Mobility and retention of heavy metals, arsenic and sulphur in podzols at eight locations in northern Finland and Norway and the western half of the Russian Kola Peninsula

JUURNAl OF 6 EXPlURATlOW

ELSEVIER

Journal of Gewhemical

Exploration

59 ( 1997) 175- 195

Mobility and retention of heavy metals, arsenic and sulphur in podzols at eight locations in northern Finland and Norway and the western half of the Russian Kola Peninsula Marja Liisa R&ken a Geological b Kola Science Centre. Institute

a.*, Galina Kashulina ‘, Igor Bogatyrev

Suwey of Finland, of North Industrial

’ Kolu Geological

Bor 1237. FIN-7021 Ecological

Information

Problems,

and Laboratop

Received 27 August 1996: accepted

I Kuopio,

Finland

Fersmun St. 14, 184200 Apatig.

Center, Aparity.

’

Russicr

Russia

18 March I997

Abstract The mobility and retention of heavy metals, arsenic and sulphur in podzols from eight areas located north of the Arctic Circle in Finland, Norway and Russia were determined by analyzing the < 2.0 mm fraction, using an ammonium acetate (pH 4.5) extraction in addition to a concentrated nitric acid digestion for the humus samples, and a hot aqua regia digestion for the mineral soil samples. Total C, H and N concentrations were determined in humus and mineral soil samples with a CHN analyser. Ni, Cu. Co and As were strongly enriched in the humus layer in the contaminated sites (Monchegorsk, Kurka, Zapoljamij) when compared to their concentrations in the parent tills and in podzols from the background sites. In most study sites the illuvial layer showed a low capacity to retain the metals and As, the exception included a strongly eroded profile at Monchegorsk, where Ni was tightly fixed in the illuvial layer while Cu was mobile. In contrast to metals, airborne S was not accumulated in the humus layer, but was accumulated in the illuvial layer, more markedly at eroded sites than in places where the humus was covered as at Monchegorsk. 0 1997 Elsevier Science B.V. Ke,vwordst

podzols; geochemistry;

heavy metals; arsenic; sulphur; mobility

1. Introduction The Ni-Cu industry in Russia, established about 70 years ago in Nikel, Kola Peninsula, over 50 years ago in Monchegorsk and about 40 years ago in Zapoljarnij, has caused damage to the environment on an immense scale (Fig. 1). Tikkanen and Niemela (1995) estimated that industrial deserts, entirely or

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almost entirely void of vegetation and surrounding the smelter towns, total 39,000 km’. Visible vegetation damage is also seen in the surroundings of the ore-roasting plant at Zapoljamij. In 1994, the relevant year for the present investigation, annual emissions from the Ni-Cu smelter complex at Nikel and at Monchegorsk and the Ni ore-roasting plant at Zapoljamij, include about 296,000 tonnes of SO,, 1700 tonnes of NO,, 1900 tonnes of Ni, 1100 tonnes of Cu, 94 tonnes of V,O,, and 92 tonnes of Co (Report of the Murmansk region Committee of Ecol-

Elsevier Science B.V. All rights reserved.

SWEDEN

Fig.

I, Location

of sampling sites in northern Finl?nd and Norway

and in the western half of the Kola Peninsula. Russia. The factory symbols show the location of Ni-Cu

melters

at Monchegorsk

and Nikel.

ogy and Nature Resources, 1995). Prevailing southwesterly winds distribute the pollution plume mainly in a northeasterly direction towards the Barents Sea (,&yr& et al.. 1997b). The Geological Surveys of Finland (GSF) and Norway and the Central Kola Expedition are at present undertaking a large environmental geochemical mapping project in an area extending from 24”E to 35”30’E and south towards the Arctic Circle in Finland and the southern border of the Mormansk

region in Russia (see http://www.ngu.no/Kola). In 1994. as a part of the project, ten different sampling media. including podzol profiles, were collected in eight locations in Russia (Zapoljamij. Monchegorsk, Kirovsk, Kurka). Norway (Skjellbekken), and Finland (Kirakka, Naruska, Pallas), see Fig. I and Tables 1 and 2. The main aim of the study is to identify the peculiarities of elemental distribution in various media at various levels of pollution and with different geological settings and thus varying background levels. Here the podzol profile data were used to illustrate: ( I ) the contamination in terms of total and leachable components; (2) the distribution of trace elements (As. Co, Cr. Cu. Mn. Ni. Pb. S. V. and Zn) in the profiles: and (3) trace element variations in relation to bedrock character. Podzols are the main pedon types in forest zones of northern Arctic areas and they are usually developed on til1.s. consisting mostly ot’ fresh (unweathered) rock material mechanically comminuted by glacial erosion. Due to the young age (2 9000 years) or podzolized tills in northern Europe, their total content of trace elements essentially reflects the composition of the bedrock (Rlisgnen. 1994; Kihkiinen. 1996). Here the soil age was evaluated from the dates (9100 B.P. in western and 9800 B.P. in eastern Finnish Lapland) of the ice retreat in northern Europe (see Johansson, 1995). Since chemi-

Table 1 Overview of the main characteristics of the eight study locations Site

Bedrock types ”

Vegetation

Annual precipitation (mm)

Monchr,qwsk

~IIV~I Basic igneous rocks. acid and

MI Monchegorsk

Mostly ban-cn (originally Boreal coniferous fore\t)

391 502

intermediate volcanic rocks M2 Kurka

Basic igneous rock5 and gneis\

Boreal conil&us

M3 Kirovsk

Alkaline igneous rocks. ultrabasic

Mountain: birch >> spruce

forest. \prucc > birch

SO?

and basic volcanic rocks Nikel-Zapoljnmjj

urew

N I Zapoljarnij

Gneiss and granite

Tundra forest: birch

4.51

N2 Skjellbekken

Metasedimentary and

Boreal coniferous forest: Pine z+ spruce and birch

322

metavolcanic rocks N3 Kirakka Background

Granite

Tundra forest: pine and birch

mw~ in Fit~lmd

FI Naruska

Gneiss and amphibolitc

Boreal coniferous forest: ~~I-UCCand pine > birch

F2 Pallas

Quartzite and amphibolite

Boreal coniferous forest: spruce and pine

” Pavlov et al. (1996).h

From the closest meterological station (data from 19YJ).

h

M.L. Riiisiinen

Table 2 Overview

of the main characteristics

(FAO-Unesco,

Monchegorsk

M3

Nikel-Zapo(jarn{j

N3 Background

Fl

F2

” FAO-Unrco

study

locations.

Exploration

177

5Y (1997) 175-195

the soil classification

is based

on the FAO Soil Classification

type

”

Sampling site

Profile No.

Glacial depoait/podzol

2P36 2P37 2P38 4PO6 4P38 4P39 3Pl5 3P5 I

Basal till/haplic Basal till/haplic Basal till/ferric h Basal till/haplic Melt-out till/ferric Melt-out till/haplic Basal till/haplic Melt-out till/haplic

Top of the hill. 158 m a.s.1. Top of the hill, 180 m a.s.1. Gentle slope. 185 m a.s.1. Foot of the hill. I55 m a.s.1. Gentle slope, 270 m a.s.1. Flat plain, 210 m a.a.1. Flat terrace, 345 m a.s.1. Flat terrace. 420 m a.s.1.

