Chlorinated phenols in sediments and suspended matter of the Weser estuary

0045-6535/80/0201-0111~02.00/0

Chemosphere Vol. 9, PP Iii - 118 ~Pergamon Press Ltd. 1980. Printed in Great Britain

AND

C H L O R I N A T E D PHENOLS IN S E D I M E N T S S U S P E N D E D M A T T E R OF THE W E S E R E S T U A R Y

G. Eder and K. W e b e r i n s t i t u t fHr M e e r e s f o r s c h u n g A m H a n d e l s h a f e n 12, D 2850 B r e m e r h a v e n Federal R e p u b l i c of G e r m a n y

Chlorinated German

phenols

Bight

ly c o n s t a n t flected

in b o t t o m

living

chlorophenol

cause

chronic

sediments

a better

particulate estuarine

Although,

a source even

of the

is r e q u i r e d

levels

of the W e s e r

occurrence

Sediments

were

collected was

approximately

acute

stress

is

toxic

levels I)

factors

might

of the e s t u a r y

discharge

of d i s s o l v e d

has declined.

chlorophenols

their p o s s i b l e

of c h l o r o p h e n o l s

with

danger

to the

Teflon are

shown

in table

After

particulates

fied water,

a grab

sampler

and s u s p e n d e d

to p r e v i o u s

data

on their

for s u p p l y i n g

into

the o r g a n i c

was

stirred

layer was

for

15 min.

sucked

by 2,5

(v:v), After

IIi

r.p.m.,

Sampling

in a l u m i n i u m

sediment

off w i t h

Sus-

10 OO0

the turbid water.

5:1

shipboard.

from the w a t e r

or total

a 100 ml c e n t r i f u g e

40 ml of n - h e x a n e - i s o p r o p a n o l

and the m i x t u r e

9593,

were w r a p p e d

20 g of m o i s t

were weighed

Typ

from

w h i c h was d r a w n w i t h a

and s e p a r a t e d

(Heraeus

2. Samples

thawing

(van Veen)

river water,

the surface

centrifuge

tubing was used

on board.

for 5 min,

in s e d i m e n t s

and related

and m e t h o d s

from turbid

I m below

min).

added

below

other

to assess

are p r e s e n t e d

with

obtained

of a c o n t i n u o u s - f l o w

matter,

with

the o r i g i n a l

interactions in order

and p a t t e r n estuary

means

frozen

but was not re-

as far as p e n t a c h l o r o p h e n o l

in the water.

pended matter

and time

and the

e s t u a r y 3). A fair-

in water,

of long term p o l l u t i o n after

Materials

bucket

estuary

ecosystem.

In this p a p e r matter

of the W e s e r

to occur

in c o m b i n a t i o n

processes

knowledge

animals shown

of the W e s e r

on the biota.

may provide

matter

was

in w a t e r

in the w a t e r were well

burden

due to r e m o b i l i z a t i o n Thus,

animals.

effects

found

living

pattern

the c o n c e n t r a t i o n s

the total

Loaded

and

recently

concentration

in b o t t o m

concerned,

still

1,2)

were

and

foil

i/

locations and deep

suspended

tube.

10 ml of puri-

5 ml of 6M H2SO 4 were

centrifuging

a capillary.

at 5000 r.p.m.

The p r o c e d u r e

was

112

No. 2

repeated with

16 ml of n - h e x a n e and the c o m b i n e d organic layers were twice ex-

tracted w i t h 5 ml of O . 1 N

NaOH.

A f t e r w a s h i n g the aqueous solution w i t h

n - h e x a n e and b u f f e r i n g w i t h s o d i u m borate, by e x t r a c t i v e

the phenol acetates were o b t a i n e d

a c e t y l a t i o n into n - h e x a n e with acetic a n h y d r i d e / p y r i d i n e .

small a d d i t i t i o n a l

A

amount of c h l o r i n a t e d phenols was o b t a i n e d by s t e a m - d i s t i l -

lation of the e x t r a c t e d sediment.

Steam-distillation,

c h r o m a t o g r a p h y w e r e d e s c r i b e d in a p r e v i o u s p a p e r

acetylation,

and gas

(4). The e x t r a c t i o n effi-

ciency was tested w i t h a 100 g s e d i m e n t sample a p p l y i n g two a d d i t i o n a l ext r a c t i o n steps w i t h equal volumes of solvent mixture. tion c o e f f i c i e n t to be c o n c e n t r a t i o n - i n d e p e n d a n t , table c h l o r o p h e n o l s was calculated. distillation

F r o m table

the total amount of extrac-

I it appears that steam-

is g e n e r a l l y more e f f i c i e n t than e x h a u s t i v e extraction.

