Sorption and mobilization of mercury in peat soil

Chemosphere,Vol.12,No.ll/12,pp Printed in Great Britain

1575-1581,1983

0 0 4 5 - 6 5 3 5 / 8 3 $3.00 + .OO © 1 9 8 3 P e r g a m o n Press Ltd.

SORPTION AND MOBILIZATION OF MERCURY IN PEAT SOIL Martin

Lodenius*,

Ari

5epp~nen

&

Antti

Uusi-Rsuva

Department of Environmental Science and Isotope Laboratory Faculty

of A g r i c u l t u r e

University SF-O0710

and Forestry

of Helsinki Helsinki

71

Finland

The sorption, lysimeters.

Most

The leaching duced

leabhing

and e v a p o r a t i o n

of the mercury

of mercury

by the addition

was

was

adsorbed

increased

of acid

rain

of mercury

at the

top of the peat

by irrigation

or

was studied

or chloride

in peat

soil

columns.

addition

and

re-

fertilizers.

Introduction

The construction causes

a mobilization

elevated

mercury

contents

have

mercury soil

discharge.

humus

and

the

eat

fish

mercury

and

lakes

may

related

of the L,~ater level which 1-5

is revealed High

mercury

without

be m o b i l i z e d 6-7

operations

as

any

known

from

the

.

high mercury contents are often from lakes with low p H - v a l u e s 8-9 In m a n - m a d e lakes the mercury content of fish is

that

of natural

chloride

of mercury

investigation

but

amplitude

of Finnish

of the regulation man-made

lakes

values

about

soils.

be extended

values are lower, 10-11 are higher adsorbed the

results

to

cover

meters.

1575

to the organic

factors

The

affecting

presented

several

and

differs

pH and oxygen

reversibly

is known

in peat

will

the

quality lakes:

and nutrient

Mercury is strongly 12-14 and water , but little and leaching

who

soil,

contents

matter 4. The water

iron,

that

and bogs

of organic

solids,

the control

from u n r e g u l a t e d

assumed

in forests

and

inundated

and people

by the age of the basin,

from

the

in fish

influenced

icantly

lakes

from

in fish

found

It has been

digging

Fish with and high

contents

also been

by ditch

of man-made

of mercury

here

the

the amount signifsuspended

matter

in soil

the sorption are p r e l i m i n a r y

physico-chemical

para-

1576

Material

and methods

lhe peat used in our experiments Finland

and was slightly h u m i f i c a t e d

directly taken

from the samples,

originated

from Torronsuo

white Sphagnum peat

extractable

chloride

lysimeter

columns,

cm. 900 g of peat was pressed 203Hg-mercuric tracer.

10.5 ~Ci

Peat was applied

(code HB5 2; Amersham Co., England)

acetate and the total mercury

nation 15

in room temperature

1.5 g KCI was added to four columns the formation of m e r c u r y - c h l o r i d e

(KNO 3) were mended

precipitation.

Phosporous

added to four columns

for the forest

to detect

any possible

20°C).

concentration

is theoretically

possible

addition was a thousandfold

(Ca3(P04)2),

of Finnish mires

that

potassium and nitrogen

in amounts c o r r e s p o n d i n g

fertilizing

contami-

(approximately

to get a 0.02 M chloride complexes

in the pH-range of peat soils 16. The chloride of S c a n d i n a v i a n

was used as

addition was lO0 pg per column.

in order

The experiment was performed

6.3

The tracer was mixed ~,Jith

To four columns no additions were made

in which

into 16

of 0.8 l in each column.

was added superficially to 12 columns.

inactive mercuric

The sample was

the length of which were 40 cm and diameter

into a volume

acetate

(v. Post H2, pH 3.3

12 mg l -l d.w.).

from the top layer of the bog and deep-frozen.

polyethylene

in south west

to the amounts

recom-

(5.5 mg P, lO.1 mg K and 26.4

mg N per column). During (8 columns) responds

34 days water was added s u p e r f i c i a l l y

or fifteen times

(8 columns).

to 60 mm of precipitation.

the other artificial

acid rain

50 u 1 -I, 40 ~ M

meter

columns were placed on funnels collecting

sured

and analysed 4-5 times during

the leachates were measured

tioned

at the wavelength

into a cysteine

no mercury

(Fig.