Melt-out Melt-out Melt-out Melt-out Melt-out Melt-out Melt-out

Top of the hill, 160 m a.s.1. Flat valley, I05 m a.s.1. Gentle slope. 95 m a.s.1. Top of the hill, I15 m a.s.1. Top of the hill, I25 m a.s.1. Gentle slope, 120 m a.s.1. Gentle slope, 125 m a.s.1.

area

M2

N’.

of the eight

ofGeochemical

1988)

Ml

Nl

et al. / Joumnl

orea

1P28 IP38 5P37 5P39 5P40 5P4l 6Pl2

till/haplic till/haplic till/ferric till/haplic till/ferric till ‘/ferric till/ferric

nrra in Finland

7PO5 7Pl8 7Pl9 8Pl3 XPl5 8Pl8

Basal till/haplic Melt-out tiil/haplic Bahal till/haplic Melt-out till/haplic Basal till/haplic Melt-out till/haplic

( 1988).h No 0 and E layer.‘ Mixed with wlphide-rich

cal differentiation into podzolic layers requires 5001000 years, as suggested by Aaltonen (1952) and Petaja-Ronkainen et al. (1992), the duration of soil development was estimated by subtracting 500 years from the dating of the ice retreat (see also Raisanen, 1996). Due to pedogenic processes, elements are variably differentiated with depth within the podzol profile (RlisPnen, 1994). Some elements are mobilized and taken up by plants, leading to their accumulation in the uppermost organic layer of the podzol profile, while others are leached out of the upper soil layers and precipitated in the illuviated layers or washed out into the groundwater (Berrow and Mitchell, 1980). The mobility of elements in soils, however, is strongly dependent on their specific chemical forms and their ways of binding. The biological and ecological effects of the elements as well as their behaviour and pathways in the terrestrial environment can be assumed to be more related to alterations in

Flat plain, 270 m Gentle slope, 305 Gentle slope, 300 Flat plain. 335 m Gentle slope, 380 Flat plain, 325 m

a.s.1. m a.s.1. m a.s.1. a.a.1. m a.s.1. a.s.1.

saprolite.

the soluble and mobile fractions than to changes in the total concentrations. It is hence important to determine, in addition to total concentrations, which part of this total pool of elements is mobile under particular conditions (Raislnen et al., 1993). A leach with 1 M ammonium acetate buffered with acetic acid to various pH (regularly 7.0 and 4.651, depending on the substrate (soil) pH, is frequently used in a single extraction procedure. Using ammonium acetate the base cations in the soil samples are released from exchangeable sites and are therefore only relatively little affected by pH. In contrast. Fe and Al are supposed to be released mainly from precipitated compounds such as hydrated oxides and hydroxides and are thus strongly affected by pH. Most heavy metals also react strongly to the pH of the solution used for extraction (Andersson, 1976). By buffering this solution to pH 4.5, which is roughly the pH of the snow meltwater and soils in the study area (Reimann et al.. 1996~1, an operationally defined

178

M.L. Riiisiinen et 01. /.lournul

qf Geochemid

fraction of elements as an estimate of the effects of snow meltwater on soils can be determined. 1.1. Geolngv and soil types The overview of the geological setting in the eight locations is described in Table I (Pavlov et al., 1996). On the basis of the main bedrock type, the study sites can be grouped as follows: ultrabasic N3 = Ml

-basic ==M2>N2>

Fl >NI

-acid >F2=N3

The Kirovsk catchment (N3) represents a special environment located on the alkaline massifs of Khibiny. The alkaline intrusion consists of various types of nepheline syenites and ijolites (see also Table I ; Gerasimovski et al., 1974). The overburden in the areas studied is mainly basal till (Pavlov et al., 1996). The surficial till, from which the podzols studied here have been developed, was in most cases meltout till (Table 2). Due to meltwater sorting during the glacial deposition, the meltout till contains less clay-size fraction and is richer in quartz and other resistant minerals than the basal till (REidnen et al., 199.5). At most sites the podzol type was a haplic podzol that has a continuous albic horizon (eluvial layer, E), thicker than 2 cm, and a distinct spodic horizon (illuvial layer) that is rich in organic matter (Bh = B 1) with or without an underlying (Bs = B2) horizon rich in inorganic sesquioxides. The ferric podzol, the other common podzol type in the subarctic area of northern Europe, is richer in inorganic iron than the haplic podzol (Table 2; FAO-Unesco, 1988). 1.2. Geochemistry

and processing

of the Ni-Cu ores

The metallurgical industry in Nikel, Zapoljarnij and Monchegorsk, processes both local ore from deposits in the Pechenga Zone and ore from deposits in the Noril’sk Province in western Siberia. The Pechenga Zone is an Early Proterozoic rift zone containing a thick sequence of picritic and tholeiitic volcanic rocks, minor intrusive bodies and intervening sedimentary units (Melezhik et al., 1994a). The ores, hosted in gabbro-wehrlite intrusions, include disseminated, breccia and massive ores (Melezhik et al., 1994b). Although mineralizations had been re-

Exploration 59 C1997) 175 19.5

ported earlier. the first major deposits in the Pechenga Zone were discovered during the 1920s. Production commenced in 1932 and has continued up to the present. Several open-pit and underground mines are in operation. The Pechenga ores contain I .5-2% Ni, 0% 1.8% Cu and 3-5s S. Annual production is estimated to be 30-35,000 tonnes Ni metal (Melezhik et al., l994b). The Noril’sk Province includes several groups of ore bodies in picritic-doleritic sills associated with the Triassic Siberian flood-basalt province. The province contains a wide range of ore types, including large volumes of massive ore. The type of Noril’sk ore processed at Nikel is thought to contain. on average. 2.35%, Ni and 2.7% Cu in ore with 70% sulphides (Boyd et al.. 1996). The smelter at Nikel processes ore from Noril’sk, rich Pechenga ore, concentrate produced from local ore, and pellets from the Zapoljamij roasting plant (which processes local ore alone). The smelter complex at Monchegorsk began production in I938 using only local. low-S (about 6.5% S) ore, and since 1968, S-rich (up to 30% S) ore from Noril’sk has been also smelted (Alexeyev. 1993). At present, the metallurgical plants process pellets from Zapoljarnij, matte from Nikel and matte and ore from Noril’sk (Boyd et al.. 1996).

2. Materials

and methods

2.1. Sampling Two to five sampling sites were selected from a small catchment area, of which the surface area varied from I5 to 35 km’. The main criteria for selection within a catchment were the elevation (low and/or medium, high), soil type, vegetation and degree of ecosystem damage (Table 2). Exceptionally, at site N3 only one profile was sampled due to the abundance of outcrops of bedrock and till rich in stones and boulders. The parent soil that was preferred for the podzol profile sampling was sandy till with a varying content of stones. To represent the natural S-rich setting. one profile (5P41 in Table 2) at site N2 was sampled from till mixed with sulphide-rich saprolite (black schist rocks).