C h l o r o p h e n o l a c e t a t e s were g e n e r a l l y

i d e n t i f i e d and q u a n t i f i e d by gas chro-

m a t o g r a p h y w i t h e l e c t r o n capture detection. was c h e c k e d by mass spectrometry. was e s s e n t i a l l y

The r e l i a b i l i t y of the results

The q u a n t i f i c a t i o n m e t h o d used in GC-MS

the same as in GC-ECD,

"detector e l i m i n a t e d

but the high s e l e c t i v i t y of the MS-

i n t e r f e r e n c e s and s i m p l i f i e d the s e p a r a t i o n task for the

d i f f e r e n t c h l o r i n a t e d phenols. (1,2).

A s s u m i n g the d i s t r i b u -

GC-MS c o n d i t i o n s were d e s c r i b e d p r e v i o u s l y

Isomers that could not be d e t e c t e d in three samples by mass spectro-

m e t r y were omitted.

3,4,5-trichloro-

and 2 , 3 , 4 , 5 - t e t r a c h l o r o p h e n o l were

q u a n t i f i e d by m a s s s p e c t r o m e t r y alone. TABLE:

I: YIELDS OF E X T R A C T I O N AND STEAM D I S T I L L A T I O N The total m a s s ratio of e x t r a c t a b l e c h l o r o p h e n o l s was c a l c u l a t e d a s s u m i n g c o n s t a n t phase e q u i l i b r i u m for the 3rd and 4th extraction.

Chlorophenols

A m o u n t isolated Extr.

I+2

Extr.

3

(ng/g of m o i s t sediment)

Extr.

4

Total calc.

Total of extr. and steam dist. observed

2,4 3,5

-DCP

1.82

0.22

O.10

2.23

2.31

2,4,5

-TrCP

0.72

0.15

0.06

0.96

0.93

2,4,6

-TrCP

O.13

0.014

0

O.14

0.28

2'3'4'~-TeCP 2,3,5,

I 49 "

0.15

0.046

I 71

2.O8

1.26

0.44

18.24

19.56

PCP

16.3

Adsorption/desor~tion S e d i m e n t and w a t e r

(pH = 7-I) were c o l l e c t e d t o g e t h e r on Aug.

B r e m e r h a v e n river bank centrifugation.

21,

1978 at

(UW-km 66) at low tide and i m m e d i a t e l y s e p a r a t e d by

A f t e r decanting,

each of 2,6 -di-,

laboratory experiment

2,5-di-,

50 ml of the w a t e r were spiked w i t h 250 ng

2,4,6-tri-,

2,4,5-tri,

2,3,4,6-tetra-,

2,3,4,5-

No .2

113

tetra- and p e n t a c h l o r o p h e n o l . w a t e r was slowly shaken with perature

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

(14,5 ° C) in a 1OO ml s t o p p e r e d E r l e m e y e r

s e d i m e n t and w a t e r w e r e separated. to the loaded sediment, Adsorbed chlorophenols

the spiked

10 g of the c o l l e c t e d s e d i m e n t at c o n s t a n t temflask. A f t e r 21 hours

50 ml of u n s p i k e d W e s e r w a t e r was added

shaken for another 21 hours and s e p a r a t e d again. from the w a t e r and d e s o r b e d c h l o r o p h e n o l s

from the

s e d i m e n t were a n a l y z e d by i n v e s t i g a t i o n of both 50 ml water volumes. All e x p e r i m e n t s w e r e run in d u p l i c a t e s and averaged. Results and d i s c u s s i o n Levels of c h l o r o p h e n o l s locations

in sediments and s u s p e n d e d m a t t e r from d i f f e r e n t

in the W e s e r e s t u a r y are listed in table 2. One sample of suspended

m a t t e r was taken in the Elbe e s t u a r y to c o n f i r m our s u s p i c i o n that c h l o r o p h e n o l levels in the w a t e r of the German Bight I) are i n f l u e n c e d by the Elbe river. These data are included for comparison. Pentachlorophenol

(PCP) g e n e r a l l y predominates.