(Sephadex

experiment

solution

contained

intended collect

1-1.

that

solution

The bromide

The volume of the traps was

the evaporated water daily.

to collect the evaporated

frac-

the evaporated

The 1% c y s t e i n e - h y d r o c h l o r i d e

in a 0.2 M Iris ( h y d r o x i - m e t h y l a m i n o m e t h a n e ) - b u f f e r 17.

kept at I0 ml by compensating

SF-16) was

An acid KMnO4-tra p ensured

~,Jas made

lO0 g KBr I -I and 15 g HgBr

of

100).

funnels collecting

trap and a HgBr-KBr-trap.

passed to the sewage system.

which ~ere mea-

270 nm (Spektrofotometer

filtration

and

lhe lysi-

I). The absorbances

A leachate from a separate

in samples of 20 ml using gel

NO3 I-i).

the leachates,

the experiment

The columns were covered with glass gases

seven

Half of the columns got distilled water

(pH 3.9, 43 ~ M

using distilled water as blanks.

to the peat columns

Each addition was 160 ml, ~,~hich cor-

The cysteine

trap was

Hg 2+ and CH3Hg +, and the bromide trap to

the evaporated Hg 0 and (CH3)2Hg 18 At the end of the experiment

the columns were deep-frozen

3.7 cm 3 were taken at distances of 2 cm. the peat samples were measured

The trap solutions,

by a g a m m a - s a m p l e

counter

and samples

the leachates

(Ultragamma

1280;

and

of

1577

"T" Fig. The

i. lysimeter

columns the

used

experiments.

l,lall~c Ca., 300 as

in

s and that

Finland).

the

The

counting

added

volume

of the

efficiency

to the c o l u m n s

samples

a3 ! 1.3

were

used

as

5.

was

5 ml,

Samples

the m e a s u r i n g

with

the

same

time

activity

standards.

Results

In the the

peat

sorbed

trap

to the ~ a l l s Most

layer

four columns w i t h o u t

samples,

of

the

added

mercury

columns

(Fig,

of m e r c u r y the

of

the

the

columns

smaller

mercury

was

and

leached

(270

a binding

rim) and

of m e r c u r y

molecular

acid

From but

in the

all

cysteine

the

4).

was

the

added

found

mercury

the u p p e r m o s t caused

Mercury

n=28)

of

was

Most

The

the

in ad-

acid

was

cm

rain

leached

fertilized

from ones. and

added.

between

leachates,

of these

the m e r c u r y

3.5

increased

significantly

~as

found

in the

an

was

decreased

to ~'~hich c h l o r i d e

substances. most

to

except

leaching

(r = 0.563,

(about

was

labelled

leaching.

soil.

(203Hg-content)

to w h i c h

(Fig.

peat

columns

(Fig.

no a c t i v i t y any

addition

a decreased

the

mm)

~hile

Fraction

activity

traps

the

~as

adsorbed

chloride

mm w a t e r

humic

acids

columns,

measurable

from

Nor

strongly The

to

(420

activity

to

fulvic

Io~

~as

correlation

the

small-molecular humie

900

additions

columns.

fertilizing

addition only

tracer

leachates.

2).

of m e r c u r y

to w h i c h

water

A significant bance

the

adsorption

any or

polyethylene

peat

leaching

all

of the

of the

enhanced

At

solutions

the

which

substances adsorbed

to

absorimplies were the large.

3).

mercury 0.01%

Hore

was of

mercury

added,

~he

total

mercury

was

addition

~0.01 - I % of the

evaporated.

was

A

accumulated

total

addition)

1578

Hg pA

DISTILLED WAFER 900 MM

6 ¸

L,!

\'b x.\/\ 'Xc/~ • ~:-o

.\

"\~"

CONTROL

\.'° C0~J::t

\ FERTILIZED

2.