M.L. Riiisiinen et ul. /Journal

of Geochemical Exploration 59 ( 1997) 17S- I95

Samples of the podzol horizons (0, E, Bl,. . , BC, BC2,. . . , Cl,. . ) were taken from a spade-dug pit. The depth of the pits varied from 50 to 100 cm, depending on the thickness of the podzolic (E, B 1, B2) layers and the location of parent till at the bottom of the pit. An exceptional podzol profile (2P38) representing strongly eroded soil was sampled in the Monchegorsk location (Table 2); the soil lacked the 0 and E layer. 2.2. Chemical analysis All samples were dried at a temperature < 40°C at the Chemical Laboratory of the Geological Survey (GSF). Mineral soil samples were sieved to < 2.0 mm; before sieving, humus samples were homogenized by milling with a domestic blender with contamination-free polycarbonate blades. The element concentrations of the mineral soil samples were analysed with hot aqua regia and those of humus samples with concentrated nitric acid (Niskavaara, 1995). A 2.0-g subsample of the < 2 mm fraction of the mineral soil was mixed with 9 ml concentrated HCl and 3 ml concentrated HNO, (aqua regia) in a borosilicate tube. The mixture was left at room temperature overnight and then heated to 90°C for 2 h in an aluminium block. The digest was diluted to 60 ml with deionized water, mixed thoroughly, decanted to polystyrene tubes and centrifuged. The clear solution was analysed with ICP-AES for 31 elements; in addition, As, Cd and Pb were determined with a graphite furnace -AAS. A humus sample (0.5 g) was mixed with 10 ml of concentrated nitric acid, digested in a microwave oven and diluted to 50 ml with deionized water (Niskavaara, 1995). The clear solution was determined with ICP-AES for 30 elements and with ICP-MS for As, Cd, Co, Cr, Ni, Pb and V. Element concentrations determined with the concentrated HNO, digestion method can be considered as total element contents as long as the humus does not contain mineral fragments. Element concentrations in the hot aqua regia leaches are not precisely total concentrations, since not all minerals are decomposed during the digestion (Fletcher, 1981). For the purposes of the present study, however, the results obtained for heavy metals, As and S in the aqua regia extraction are considered as total concen-

119

trations. This may be justified due to the fact that hot aqua regia totally decomposes sulphides, trioctahedral micas, clay minerals and amorphous compounds, which are the major sources of these elements in tills (RBisBnen et al., 1992). Total concentrations of C, H and N in the humus and mineral soil samples were determined with a CHN analyser (Leco CHN-600 apparatus). The method used here for determining the element concentrations in the easily leachable (mobile) fraction of the humus and mineral soil samples is based on extraction with buffered ammonium acetate (Raisanen and HlmalPinen, 199 1). A 6-g subsample was extracted in a horizontal shaker for 2 h with 30 ml of 1.0 M ammonium acetate solution buffered with acetic acid to pH 4.5. After filtration through a 0.45 Frn membrane filter, solutions were analysed with ICP-AES for 26 elements and with a graphite furnace -AAS for As and Cd.

3. Results and discussion A typical podzol profile is characterized by the presence of a poorly decomposed organic layer (0, humus), a light eluvial (E) layer, brown illuvial (B 1, B2) layers that are considerably enriched in amorphous Fe, Al, Si and organic matter (leached from the E layer), and the yellowish-grey or greenish-grey lower layers of less altered parent till (BC, BC2.. , Cl >. Since Fe and Mn hydroxides have a high sorption capacity for trace metals (Coughlin and Stone. 1995) it could be expected that the illuvial layer retains airborne as well as native heavy metals when they are leached from the surface layer (Kabata-Pendias and Pendias, 1992). Kabata-Pendias and Pendias (1992) have nevertheless pointed out that the humus layer is the most significant sink for trace elements in polluted soils. Due to the above factors, for data-processing purposes soil samples of the profile were grouped here into a humus layer, an eluvial (E) layer, two illuvial (B 1, B2) layers, and an upper transitional zone (named here BC) layer and parent till (C). Concentrations of heavy metals, As and S did not markedly vary in the lower layers below the BC layer, hence samples from the lower transitional zone (BC2, . . . Cl, . > layers were grouped with the C layer or

180 Table Means

3 of the concentrations

soil (E. B I. B2, BC. Horizon

II

of Ni, Cu and Co in the aqua regia (total)

C) layers

at the study

acctatc

total

leach

(mg/kg)

(mg/kg)

(leach)

extracts

in the humus

(0)

and mineral

co

CU

Ni

Monchegorsk

and ammonium

location\

% leach

total

leach

(mg/kg)

(mg/kg)

2590.00

454.00

I x.23

103.10

6.67

6.47

33.70

lh.55

3.47

0.37

IO.62

I-IlY

k leach

total

leach

(mg/kg)

(mg/kg)

Q leach

area:

MI Monchqor.vk

0

2

104.55

4.73

E

2

2205.00 28.95

7.5’)

26.20

72.40

10.80

BI

2

68.95

15.66

42.65

6. IX

I I.69

0.5’)

5 .os

B2

2

59.00

4.4 I

1.37

33.60

0.53

1.5X

14.77

0.26

1.79

BC

2

S6.65

3.22

5.68

37.20

0.6Y

I .x5

13.12

0. I x

I.32

C

7

52.3

2.40

4.59

3X.Y1

0.3X

I.24

13.31

0.13

0.96

0

3

669.00

71.87

10.74

377.61

40.03

10.60

29.07

5.64

19.39

E

3

7.22

2.52

34.93

4.27

0.82

IY.1 I

I .SY

0.22

13.97

BI

3

25.47

I .49

S.83

25.Y7

0.89

3.44

x.09

0.19

7.30

82

2

27.75

0.94

3.40

34.75

I.41

-1.12

8.81

0. IS

I .70

BC

3

33.57

0.30

0.90

17.03

I.14

2.42

9.79

0.06

0.65

C

8

34.85

0.26

0.76

60.7 I

0.6X

I I2

12.72

0.05

0.37

0

2

36.30

2.89

6.74

26.YO

I .04

3.x5

3.35

0.30

X.85

E

2

3.27

0.36

I I.10

2.16

0. I x

x.17

I .55

0.05

3.23

BI

2

20.35

0.15

0.75

18.20

0.27

I .1X

6.X5

0.06

0.90

B?

