant

in r a w

The

and

waters

as

doses.

raw

lower

in TA than

a n d 0.557,

best

the

fit

equation

decreased,

added

to

the

98 o r TA 97 to

in TA

i00

(range

activities

activities

total

was

of the

organic

in TA

respectively.

the mutagenic of

of

it

or

of t h e m u t a g e n i c

0.537

The

but

water

activities

a function

an e x p o n e n t i a l

amount

disinfectant in

were

correlations

waters

ammonia

step

or

present

to model

increasing

in TA i00

organic

obtained

by

carbon

and

using

for

form

f= A ( l - e -k¢ )

f is is

the a

mutagenic

activity

concentration

to this two

following

of

parameter.

drinking The

water.

raw

water

A

and

k are

mutagenicity

constants, is

not

in-

used

in

the

equation.

chlorination

steps

were

used,

equation

(I)

was

form: f=

where

values

with

of mutagenic

to be possible

chlorination

c

correlations

colour

(I)

and

as

ammonia

in T A 98 a n d T A 97 w e r e

chlorinated

where

increased

used of

to 0.413).

found

of

each

The

0.284

i00 to t h o s e

doses

amount

water.

of R f r o m

activity

T O C v a l u e s in r a w w a t e r s a n d t h e m u t a g e n i c waters. The correlation coefficient R was

fR

R refers

the parameters

+ fD' to the

parameters

of drinking

The variable

c was

waters

defined

of the

raw waters

(prechlorination)

a n d D to

(postchlorination).

as

c = [ T O C ] [CI 2 ], where dosed

[TOC]

and

chlorine,

is both

the

concentration

in units

of mg per

of

total

liter.

organic It w a s

carbon

possible

[C12]

the

to replace

and

the

196

parameter value

[TOC]

(mg

Urano

and

by

is t h e

our

stay,

If

the

effect

waters

cases mg/l

in

activity

in

c by

as

have

form

free

(mg

KMnO 4

presented

when

an

per

water

equation

is

liter)

for

the

chlorinated.

[TOX]=kT0x [TOC][CI~]t,

was

or

ammonia

in

in t h e

improved into

The

where

as m g / l .

The

water.

or

colour

formation equation

k is

some

factor

the it

ammonia were

of

pre-

constant

and

drinking

water

activity

degree One

t

when

to

method).

or

0.001

added

mg/l

concentrations

to the

where

allowed

to

in of

44 0.8

H. the

measured

influence

possibility

for modelled

was

present

above

highest

of t y p e

(I-[NH3])2,

equation

in

sample,

starch-iodine

of

The

mutagenic

to

left

the

(by t h e

waterworks

account.

a dimensionless

in

concentrations

drinking

modelled

taken

usually

found

concentrations

ammonia

were

of

i00

The

The

was

was

chlorine-free

ammonia.

waters

also

chlorine

chlorine

low.

TA

was

ammonia

then

no

correlation

waters able

the

free

of

added

The

(33)

sample

were

raw

of

value

chlorination.

any

until

The

of

of

permanganate

compounds

has

study,

samples.

the

organic them

time

In

the

liter).

Takemasa

halogenated sented

by

Pt p e r

is

of

mutagenic ammonia

to m u l t i p l y

[NH3]

is

mutagenic

the

the

in

vari-

concentration

activity

in T A

i00 is

follows: -kc R

(II)

-kc D

f= A ( l - e

) + A(l-e

)

where C R = [ T O C ] R [CI2]R ( I - N H 3 R ) 2, CD=[TOC]D[CI2]D(I-NH3D A

= constant

k

= constant

2000

for The

(net

for

rev./l),

colour

TOC values,

3000

for

KMnO 4 values,

and

0.054

for

TOC

values,

0.035

for

KMnO 4 values,

and

0.2

of

the

values.