The a b s o l u t e c h l o r o p h e n o l

levels v a r i e d w i d e l y so that m i n o r c o m p o n e n t s w e r e o c c a s i o n a l l y b e l o w the d e t e c t i o n limit.

2,3,4,6- and/or 2 , 3 , 5 , 6 - t e t r a c h l o r o p h e n o l s

(TeCP), w h i c h

w e r e not a n a l y t i c a l l y separated,

could always be found t o g e t h e r with PCP.

The high level of d i c h l o r o p h e n o l

(DCP)

in one sediment sample

be due to the p r e s e n c e of tubes of L a n i c e conchilega, r e v e a l e d an unusual h a l o g e n m e t a b o l i s m 5)

(No. 10) may

a polychaete,

that

Data on this s e d i m e n t are e x c l u d e d

from the f o l l o w i n g discussion. At first sight,

chlorophenol

levels in sediments appear quite arbitrary,

no r e l a t i o n w i t h site or time of s a m p l i n g can be detected. however,

There exists,

a p o s i t i v e c o r r e l a t i o n between the c h l o r o p h e n o l content and the

w a t e r - h o l d i n g c a p a c i t y of the sediments.

If c h l o r o p h e n o l mass

p l o t t e d versus p e r c e n t m o i s t u r e on a b i l o g a r i t h m i c scale, lines are o b t a i n e d sality.

and

(fig.

I)~ This r e l a t i o n s h i p

fractions are

roughly straight

is not based on strong cau-

C l a y m i n e r a l s and humic substances are the m a i n a d s o r b e n t s

ganic p o l l u t a n t s

in sediments;

b o t h take up water,

h o l d i n g c a p a c i t y of up to 90 % 6 )

for or-

and humus has a water-

In the m o i s t state the a d s o r b i n g c a p a c i t y

of pure clay is m o d e r a t e and g e n e r a l l y r e s t r i c t e d to p o l a r compounds.

Humic

s u b s t a n c e s have a high a d s o r b i n g p o w e r for a v a r i e t y of chemicals.

They are

known to bind h y d r o p h o b i c

as well 7)

substances

Studies on PCP a d s o r p t i o n have shown, q u a n t i t i e s of the p o l l u t a n t

like c h l o r i n a t e d h y d r o c a r b o n s

that h u m u s - r i c h soils take up higher

than m i n e r a l

soils 8). The lower c h l o r i n a t e d

p h e n o l s can be e x p e c t e d to behave similarly. To compare c h l o r o p h e n o l

levels and p a t t e r n s

p e n d e d m a t t e r and in water, calculated

in sediments with those in sus-

the a r i t h m e t i c m e a n of the mass fractions was

for each c o m p o u n d u s i n g a n a l y t i c a l data on the three s e d i m e n t

3/77

Sampling

78 e

533 e

-TrCP

-TrCP

-TeCP

-TeCP

PCP

2,4,6

3,4,5

2,3,4,5

2,3,4,6 2,3,5,6

-

-

18 e

-

-TrCP

2,4,5

56 e

-DCP

2,4 2,5

compound

1.78

11.3

26

UW-km a

% moisture

1

date

River

c)

Elbe

95 e

34e

1.75

10.7

3/77

76 e 534 e

-

-

-

4oe

408 e

1.99

20370 g

2110 g

1486 f

434 f

264 g

804 g

2092 f

1.25

6

19.1

3/77

53

259 e

51 e

81 e

mass

1.91

2357 e

350 e

iO1 e

295 e

897 e

fraction

1.69

sediments

35.0

average

1.78

18.7

5/77

65

8

16420 e

2230 g

2450 f

415 f

511 e

2070 e

iO10 f

73 e 412 e

-

-

-

-

138 e

from

1230 g

299 g

155 f

82 f

I12 g

629 g

391 f

15 e

15 e

134 e

-

-

-

1382 e

II

13800 f

450 f

950 f

330 f

180 f

2000 f

130 f

180

10/77

60

67.2~1.3 d

10/78

101

10/77

101

matter

14

3860 f

220 f

190 f

60 f

60 f

300 f

190 f

330

4260 f

iiO f

3OO f

50 f

60 f

330 f

300 f

50

190 f

890 f

50 f

120 f

17OO f

480 f

116

6800 f 14800 f

n.m.

n.m.

n.m.

n.m.

n.m.

n.m.