2

17.70

0. I4

0.7X

14.00

0.28

I .YY

6.40

0.07

I.15

BC

2

18.20

0.03

0.14

23.50

0.62

2.62

7.31

0.04

0.5x

C

5

Il.54

0.03

0. I4

3 I .36

1.18

3.7X

7.51

0.03

0.36

I .7x

3.62

14.90

6.05

40.60

0.13

IO.25

I .4x

0.3 I

20.92

8.5 I

0.05

I

M2 Kurka

M3 Kirwhk

Nikel-Zapoljarnij NI Zqoljmi~ 0 2 E 2 BI 2 B2 2 BC 2 c 4

area: 359.50 7.74 16.25 20.55 23.20 29.00

87.65

24.3X

3.48

W.Yh

0.69

4.26

21.25

0.45

2.1 I

0.26

I .26

33.85

0.67

I .52

10.72

0.03

0.24

0.86

65.65

0.95

I.42

12.80

0.05

0.36

0.9 I

104.10

I.61

I 53

14.77

0.04

0.29

0.2

I

0.26

39.20 I .26

0.62

N2 Skjellhekkrn 0

3

4.02

12.13

23.43

0.37

1.77

0.39

22.18

E

3

1.15

0.18

16.01

0.25

0.06

23.Y2

0.81

0.03

3.87

BI

3

9.64

0.24

2.45

7.77

0. I6

7.03

6.36

0.0x

I .2s

82

2

14.13

0.1

0.X0

16.53

0.35

7.10

9.55

0.1s

1.60

BC

3

19.10

0.13

0.66

3 I .60

0.53

I.69

10.00

0.17

I .70

C

IO

29.X2

0. IO

0.33

46.2 I

0.60

1.2)

13.95

0.09

0.67

33.17

I

1.5X

N3 Kirukku 0

I

6.4 I

0.52

8.13

6.77

0.04

0.59

0.44

0.09

20.05

E

I

0.50

0.03

5.00

0.25

0.05

20.80

0.25

0.02

9.52

BI

I

4.45

0.06

I .34

3.21

0.08

2.18

2.67

0.03

I .23

B2

I

6.07

0.03

0.4 I

5.40

0. I4

2.52

3.05

0.03

I.14

BC

I

4.74

0.03

0.53

6.55

0. IX

2.75

3.06

0.05

I.53

C

3

5.85

0.03

0.33

13.47

0.24

1.77

4.52

0.03

0.57

M.L.

Table

Riiisiinen

et al. /Journal

ofGeochemical

Exploration

5Y

CI YY7)

175-

181

lY5

3 (continued)

Horizon

co

CU

Ni

n

total

leach

(mg/kg)

tmg/kg)

B leach

% leach

total

leach

(mg/kg)

(mg/kg)

total

leach

(mg/kg)

(mg/kg)

% leach

Background area in Finland: FI 0

Naruska 3

6.73

0.51

8.03

1.55

0.07

E

3

1.69

0.05

2.03

0.68

< 0.01

BI

3 3

22.40 29.27

0.1 I 0.08

0.50

BZ

0.26

6.42 7.62

0.10 0.1 I

3

31.73

0.08

0.25

IO.33

11

28.6

0.03

0.12

12.87

BC C

I

0.97

I

1.16

0.27

23.1

0.76

0.02

2.0

I .48

7.07

0.08

1.16

I .48

8.91

0.08

0.87

0.15

I .4?

IO.45

0.08

0.76

0.27

2.17

9.93

0.05

0.47

27.31 5.87

FZ Pallas 0

3

4.70

0.51

IO.‘)7

0.X1

2.1 I

0.09

3.21

0.1 I 0.03

2.98

3

6.54 0.59

I .64

E

4.4 I

1.05

0.06

Bl

3

10.84

0.09

0.82

6.02

0.07

I.15

4.48

0.05

I.15

B2

7

I I .78

0.08

0.68

6.1 I

0.07

I.12

4.83

0.04

0.82

3

12.25

0.04

0.35

6.79

0.07

I .09

5.39

0.04

0.66

IO

10.48

0.03

0.27

6.28

0.07

1.16

5.1 I

0.04

0.82

BC C

The c/r leach is a percentile proportion of the mean concentration of an easily leachable element from its total concentration: n is number of samples of a layer.

parent till. To facilitate easy comparisons among the eight locations, mean values were calculated for the various layers of all samples from each location and are presented in Tables 2-7. The two abnormal profiles (2P38 and 5P41) were not used for the mean calculations of the profiles at locations Ml and N2. The distribution of S, Ni, Cu and As within the profiles is presented in Table 8. 3.1. Distribution the projile

Caritat et al.. 1996; topsoil O-5 cm, Reimann et al., 1996b; moss, Ayras et al., 1997a). In Fig. 2 the annual atmospheric deposition of Ni and Cu is estimated from the data of rainwater and snowcover samples by Chekushin et al. (1996). Cobalt, Cr, V and As showed a similar distribution patterns with considerably lower contrast between the strongly polluted sites and sites further from the emission sources (Tables 3-5). The highest

of hetrly metals, As and S within

3. I. I. Total concentrations of the elements in humus Table 3 shows that means of the total concentrations of Ni and Cu were several hundred times greater at site Ml in Monchegorsk than at background sites Fl and F2. At sites M2 and NI, they are lo-100 times greater and at sites M3 and N2, which are situated about 40 km downwind from the pollution sources, 4-6 times greater than at sites N3, Fl and F2. As seen in Fig. 2, the Ni and Cu concentrations in the humus layer become elevated as the rate of Ni and Cu load (deposition) rises in the study location. The same trend was observed for many of the media in the investigation (snow, Ayrls et al., 1995; rain, Reimann et al., 1996a; streamwater, De

0 I

0.1 MI

M2

M3

NI

N2

N3

FI

FL

locarions

Fig. 2. Distribution of the sum of total Ni and Cu concentrations in the humus layer and the annual atmospheric deposition of Ni and Cu (Ni+Cu

load, dashed line) at the study locations. The

deposition is calculated from the data of rainwater and snowcover samples by Chekushin et al. (1996). the means in Table 3.

For total concentrations see

M.L. Riiisiinen et (11./ Journul

182 Table Means

of Geochemicul Exploratton 59 f I9971 175-195

4 of the concentrations

soil (E, B I, B2, BC, Horizon

n

of Cr, Mn and V in the aqua regia (total)

C) layers

at the study

and ammonium

acetate

Cr

Mn

total

leach

(mg/kg)

(mg/kg)

(leach)

extracts

in the humus

(0)

and mineral

locations

% leach

V

total

leach

(mg/kg)

(m&/kg)

r/r leach

total

leach

(mg/kg)

(mg/kg)