inclusion

of

the

between

correlations

for

values

(mg-212),

colour

)2,

4000

from

0.856

to 0 . 8 8 0 ,

TOC,

KMnO 4

or

and

measured

ammonia

concentrations

improved

and measured

mutagenic

the modelled from

colour

0.853

values,

mutagenic

to

0.877,

or

respectively.

activities

of

from The

drinking

the

0.778

to

0.786,

correlation waters

R-values

activities

is

in TA I00 when

between

presented

using

modelled in

Figure

2. Chloramine the

type

G,

expression extremely normal was that

the (II).

high.

in

and the

with

in this

was

mutagenicities TOC values The

treatment

added

minutes (II)

disinfection

first

the

of d r i n k i n g

chloramine

disinfection

excluding

20 m i n u t e s , step,

because

water It

is

the

all

0.7-0.8 was

was

of

disinfected not

types

in good

waterworks

done

as

with

dose

was

and

agreement

In

with

mg/l

after of

added.

use

is n o t

H.

of type H were

chlorine to

G

follows:

1.7-2.0

ammonia

possible

chlorination

of

were

in the

oxidants,

mg/l

therefore true

waterworks

waters

the raw water

chloramine. case,

in

of

processes

after

used

and the

known.

the

chlorine

This means after

20

expression

197

8000-

6000

•

"

%,

8 v,-

< I-

2OO0

C

r

~

I

,

0 Figure

4ooo

2.

net rev/l

The c o r r e l a t i o n between modelled mutagenic activities according to the e q u a t i o n (II) and m e a s u r e d m u t a g e n i c a c t i v i t i e s of c h l o r i n a t e d (62) or nonc h l o r i n a t e d d r i n k i n g w a t e r s (35) in TA i00 as net rev./l. The c o r r e l a t i o n c o e f f i c i e n t R for 97 s a m p l e s was 0.880, the c o n s t a n t was 20, the s t a n d a r d e rror of c o n s t a n t was 790, the slope was 0.984, and the s t a n d a r d error of the slope was 0.055. The

effect

mutagenic modelled

of pH.

activity

The

was

and m e a s u r e d

factor

A

factor

A

improved

in in

the the

effect

mutagenic

expression

only

Using

our

activities

(II)

expression

the R - v a l u e

of pH d u r i n g

minimal.

by

with

slightly,

the

the

chlorination

material, was

found

factor

6000-

best

process

However,

on the

correlation

by m u l t i p l y i n g

(15-pHR)/pH R

(]5-pH0)/pH D . from 0.880

the

and this

the the

of

first second

correction

to 0.886.

o o

o

D

o

o

Q

4x~ D

O

¢

o o

0

40

Figure 3. The C o r r e l a t i o n between m u t a g e n i c i t i e s in TA 100.

trihalomethane

0 THM @g/I concentrations and d r i n k i n g

water

198

Correlation water

of

mutagenicity

coefficient which

can

when

high

R be

matter

for

TA

samples

THMs

must

shown

from

activity

in

and

i00

mutagenic

in T A

mutagenic effluent

of

possible

effluents

mutagenic that

or

Grabow

of

some

some et

al.

Africa,

rivers

algae

Rhine

low

did

of

humic

waters

mills in

at

of

the

have TA

of

the

organic

equation

for

substances

has

as

raw

waters

are

slightly

in

have

caused

water

type a

mutagenic was

of

97

in

the It is

influenced

is

the

unknown.

in

some

the

elevated It

is

bacterial

of w a t e r s .

activity found

high

systems.

for

mutagenic

the m u t a g e n i c i t y

activity

had

reason

in

were

J supply

lake

raw

high

samples

consequence

or

TA

of

surprisingly

elsewhere

The

of

find

the

even

i00.

activities

raw

rivers

waters

not

but

the

apparently

pulp

mutagenic

and Meuse

0,633,

raw waters

from

empirical

mutagenic

in A p r i l , all

Raw

waters

toxins

(26)

but

low

upstream

activity

was

mechanism

compounds

the

drinking

correlation

in t h e

the

dissolved

The

Almost

strains,

of

The

April

present

mutagenic

of

3. in

However,

because

very

seasons.