10

0

20

30

,_, FE;-:_:ZED

2-

cm

10

0

2'0

30

cm

H9~w ACID RAIN

pA

DISTILLED WATER

420 MM

420 MM 6

~e '~

\

5

4

~'O. O

°Xo

qxe~ * ~,A ~F*\" x~L

3.

CL-

C,-

y~ CONTROL

2.

2-

Y FE--:_:2ED ~ FERTILIZED 0

Fig. at

2.

The

different

activity

of

10

20

30

amount

of m e r c u r y

depths

of

the

peat

the 2 0 3 H g - a d d i t i o n

cm

(as

O

a logarithm

columns ~,~as 6.7

at pA.

the

of end

1'0

20

the

activity

of

the

30

cm

(cpm

experiment.

of

203Hg)

The

1579

was

usually

izers

found

increased

from the bromide

the amount

traps.

of mercury

The addition

trapped

of chloride

by the bromide

or

fertil-

solutions.

Abs. % -

- 70

Hg cpm

i00

80

HG

/

= 60

" 50

80" =

60"

40

-. 30

40-

\

If

\\ "\

20-

-

20

-

10

t Fig. 3. The differentiation of mercury (cpm 203Hg) in the water leached in six days through a peat column in relation to the absorbance (270 nm) of the leaehate The leachate was gel filtrated into samples of 20 ml.

Discussion

The amount with humus

the amount

of leached

in the transport

to both

promote

ca1 methylation mote

of leached

mercury

organic

of mercury

in our experiment

matter, which between

soil

correlated

implies

positively

the essential

and water.

Humus

has

role

been

of

found

the leachability of mercury 17' 19-20 and to cause a non-biologi21-22 of mercury . A high pH-value and chloride content will pro-

the solubility

of mercury 23-24

stronger

binding

promotes

the b i o a c c u m u l a t i o n

to the organic

and an increased

matter

of mercury.

(soil, Acid

acidity

water

humus

rain

reduced

obviously

causes

and organisms), the

a

which

leachability

of

1580

Hg !

Hg

DISTILLED WATER

pA

pA

ACID RAIN 900 MM

LEACHED B EVAPORATED (CYSTEINETRAP)

3

3"

2.

2'

1'

CONK ' RDL

CI"

FERTILIZED

Hg I

DISTILLED WATER

pAI•

420 MM

CONTROL ElHg I

FERTILIZED

ACID RAIN

pA,

420 MM

I ~ LEACHED 4EVAPORATED (CYSTEINETRAP) I EVAPORATED (BROMIDE TRAP) 3.'1

BB

I~

3

m

1

2

1"1

~

CONmoL Fig.

~

CS"

4. The amount of mercury

leached

through

The activity

FERTILIZED

C'O~.~OL

(as a logarithm

the peat columns

or trapped

of the 203Hg-addition

CS-

of Lhe activity

by the cysteine

was 6.7 pA.

FERTZLZZEO (cpm) of 203Hg)

or bromide

traps.

1581

mercury

from our peat

mobilization

soil

of m e r c u r y

In our e x p e r i m e n t but

increased

microbe

mercury

it is p o s s i b l e

Our results

of mercury. indicate

at the pH and c h l o r i d e

despite

as road d e i c i n g

of the strong

binding

rain could

fertilizers

reduced

This may be a result

that

ranges

selts may p o s s i b l y

that acid

cause

a

soils 25-26

the c h l o r i d e - f r e e

the e v a p o r a t i o n

activity.

occurring

but

from mineral

the m e r c u r y - c h l o r i d e

of peat

may

influence

to the o r g a n i c

mobilize

the l e a c h a b i l i t y of s t i m u l a t e d

mercury

matter,

complexes

the m o b i l i t y lhe c h l o r i d e s

of used

from the soil 27.

Acknowledqements

We are i n d e b t e d the A c a d e m y

of F i n l a n d

to the F o u n d a t i o n for

financial

for R e s e a r c h

of Natural

Resources

and

support.

References

i. 2. 5. 4.

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5 July

1983)