W leach

Monchegorsk area: MI Monchegorsk 0 2 29.95

0.47

1.58

44.85

IO.18

22.69

30.95

0.75

2.44

E

2

17.35

0.28

1.62

60.50

0.46

0.7s

24.35

0.15

0.62

BI

2

70.35

2.97

4.21

193.00

7.00

3.62

58.15

0.15

0.26

82

2

57.40

I .56

2.71

183.00

2.36

I.29

48.05

0. I8

0.37

BC

2

55.45

1.00

1.80

195.50

I.61

0.82

46.40

0.21

0.46

C

I

46.76

0.30

0.65

233.71

1.19

0.5 I

42.50

0. IO

0.24

3 3

12.21

0.15

I .20

25 I .67

158.90

63.1-l

13.37

0.22

I .63

6.96

0.14

I .9x

50.37

2.44

4.85

17.40

0.24

I.38

Bl

3

55.20

2.09

3.78

155.67

3.31

7.77

52.33

0.24

U.46

B2

2

56.85

I .44

2.52

160.50

2.50

I .5s

37.cil

0.20

0.53

BC

3

52.67

0.92

I .74

170.33

0.74

0.43

36.20

0.17

0.47

C

8

52.89

0.40

0.77

255.00

0.67

0.26

42.35

0.08

0.19

0

2

10.29

0.12

1.20

17 I .50

39.66

19.05

0.23

I .20

E

2

7.56

0.09

I.19

54.55

6.34

27.55

0.12

0.45

M2 Kurhz

0 E

M3 Kirocsk I87.00 3.46

Bl

2

42.30

1.83

4.33

171.00

3.29

I .92

37.15

0.16

0.43

B2

2

34.40

1.20

3.47

145.50

2.00

I.37

46.90

0.33

0.70

BC

2

27.70

0.34

1.24

165.50

0.76

0.46

30.00

0.15

0.50

C

5

27.42

0.13

0.49

189.20

0.63

0.33

32.52

0.07

0.20

Nikel-Zapoijarnij NI Zapoljumij 0 2

area: 3.42

0.05

I .54

45.65

30.85

67.58

5.49

0.09

I .60

E

2

5.68

0.06

I.11

29.20

0.68

2.34

31.15

0.16

0.5 I

Bl

2

34.35

0.83

2.42

184.50

0.34

0.24

72.00

0.16

0.22

B2

2

34.70

0.65

1.88

232.00

0.53

0.33

56.95

0. I3

0.22

BC

2

36.80

0.47

I .28

293.00

I.25

O.-l3

64.35

0.1 I

0.18

c

3

47.13

0.36

0.76

341.67

I .45

0.42

68.20

0.08

0.12

0.1 I

4.33

484.33

32 I .67

66.4 I

5.33

0.06

I.18

0.04

0.82

44.37

2.44

5.50

16.40

0.08

0.49

N2 Skjellbekken

0 E

3 3

2.53 5.39

Bl

3

27.70

0.58

2.10

164.00

7.33

4.17

70.30

0.13

0. I 8

82

2

27.73

0.97

3.51

230.00

4.56

I .98

45.70

0.15

0.33

BC

3

27.20

0.70

2.56

2 12.67

3.57

I.68

45.60

0.13

0.32

C

IO

25.66

0.26

I.02

286.22

I.13

0.40

54.22

0.05

0.08

N3 Kirakku 0.03

2.09

II.00

0.03

0.26

0.18

102.00

0.15

0.14

0.19

20.50

0.02

0.10

I .s4

12.20

0.01

0.08

0.46

21.10

0.03

0.16

0

I

I .27

0.03

2.20

38.50

25.50

66.23

E

I

2.95

0.04

1.24

25.00

0.19

0.74

Bl

I

16.10

0.17

I .05

73.90

0.13

B2

I

12.30

0.36

2.89

96.70

0.47

BC

I

6.49

0.19

2.94

114.00

I .76

C

3

7.74

0.11

I.46

170.67

0.79

I .67

M.L. Riiisiinen

et al. /Journal

of Geochemical

5Y I IYY71 175-195

Exploration

183

Table 4 (continued) Horizon

Background FI Narusku 0 E BI B2 BC C

n

V

Mn

Cr % leach

total

leach

(mg/kg)

(mg/kg)

% leach

total

leach

(mg/kg)

(mg/kg)

% leach

total

leach

(mg/kgJ

(mg/kg)

area in Finland: 3 3 3 3 3 II

2.65 8.06 41.20 45.93 48.00 45.93

0.06 0.08 I .47 0.78 0.44 0.2 I

2.11 0.95 3.1 I 1.70 0.91 0.46

144.43 26.43 214.03 187.33 178.00 196.29

93.00 0.75 6.77 2.99 I.16 0.44

64.39 2.84 3.16 I .59 0.65 0.22

3.60 8.78 57.00 40.53 41.73 44.19

0.08 0.02 0.31 0.21 0.16 0. I3

2.29 0.17 0.54 0.52 0.38 0.31

3 3 3 3 3

2.66 8.67 21.70 24.90 27.07

0.05 0.19 1.15 0.97 0.79

2.04 2.16 4.16 3.90 2.91

148.67

10

21.03

0.28

1.35

82.01 I .47 0.32 0.23 0.2 1 0.57

55.16 3.88 0.31 0.21 0.17 0.3 I

5.02 18.83 37.60 30.35 35.33 28.36

0.1 I 0.05 0.29 0.20 0.14 0.09

2.21 0.27 0.78 0.66 0.40 0.33

F2 Pallas

0 E BI B2 BC C

The % leach is a percentile proportion samples of a layer.

37.83 102.83 110.00 127.33 181.60

of the mean concentration

of an easily leachable element from its total concentration;

total concentrations were measured at site Ml and the lowest for Co, Cr and V at site N3 and for As at site F2. For Cd, Mn, Pb, Zn and S (Tables 4 and 51, podzol profile sampling revealed no significant correlation between the element concentration in the humus layer and distance to the industry, even though these elements are part of the emission spectrum of the Russian mining and smelting industry (AyAs et al., 1995, 1997a). The low total concentration of S in humus near the Ni-Cu smelters is noteworthy, even though total annual emissions of SOz were 300 times as high as those of Ni and Cu (Table 6). In previous research from the surroundings of Nikel and Zapoljamij, Niskavaara et al. (1996) concluded that humus samples cannot be unambiguously used to outline the anthropogenic input of S in the forested area, but they well reveal the contamination of Ni and Cu; a similar finding was also reported by Nikonov (1993). In contrast to Ni and Cu (Fig. 21, the total S concentrations of the humus layer do not correlate with the S load (Fig. 3). The concentrations of organic S in Fig. 3 become elevated slightly from the strongly polluted site Ml to the background site F2, independently of the estimated amount of the S deposition; this trend was less detectable in the concentrations of inorganic S (see Table 6). The

n is number of

concentration of organic S was calculated by multiplying the total S concentration by (C + H + N)/ 100. The residual, after subtracting the concentration of organic S from the total S concentration, is then the concentration of S in the inorganic fraction. 3.1.2. Element concentrations in the mobile fraction of the humus layer The mean concentrations of the easily leachable Ni. Cu, Co, As, V and Cr revealed similar dispersal

i 0

s load,

-/

I

MI

M2

I

M3

Nl

N2

N3

Fl

0

Fz

localions

Fig. 3. Distribution of total S concentrations (thin line) and concentrations of organic S (thick line) in the humus layer and the annual atmospheric deposition of S (S load, dashed line) at the study locations. The deposition is calculated from the data of rainwater and snowcover samples by Chekushin et al. (1996). For concentrations of S see the means in Table 6.