natural

of

waters.

i00.

raw

Figure

of

(34).

were

located

in

correlation

of h u m u s

formed.

other,

The

mutagenicity

content

raw

all

mills

shown

for

chlorination

TA

in

is

formation

of

98

THMs.

was

on pH

in b o t h

activity

of

possible

the

pulp

that

mutagenic values

97

TA in

activity

high

each

mutagenic

especially

THMs

to

tested

THMs

in

dependent

TA

to

the

formation

November,

South

of

t o be

The

strains

i00

by the

and

differ

trihalomethane

waters

in

explained

of

activity

28

concentrations

formation

been

mutagenic

in the

waters

from

Netherlands

raw

from

(35).

Table 4. The mean values of raw water mutagenicities of acid/neutral f r a c t i o n s o f d i f f e r e n t t y p e s o f w a t e r w o r k s in T A I00, T A 98 a n d T A 97 w i t h o u t e n z y m a t i c a c t i v a t i o n , g i v e n as n e t r e v e r t a n t s p e r l i t e r w a t e r in A p r i l and in N o v e m b e r 1985. ( n . t . = n o t t e s t e d ) Type of waterworks Ground

April

1985

November TA

i00

TA

98

1985

TA i00

T A 98

T A 97

TA 97

370

<50

670


120

290

waters

A Artificially

recharged

B

ground

waters


<50

270


<50

430

C


<50

250

840

140

1170

D


<50

170


<50


E


<5O

130

1250

210

2000

n.t.

n.t.

270

<50

190

n.t.

Surface

F

waters

n.t.

G


<5O


n.t.

n.t.

H


<50



<50


I

n.t.

n.t.

n.t.


<50


J

1200

90

ii00

3800

<50

2900

199

The

seasonal

s eason a l

variations

variations

variations Mutagenic

of

raw

of m u t a g e n i c activities

of

mutagenic

water

quality

activities

seem

activity were

in d r i n k i n g

to be s l i g h t l y

in

drinking

insignificant. waters

higher

waters.

are

in w i n t e r

The

shown than

The

seasonal

in Figure

4.

in summer.

/ 0 9

11 month8

3000

I000

0 Figure

4,

months

The m e a n s e a s o n a l v a r i a t i o n s of d r i n k i n g w a t e r m u t a g e n i c i t i e s in TA i00 and TA 97 in the types of w a t e r w o r k s from A to F (A=[] ,B= • , C = Q ,D= ZS , E = • , F=O).

The

effect

chlorine dioxide

was

ide/chlorine that In

of

used

in

number

of

of

Ozone

was

with

recently used

in

studied

(equation studies

water

aquatic

chlorine.

by

II),

from

us.

assuming

several

(36-38).

A

as The

activity

the effects

organic

Waterworks

permanganate

the m u t a g e n i c

concerning

drinking

dioxide

published

waterworks

other

mutagenicity

than

potassium

raised

by the m o d e l

were made

been

and

two

observations

chlorine

oxidants

ozone

treatments

predicted a

other

dioxide,

use

of

by a b o u t

countries,

review and

chlorine, Chlorine

chlorine

diox-

one third

from

only po~tchlorination.

of c h l o r i n e

material

used

preoxidants.

paper their

widely

dioxide of

the

health

differing on the

reactions effects

of has

(39). our

material

only

in

one

waterworks

which

employed

200

chloramine If

the

as p o s t d i s i n f e c t a n t .

factor

activities i.e.

of

ammonia

of d r i n k i n g

ozone

mutagenic

activity

disinfection

prior

more

alone.

than

the

ozonated/chlorinated

the

water

rising

fulvic

acid

to

in good

chlorine of

waters

combined

be

during

with

et al.

water the

the

did

prevented,

was

low.

mutagenic

expression

not

ammonia (40),

ozonation.

its (II),

with

disinfection

Kowbel

could

solution

of

equation

agreement

chloramine

study

activity

the

(equation

mutagen

the

II) in

formation

depending

on

Mutagenicity

(II)

increase

the

pH

decreased

of

with

pH value.