30

10/78

c

15

by GC/ECD,

concentration of suspended m a t t e r (wet w e i g h t in e s t u a r i n e w a t e r (mg/l))

10/78

13

e) q u a n t i f i e d

otherwise,

Suspended

12

samples,

indicated

limit

30

weight)

1.94

22.9

5/77

102

iO

detection

(pg/g wet

1.60

39.6

5/78

66 b

9

if n o t

5 separate

fairway

- = below

in p a r t i c u l a t e s

1.37

(g/ml)

60.4

5/77

57

7

in t h e

determined

= not measured,

d)

5/77

54

Sediments

5

n.m.

Cuxhaven,

collected

ESTUARY

were

WESER

samples

THE

averaged,

near

Bridge;

OF

of m o i s t

76.0

3/77

45

4

density

17.7

3/77

44

3

and GC/MS

estuary

Great

PARTICULATES

g) G C / E C D

34

2

IN

from Bremen

Bank,

by GC/MS,

Number

f) q u a n t i f i e d

b) B r e m e r h a v e n

= km d o w n s t r e a m

2 : CHLOROPHENOLS

a) U W - k w

TABLE

e

4~

No.2

115

Fig.

1:

Fig.

L e v e l s of c h l o r o p h e n o l s vs. % m o i s t u r e in sediments

2: E x p e r i m e n t a l d i s t r i b u t i o n of c h l o r o p h e n o l s b e t w e e n w a t e r and s e d i m e n t

100 a) % c h l o r o p h e n o l a d s o r b e d from e q u a l l y loaded w a t e r

Pg/g z~

80

/

i

I

~t

i

119

m

/ /

10000

6O

i:i:!:iii!i!i:!:

e,i

i!i!ii!i!iiiiii

~."

~

/ /

/ /

•40

'"'

:

iiiii!ii!i .......

::~

! v.v.v,',:':':':':':':': ipK iiiiiiiiiiiil,.,v,'.v.v . . . . . . . .>:.:.:.>:.:~ .................. .:i:i:i:i:i:i,:i:iSi:i:i:i .............. .'-'-'-'.'.'."

/

/ /

7

20

@

:.:-:.-::,.

.............................. .','.'.'.-,v,

i

16.0i

:. . . . . . .': . . . . .

::::::::::::::: v.v,v,~ ....... .:,:.:,:.:.:,:, :;:i:i:i:;:!:i~ ..:.:.:.:..:~ ..v.,...v,~.:.:..,.,... .v.,....z,~<,>>>>>: v . v . v . v :i:i:i:i:i:::i~ ':':':':':':': ~';':
/

i:i:i:i:i:i:i:i :i:i:i:i:i::::l :':':':':':': ~ ......

/ /"

[]

Chlorophenol

.'

..')

~ I"/

...'/l

/

O

,~,k

:

A

/"

z~

.3:

,.,.'.','..,': b,', .:,v.<

i:i:i:i:i:!:!:i: i:iii:i:i:!i!!~:':':':':+: ......... """

/ 1000

v.-.v.v."

7 . 0 i 5.

b)

//

I/~ /.~°

100-

% chlorophenol desorbed from loaded s e d i m e n t

i'

/o

,

/,.."/

/ 100" ',. /

/

..: /

/

/o : / / ,', ...." ii

,/' ..,~, /

0

./

80-

..I /o

~

"O

60-

..,: -II / [] / / @ , /

~_

..:" /~/ ~': / I i/./'" l/

~

t~

o

...... ......... ............. .......

• o • A

2.4-(2.5-) DCP 2.4.5-TrCP 2.4.6-TrCP 2.3.4.6-TeCP PCP

40-

~- 20

~3

~

•-

I-./

t,~

~..

.......

10

Moisture

(%)

100

Y////Z

......... ~/////, <<<<<~,........ ..... ~/,,~

0

10

,/i///z

....... ;S~%~; """"

Chlorophenol

116

No.2

samples

in w h i c h

and w a t e r Patterns

and levels

semblance, culates

river must

load

be denied,

matter

The o b s e r v e d chemi c a l

because

be e x p e c t e d

levels

and p a t t e r n s

The

in surface

for s e d i m e n t s

into the w a t e r phase

simplest water

though

column

Even

some m u t u a l

levels

The question,

to contain more

if s u s p e n d e d by the

of s u s p e n d e d

of high

than

re-

in parti-

transport

amount

in areas

matter 3).

turbidity,

10 % of the total

may be due to physical,

case

form

is adsorption.

stable

with

suspensions,

the aqueous

transient

transfer

due to tidal m o v e m e n t

chemical,

Provided

chlorophenols

phase.