Table Means mineral

5 of the concentrations

of Pb, Zn, As and Cd in the aqua regia

soil (E. B I, B2, BC,

Horizon

,I

C) layers

at the study

Pb

Zn

total

leach

(mg/kg)

(mg/kg)

Monchegorsk

(total)

% leach

and ammonium

acetate

(leach)

extracts

in the humus

(0)

A\

total

leach

(mg/kg)

(mg/kg)

% leach

Cd

total

leach

(mg/kg)

(mg/kg)

c/c leach

total

leach

(m&kg)

(mg/kg)

% leach

area:

MI Monche,qorsk 0

2

41.90

IO.13

24.18

32.90

5.41

16.44

28.15

E

2

1.89

0.32

16.76

5.29

0.28

5.32

I.58

0.03

BI

2

1.02

< 0.1

33.10

0.82

2.39

0.92

0.08

02

2

0.59

< 0.1

36.90

0.76

2.06

0.20

0.07

BC

2

0.7 I

< 0.1

32.05

0.60

1.X8

0.26

0.0s

C

7

0.89

< 0.1

26.13

0.2 I

0.80

0.24

0.05

0

0.7x

3

31.60

IO.31

32.64

43.87

I Y.83

45.21

5.26

E

3

4.67

0.42

9.06

4.12

0.67

16.35

0.57

0.04

2.77

0.55

0.16

7x. I I

0.3x

57.86

0.18

57.05

0. I9

56. I3

0.17

57.34

0.17

66.67

M2 Kurku 0.0’)

I .65

0.65

BI

3

1.25

< 0.1

36.03

0.9 I

2.54

0.49

0.03

B2

2

I.27

< 0.1

3 I .45

0.4 I

I.31

0.48

0.03

BC

3

1.38

< 0.1

35.37

0.25

0.7 I

0.44

0.04

C

8

I .70

< 0.1

36.30

0. I3

0.36

0.46

0.03

M3 Kirwsk 0

2

33.60

8.96

26.65

34.55

18.25

40.97

2.7’)

E

2

8.29

I.17

14.10

5.64

0.79

13.98

I .05

< 0.02

Bl

2

I .65

< 0.1

31.40

0.39

I.23

0.80

0.04

B2

2

1.25

< 0.1

24.45

0.56

2.29

0.84

0.04

BC

2

I.16

< 0.1

23.90

0.1 I

0.45

0.46

0.04

C

5

I.10

< 0.1

22.72

0.1 I

0.47

0.57

0.04

Nikel-Zapoljarnij NI Zapoljarnij

0.05

I.61

0.30

area:

0

2

13.10

35.65

18.70

52.45

3.62

E

2

3.78

< 0.1

3.86

0.93

24.08

0.23

0.03

B1

2

1.63

< 0.1

30.15

0.29

0.97

I .08

: 0.02

B2

2

1.28

< 0.1

38.20

0.13

0.33

I.11

0.03

BC

3

I .22

< 0.1

40.35

0.08

0.20

1.27

0.05

C

4

1.20

< 0.1

43.27

0.10

0.23

4.29

0.06

2.90

22.14

0.08

2.21

0.34

N2 Skjellhekkm 0.03

I ,74

0

3

13.47

3.44

23.78

70.03

3 I .40

44.84

1.73

E

3

2.36

0.24

IO.18

4.35

1.56

35.84

0.49

< 0.02

BI

3

1.34

< 0.1

41.47

2.40

5.78

4.29

0.03

B2

2

I .89

< 0.1

53.07

I .07

2.0 I

5.78

0.04

BC

3

1.66

< 0.1

49.03

0.39

0.80

6.78

0.04

C

IO

1.32

< 0.1

45.80

0.36

0.78

3.62

0.06

0.29

N.3 Kirakku < 0.02

0.26

0

I

12.40

2.66

21.45

43.10

15.00

34.80

1.58

E

I

4.04

0.23

5.72

2.10

0.40

19.14

0.12

< 0.02

Bl

I

4.15

< 0.1

13.80

0.36

2.62

0.33

< 0.02

B2

I

2.46

< 0.1

22.00

0.24

1.09

0.16

< 0.02

BC

I

3.74

< 0.1

20.90

0.14

0.65

0.05

< 0.02

C

3

3.74

27.33

0.07

0.24

0.05

< 0.02

0.24

and

locations

M. L. Riiisiinen et al. / Joumul of Geochemical Exploration 59 CI9971 175-195

185

Table 5 (continued) Horizon

n

total

leach

(mg/kg)

(mg/kg)

Background area in Finland: Fl Narusku 3 32.50 7.92 0 3 2.16 0.50 E 3 2.76 < 0.1 Bl 3 1.63 < 0.1 B2 3 1.86 < 0.1 BC II 2.0 1 < 0.1 C F2 Pallas 3 22.53 0 3 2.82 E 3 1.24 Bl 3 1.26 B2 3 1.15 BC 10 1.32 C

< < < <

s.42 0.20 0.1 0.1 0.1 0.1

8 leach

Cd

AS

Zn

Pb

8 leach

total

leach

(mg/kg)

(mg/kg)

total

leach

(mg/kg)

(r&kg)

24.36 23.22

61.90 4.17 43.90 53.40 41.43 40.93

25.03 0.46 0.80 0.57 0.22 0.04

40.44 11.14 1.81 I .06 0.53 (I.10

1.49 0.12 1.Oh 1.04 I.18 1.18

0.03

24.05 7.22

27.43 2.72 14.24 13.20 13.33 11.40

12.21 0.25 0.12 0.05 0.02 0.04

44.5 1 9.05 0.86 0.4 1 0.19 0.35

I .21 0.10 0.24 0.24 0.22 0.32

< 0.07

The Q leach is a percentile proportion samples of a layer.

of the mean concentration

% leach

2.13

total

leach

(q/kg)

(mg/kg)

0.56 < 0.02 < 0.02 < 0.02 0.04 0.04

0.30

52.91

0.50 0.02 0.02 0.02 0.02 0.02

0.25

49.87

< < < < <

of an easily leachable element from its total concentration;

patterns as did the means of their total concentrations, while concentrations of the easily leachable S, Cd. Mn, Pb and Zn were not influenced by emissions of the smelters at Monchegorsk and Nikel and the ore-roasting plant at Zapoljamij (Tables 3-6). It is stressed here that in contrast to the total concentrations, the mean value of the easily leachable Ni in Table 3 was 200 times greater, while that of Cu was 4000 times greater, at site Ml than in the background area (Fl, F2). The differences in means of Co, As, Cr and V were lo-20 times higher at site Ml than in the background (Tables 3-5). In comparison to the background, the increase at site Nl was marked only for Ni, and to a minor extent for Co and Cu, whereas for As, Cr and V the contrast was insignificant. Moreover, the mean concentrations of the easily leachable Ni and Cu were abnormally elevated at site M2 compared with those at other sites further from the emission sources. 3.1.3. Total concentrations of the elements in the mineral soil layers It is assumed here that the concentrations of metals, As and S in the C layer, i.e., the less altered transitional zone layers and parent till, represent the ‘natural background’ levels reflecting lithogeochem-

o/c leach

n is number of

istry. As seen in Table 7, the means of the total concentrations of S, Ni, Cu, Co and Cr were higher in the C layer of tills covering basic igneous bedrock (M 1, M2) than in the C layer of tills over granitic or quartzitic bedrock (N3, F2). For the metals, the difference is comparable with that between tills on greenstone belts and granitoids in Finnish Lapland (Koljonen, 1992). The difference in concentration levels between those of this study and data of Koljonen (1992) is partially due to the various fraction sizes analysed. According to Tarvainen (1995), concentrations of most heavy metals and S are commonly greater in the < 0.06 mm (used also by Koljonen, 1992) than the < 2.0 mm fraction. At Zapoljamij (Nl) the moderately high concentrations of S and Cu may be due to rock material derived from the Pasvic-Pechenga greenstone belt or an unknown mineralization in bedrock. This firstmentioned suggestion is supported by the fact that greenstone boulders occur in the till at sampling sites of podzol profiles. As also seen in Tables 3-6, differences in metal concentrations between the C layer and the overlying B 1, B2 and BC layers were in most cases surprisingly small compared with the difference between the eluvial layer and the illuvial (B 1, B2) layers. HamPl’ainen et al. (1997) reported a