Permanganate

preoxidation

one

of the w a t e r w o r k s ,

and

cheap

dation about

were

to

In the

mutagenic

included

waters

oxidation

The

was

method

as

a

30

%

chlorine

to

lower

replacement lower

and

ments

have

been

(41).

With

low

two-step

use,

mutagenicities

published levels

of

did not

is

rather

activities

when

activities

prechlorination

mutagenic

increasing

in

was was

permanganate/chlorine

chlorination

however,

the

Permanganate

the

by c h l o r i n a t i o n ,

nowhere

the m u t a g e n i c

for

with

treatment.

waterworks

was

where

seldom

high

needed.

tested.

treatment

of

study

our

were

Permanganate

oxiwere

as

after

with

chlorine/-

preoxidant

only

concerning

artificially

recharged

material,

permanganate

preoxidation,

did.

the m u t a g e n i c

Permanganate

effects

on

THM

activity

and

formation

ozone when

in

permanganate

humic

increase

In

a simple

Mutagenicities than

used

waters

started. (i),

of

ground

water

followed

finished

oxidations

combined

water

might

with

the

treat-

as

have,

chlorination

(42-43). The

existence

carcinogenicity of

cancer

of

quality work

correlation

however,

drinking

equation

mutagenic

the

can be e n l i g h t e n

takes,

activities using

of

a

period

before

(II)

it

is,

activities

of

drinking

parameter

values

in

that

drinking

water

by an e p i d e m i o l o g i c a l

long

waters

between

the

of

time.

end

of

principle, waters

have

been

in

mutagenicity

study.

No

70's

data are

The d e v e l o p m e n t on

the

mutagenic

available.

However,

possible

to

approximate

Finland,

by

employing

accumulated

during

and

past

the water

years.

This

is in p r o g r e s s .

CONCLUSIONS

This a)

study

it

is

water,

processed

mutagenic amount the

activity

and d o s e d

chlorine

finished

oxidation

activity

raw

the

mutagenic

water

or

present added

activity

containing

in TA i00 w i t h o u t

to

the

metabolic

water.

of

chlorinated

natural

organic

activation

in the water,

on the

A

w h e r e A and k are c o n s t a n t s

is d e p e n d e n t

dosed

formula

drinking

matter.

of

chlorine,

the

type

and c is the p r o d u c t

The

on the and on

A(l-e -kc ) of organic

chlorine.

dioxide/chlorine

water

ozone/chloramine nate

that model

matter

present

be derived,

matter

to from

of o r g a n i c

ammonia

could

b)

demonstrates possible

only by prior

in d r i n k i n g

by the

treatment

30%, same

if amount

to c h l o r i n e water

than

increased

compared

to

as p l a i n

disinfection

the

mutagenic

plain

chloramine causes

postchlorination

activity

postchlorination, treatment.

somewhat

alone.

less

of and

Permangamutagenic

201

c) se a s o n a l higher e)

surface

low

matter

were

TA i00

found.

and m u t a g e n i c

activities

seem

to be s l i g h t l y

in summer.

containing

surface

waters

correlations

mutagenic

was weak

than

water

some o t h e r f)

variation

in w i n t e r

of

effluents

with

mutagenic

In a d d i t i o n

activities

of

of

pulp

mills

no d e m o n s t r a b l e activities

to this,

drinking

in

there

waters

in

was

sources TA

was

TA

mutagenic,

98

or

TA

correlation

I00

but

also

of p o l l u t i o n .

and

97

to

organic

between

the

TA

98,

between

of

Finland

in

and

and TA 97. ACKNOWLEDGEMENT

This work has been f i n a n c i a l l y s u p p o r t e d Natio n a l Boar of H e a l t h of Finland.

by

the

Academy

and

the

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