This

further

adsorbed

on

is not n e c e s s a r i l y

of p a r t i c u a l t e s may

and bio-

that p a r t i c u l a t e s

from sediment

the a t t a i n m e n t

of

equilibrium.

Particulate/water values

distribution

for c h l o r o p h e n o l s

experiment

was

intended

in fig.

2. B e c a u s e

initial

chlorophenol

distribution experiment,

are

of the

ratios

ratios

shown

limited

adsorption

some

were

enter

solid phase

constants

taken

from L a n d o l t - B ~ r n s t e i n 9) were

because

for 2,6-DCP order:

2(3(4;

2,3(2,4. strong

more

recent

is most

consequently,

acid with

the d i s t r i b u t i o n

c oncl u d e

ratio

the order

for PCP

anion-exchange

Production,

transformation,

actions

also

formation

of 2,4-DCP

2,4,5-T

appearance

affect and

in a n a e r o b i c of PCP

The

available

PCP

for two chlo-

Dissociation

should

pK a

pK a value

have pK a values be:

in the

2,6<2,5

is a c o m p a r a t i v e l y

to recent

sources,

nevertheless,

than

that

for 2 , 3 , 4 , 6 - T e C P

with

other

are r e s p o n s i b l e

laboratory

that

In a g r e e m e n t

in the

i n v e s t i g a t o r s 8) we

for the h i g h e r

adsorption

water.

and d e g r a d a t i o n

chlorophenol 2,4,5-TrCP

and lower

shown

used to c a l c u l a t e

for d i c h l o r o p h e n o l s

processes

sediment

But

proving

molecules.

~enerally

our results.

is higher

by the

are noticeable.

incomplete.

are

(5 Dg/l) , the high

Monochlorophenols

of 4.8 a c c o r d i n g

of PCP at the pH of the e s t u a r i n e

may

are

too high.

as in nature.

phase

as u n d i s s o c i a t e d

be in accord w i t h

a pK a value

as well

that

sources

probably

This w o u l d

laboratory

generally

Results

(21 h) and the higher

of the pK a values

rophenols

values

time

and pK a

adsorption-desorption

not r e p r o d u c e d

features

common

the o r d e r

the averages,

processes.

in the aqueous

in the estuary

follows

from

3. A simple

the natural

equilibration

concentration found

calculated

in table

to s i m u l a t e

nevertheless,

exceptions

and

bear

in c h l o r o p h e n o l

the r e l a t i v e

is too small.

them should be in e q u i l i b r i u m true

in water. part

matter

Chlorophenol

(table

column.

actions.

appearing

however,

cannot

in the w a t e r

than

Data on s u s p e n d e d

in the same way

and s u s p e n d e d

an e s s e n t i a l

water

abundant.

averaged

of the water.

higher

take

in e s t u a r i n e

suspended

were

from those

are a p p r e c i a b l y might

were m o s t

estuary

in sediments,

distinct

particulates

matter

chlorophenols

of the W e s e r

levels

due to c h e m i c a l and p a t t e r n s

respectively

was

observed

chlorinated

phenols

and b i o c h e m i c a l

in the estuary.

from the h e r b i c i d e s

in our

The

2,4-D

l a b o r a t o r y IO) . The

on m i c r o b i a l

transformation

PATTERNS

6.0

2,4,6-TrCP

2,3,52'3'4:~-TeCP 12670

1546

5.4 5.5

5.3

1360

7.0

2,3,4,5-TeCP

PCP

310

3,4,5-TRCP

300

1170

7.4

2,4,5-TrCP

(68.4)

(8.3)

7.3)

I .7)

I. 6 )

6.3)

6.3)

1170

7310

260

480

150

100

880

210

(77.9)

(2.8

(5.1

(1.6

(1 .1

(9.4)

(2.2)

Matter

(Pattern

Suspended

in pg/g

water

No.

233.0

41.O

2.0

5.8

4.2

1.8

(81.O)

(14.2)

(0.7)

(2.0)

(I .5)

54

38

680

52

279

650

matter

No.

OF THE W E S E R

31

6.3

240

17

210

117

Suspended Matter Water

suspended

AND W A T E R

Sediment Water

and

MATTER,

7, 9,

(0.6)

Water

in Z%)

2).

4,

SUSPENDED

(ref.

on s e d i m e n t s

RATIOS.