186

M.L. Rh’isiinen et ul./Joumal

of Geochemicul

Table 6 Means of the concentrations of S in the aqua regia (total) and ammonium B2, BC, C) layers at the study locations Horizon

n

s

Exploration

59

CI9971

175-195

acetate (leach) extracts in the humus (0) and mineral soil (E, B 1,

C+H+N

Organic S

Minerogenic

total (wt.%)

total

total

(mg/kg)

(mg/kg)

7.80 9.21 54.00 61.99 65.82 57.75

32.79 1.33 3.16 1.52 0.98 0.31

389.55 0.79 15.78 5.40 3.07 0.2 I

798.45 58.81 4X4.23 351.10 3 I I .43 66.16

85.53 6.05 129.17 90.65 37.60 12.34

6.05 8.84 38.21 50.93 39.68 28.5 I

39.25 I .59 3.05 1.35 0.80 0.29

554.69 I .09 10.32 2.39 0.75 0.13

X58.65 67.38 327.68 175.61 94.0 I 43.16

I220.00 75.85 279.50 159.50 78.60 39.00

66.20 7.68 72.10 53.95 24.55 10.27

5.43 10.12 25.80 33.82 31.23 26.34

37.55 I .68 4.25 I .93 0.69 0.31

458.15 I .27 Il.88 3.08 0.54 0.12

761.85 74.58 267.62 156.42 78.06 38.88

2 2 2 2 2 4

1435.00 94.65 288.50 180.50 87.70 72.03

55.05 7.05 117.50 87.05 35.80 16.43

3.84 7.44 40.73 48.23 40.82 22.8 1

42.85 2.39 3.20 I.64 0.76 0.48

6 14.83 2.26 9.22 2.96 0.66 0.34

820.17 92.39 279.28 177.54 87.04 71.69

0

3

1526.67

E BI B2 BC C

3 3 2 3 10

42.60 156.27 126.33 109.93 42.94

89.50 4.82 50.63 32.47 27.63 8.85

5.86 II.31 32.40 25.70 25.14 20.6 I

45. I9 0.95 1.80 1.95 1.32 0.43

689.87 0.40 2.81 2.46 I .45 0.19

836.80 42.20 153.46 123.87 108.49 42.76

1 I I I 1 3

1360.00 32.60 146.00 128.00 43.90 28.73

74.70 2.52 40.80 44.90 17.90 7.89

5.49 7.73 27.95 35.08 40.77 27.45

54.01 0.67 I .46 I .26 0.32 0.19

734.54 0.22 2.13 1.61 0.14 0.05

625.46 32.38 143.87 126.39 43.76 28.68

total

leach

(mg/kg)

(mg/kg)

I 188.00 59.60 500.00 356.50 314.50 66.91

92.65 5.49 270.00 221.00 207.00 38.68

3 3 3 2 3 8

1413.33 68.47 338.00 178.00 94.77 43.29

2 2 2 2 2 5

Monchegorsk area: MI Monchegorsk 0 2 E 2 Bl 2 2 B2 BC 2 7 C

c/c leach

M2 Kurko 0

E BI B2 BC C M3 Kiroc,sk 0 E

BI B2 BC C Nikel-Zapoljarnij Nl Zapoljamij 0

E Bl B2 BC C

area:

N2 Skjellbekken

N3 Kirakka 0

E BI B2 BC C

S

M.L. Riiisiinen

et al./Joumal

of Geochemical

Exploration

59 (1997)

175-195

187

Table 6 (continued) Horizon

Background

n

C+H+N

Organic S

Minerogenic

total (wt.%)

total

total

(mg/kg)

(mg/kg)

6.40 9.15 26.6 I 43.59 46.57 42.53

49.86 0.54 2.42 1.04 0.66 0.44

729.65 0.15 3.90 1.60 0.63 0.21

733.68 27.32 157.43 152.73 95.00 48.9 I

101.73

6.83

49.97

744.48

745.52

4.41 35.03 21.43 17. I6 6.46

6.56 28.36 25.56 28.79 26.86

S total

leach

(mg/kg)

(mg/kg)

3 3 3 3 II

1463.33 27.47 161.33 154.33 95.63 49.13

93.67 2.51 42.93 67.27 44.53 20.89

3

I490.00

8 leach

S

area in Finland:

FI Naruska 0

E Bl B2 BC C

3

F2 Pallas 0

E BI 82 BC C

3 3 3 3 I0

67.23 123.53 83.83 59.60 24.03

The % leach is a percentile proportion samples of a layer

of the mean concentration

1.32 1.89 I .43 0.92 0.30

0.89 2.34 1.20 0.55 0.07

66.35 121.19 82.63 59.05 23.96

of an easily leachable element from its total concentration;

similar distribution pattern in nonpolluted podzol profiles in Finland. In the present study most metals show the lowest concentrations in the eluvial layer and increased in variable amounts downwards in the profile. Cobalt (except at site MI), Cu, Mn (except at sites M3 and Fl) and Ni show a tendency towards increasing element levels with increasing depth. The mean concentrations of Cr and V were at maximum either in the upper (Bl) or lower (B2) illuvial layers while the means of Mn, Zn and As show no general pattern. The exception to this occurred at site Ml, where Cu and As were markedly enriched in the eluvial layer. In addition, at sites M2 and M3 (located further from Monchegorsk) the eluvial layer contained more As than the underlying layers. In contrast to the general pattern of the metal distribution within the profile, Pb had the highest concentration in the eluvial layer, except at sites N3 and Fl where the greatest concentrations of Pb are exhibited in the Bl layer (Table 5). The contrast in the mean Pb concentrations between eluvial layer and the upper illuvial layer was unusually big at site M3, where humus was not characterized by abnormal concentrations of Pb. The distribution pattern of Pb within the profiles of the present study is never-

n is number of

theless compatible with that in non-polluted podzols reported by HPmPlBinen et al. (I 997). Sulphur displays a somewhat different distribution than the heavy metals and As in the mineral soil layers (Table 6). The lowest S content occurs in the eluvial layer and the highest in the underlying Bl layer from which the concentration decreased downwards in the C layer. This pattern is, however, more distinct here than that for the heavy metals and As. H’~m~l%inen et al. (1997) reported the same finding from nonpolluted podzols in Finland. The S content within the profile was related to the distance from the emission sources (Fig. 4). The highest mean concentration of S was found in the B 1, B2 and BC layers at site Ml, where the contrast in concentrations between the C and Bl layer is also greatest. At sites Nl, M2 and M3, the mean concentration of S is distinctly elevated only in the Bl layer, whereas at sites N2 and N3 the distribution of S is similar to that at the background sites (Fl, F2). Unusual element concentrations were exhibited in the following profiles: profile 2P38 without the 0 and E layer at site Ml and profile 5P41 at site N2. As seen in Table 8, profile 21338 contained abnormally high concentrations of Ni, Cu and As in the upper illuvial (Bl) layer and S in the B 1. B2, BC

-a

PI

c1

c,

P,

01

=!cclcqc 3s

000s

v

-

y; --

0

-. c,

‘J

v v v

rc. ry PI Q

P1

7

‘c

c

uz u-8 d

M.L. Riiisiinen et d/Journal

,v \s N2

Bl

82

i’

BC

BC

189

of Geochemical Exploration 59 11997) 175-195

~

Bl

B?