IN SEDIMENT,

on e s t u a r i n e

from d a t a

Levels

7,7 7.4

Mean

from data

calculated

2'~-DCP,~

2) and

were

Sediment

(table

means

DISTRIBUTION

OF C H L O R O P H E N O L S

pK a

11,12,13

AND

AND PARTICULATE/WATER

Arithmetic

ESTUARY

3: MEAN LEVELS

Chlorophenol

TABLE

bJ

o

118

No.2

of lindane soil PCP aerobic within

and c h l o r o b e n z e n e s

is d e g r a d e d sediment

34 days

was

also

For

lack of

In aerobic

2,3,4,6-TeCP

and

chlorophenol

14C-labeled

PCP

mixture

in a n a e r o b i c

as 14CO 2 at 17 ° C w i t h i n

of PCP 15'16)

and

2,4,6-TrCP 16)

under

and a n a e r o b i c

2 , 3 , 6 - T r C P 13) . In anwas d e g r a d e d sediment

yielded

7 m o n t h s 14) . Total

simulated

natural

photo-

conditions

reported.

and their c hemi c a l almost

r e p o r t e d 11'12) and

40 - 60 % of an added

at 13,5 ° C 14)

24 % of the r a d i o a c t i v i t y degradation

was

to 2,3,5,6-

information

predecessors,

on the a b s o l u t e

and r e l a t i v e

introduced

the river,

and b i o c h e m i c a l

certain

disappear

that

within

into

processes

if e m m i s s i o n

cannot

were

amounts

the q u a n t i t a t i v e

be estimated.

stopped,

of c h l o r o p h e n o l s

It seems,

effects

of

however,

chlorophenols w o u l d c o m p l e t e l y

some years. Acknowledgements

The

authors

and Mr.

are g r a t e f u l

W. Pieles

by the D e u t s c h e

to Mr.

W. Drebing,

for e x c e l l e n t

technical

Forschungsgemeinschaft

Miss

R. Fr~hlking,

assistence.

Mrs.

The w o r k was

and the B u n d e s m i n i s t e r

A. Hansen, supported

fur F o r s c h u n g

und T e c h n o l o g i e . References I. W. E r n s t

and K. Weber,

VerSff. I n s t . M e e r e s f o r s c h . B r e m e r h . 1 9 7 8 , 1 7 , 4 5 .

2. K. Weber

and W. Ernst,

Chemosphere

1978,7,873.

3. W. E r n s t

and K. Weber,

Chemosphere

1978,7,867.

4. G. Eder,

VerSff. I n s t . M e e r e s f o r s c h . B r e m e r h . 1 9 7 9 , 1 7 , 2 2 5 .

5. K. W e b e r

and W. Ernst,

Naturwissenschaften

6. F.M. Swain, In O r g a n i c O x f o r d 1963.

Geochemistry

7. R.H. Pierce, Jr., 1974,38,1061.

Olney

8. J. Choi

C.E.

and S. Aomine,

Soil

and G.T. Sci.Plant

9. L a n d o l t - B S r n s t e i n , Zahlenwerte Springer, B e r l i n 1960. 10. G. Eder, R. Engst,

12.

K. B a l l s c h m i t e r ,

R°M.

Murthy,

14. G. Eder,

1978,65,262. Breger,

Felbeck,

Macholz Ch. D.D.

Unglert

Geochim. C o s m o c h i m . A c t a

Nutr.,1974,20,371.

und Funktionen,

and M. Kujawa,

Kaufmann

ed.)pp.93-94,Pergamon,

Jr.,

6.Aufl.

VerOff. Inst. M e e r e s f o r s c h . Bremerh. 1980,

11.

13. N.B.K. B14,1.

(I.A.

and G.F.

Fries,

7.Teil,p.878

in press.

Chemosphere

and P. Heizmann,

II.Band

1977,6,401.

Angew. C h e m . 1 9 7 7 , 8 9 , 6 8 0 . J.Environ. S c i . H e a l t h

1979,

unpublished.

15. A.S. W o n g and D.G. Crosby, In P e n t a c h l o r o e h e n o l P l e n u m Press, N e w York 1978. 16. D. Kotzias,

W. Klein,

F. Lotz,

(Receivedin Germany 31 Jantmry 1980)

S. Nitz

(K. R a n g a

and F. Korte,

Rao,

ed.)pp.19-25,

Chemosphere

1979,8,301.