BC

i:

I

1,

C

C 0

200

400

Total concenhation

(mg/kg)S

i

C 200

600 Total

600

concentration(@kg) S

Fig. 5. Distribution of total concentrations of S in mineral soil layers

concentrations

400

in the Monchegorak,

I-m

0

200

Total ccmenuation

Nikel-Zapoljamij

400

600

(mgkg) S

and background

areas. For

see the means in Table 6.

layers. The concentrations decreased markedly in the C layer, but are slightly higher here than the mean values of the C layers of two other profiles. Similarly, the total concentrations of S were high in the mineral soil layers of profile 5P41, but increased downwards from the eluvial layer to the C layer. Here total concentrations of the heavy metals, except As, did not differ greatly from those of the other profiles at the same study location (Tables 3-6 and 8). 3.1.4. The element concentrations in the mobile,fraction of the mineral soil layers As seen in Tables 3-6, the distribution of easily leachable elements follows in many ways the pattern described above for the aqua regia extraction. The mean values for As and Cd were not reported in Table 5 because the concentrations obtained were very similar to or below the detection limit (0.02 mg/kg). Abnormally high concentrations of the easily leachable Cu, Ni and S were measured only from the profiles at sites M 1, N 1 and M2, which have the highest input of these elements. The mean concentrations of easily leachable Co, Cr, Mn, Pb, V and Zn were low and varied from site to site. The eluvial layer at site M3, however, exhibited an unusually high concentration of easily leachable Pb. It is emphasized here that at site Ml nearest the Monchegorsk smelters, the mean concentrations of easily leachable Cu and Ni were distinctly higher in the eluvial (E) and upper illuvial (Bl) than C layer

(Table 3). Moreover, Cu was on average more leachable than Ni in the eluvial layer, but not in the underlying layers. Here, the contrast in leachability of Cu between the surface and lower layers was the most marked in the eroded profile 2P38, whereas Ni was mostly unleachable in the ammonium acetate solution throughout the profile. The finding is confusing, since Ni and Cu were abnormally concentrated in the surface (i.e., in the Bl layer, Table 8). In contrast to site Ml, at sites Nl and M2 the leachability of Ni, but not of Cu, was distinctly higher in the E than C layer (Table 3). The same distribution pattern was also characteristic of concentrations at sites further from the emission sources. The mean concentrations of easily leachable S were almost ten times greater in the illuvial (B 1, B2) layers than in the C layer at sites Ml, M2 and Nl, while in all other locations the difference was at most fivefold (Table 6). The difference in concentration levels of the E and C layer between the contaminated and background sites could not be similarly linked with the distance from the emission sources. In the eroded profile 2P38 at site M 1, the concentration of easily leachable S was highest in the B2 than Bl layers and the lower layers (Table 8). The difference in concentrations between the aqua regia and acetate extracts slightly greater in the last-mentioned extract) is within the range of precision. In profile 5P41 which also showed high S content, the concentration of easily leachable S was surprisingly low. The concentrations in the Bl, B2 and BC layers

190

M.L. Riiisiinen

et al. /Journal

of Geochemical

Monchegorsk

S9 (1997)

3.2. Mobil&

were only slightly greater than the mean values of other profiles at the same site and those in the background (Tables 6 and 8). In the C layers the contrast was insignificant.

(a)

Exploration

17% 19.5

and retention of healq met&,

As and S

Rj_iGnen et al. (1993) suggested that polluted soils and sediments can be recognized by an increase

area

P M2

M3 ‘/

BI

Ml

82

I:

BC

leachable

(b)

pmpmtion

Nikel-Zapoljamij

leachable

(%) of Cu

proportion

20

40

leachable

(“lo) of Ni

1 8(

60

propomon

(I)

of S

area 0

E

\

\ ‘\

RI

‘j

Nl

HZ

‘\ N3

BC N2

io leachable

(c)

Backround

proportion(%)

0

IO

leachable

of Cu

20

30

proportion

I

/

C :3 0

40

20

i a(

40

60

40

60

(46) of Ni

area

E

0 leachable

BI

81

82.

82

BC--

BC

c4. 20 proportion

40

60 (%I of Cu

Fig. 5. Distribution of the proportions (7%) of leachable background areas. See Tables 3 and 6.

IO

-..,,..,...I 20 30

leachable

proportion

0

C 40

50

(%) of Ni

Cu. Ni and S within the profiles

c

-7

0

20 leachable

proportion

cl

(46) of S

in the Monchegorsk,

Nikel-Zapoljamij

and

M. L. Riiisiinen

et al. /Journal

of Grochrmical

site MI

Profile

2P38.

SY

(I YY7J 175% I Y.5

191

due to the variable nature of the emissions issuing from the smelters and the ore-roasting plant, as suggested by Ayras et al. (I 99.5). The proportions of leachable S distribution are opposite to those of the metals within these profiles. The lowest value is obtained in the humus and eluvial layers, from which they increase abruptly (Fig. 5). The maximum is obtained either in the illuvial (B 1. B2) or BC layers; here, the increase was more prominent at site M 1 than N 1 or the other less contaminated sites. Since > 50% of the S content is in the mobile form in the illuvial layer at Monchegorsk (Table 6), it can disturb the stability of Al-rich compounds and promote soil acidification as reported by RaisPnen et al. (19941. In Fig. 6. the eroded profile 2P38 at site Ml shows the abnormally high leachability of S: in contrast to the other profiles at site Ml, S is entirely in the mobile form in the topmost layer (B 1). whereas in the layers below the B 1 layer the proportion of the leachable S was similar to that in the other profiles. It should be noted that in Table 8 the concentration of S. which is higher in the acetate than aqua regia extracts of the Bl layer, is within the range of precision. In contrast to profile 2P38, profile SP41 at site N2 (also with high total concentration of S) shows a low proportion of leachable S (see the right-hand diagram in Fig. 61. which confirms the suggestion on the different source of S at sites Ml and N2. The mobility of As. Cd. Co, Cr. Mn, Pb and Zn

in element concentration of the mobile fraction. Fig. 5 compares the mobility of Cu, Ni and S within the profiles at polluted and background sites; here, mobility of the element in a layer was calculated as a proportion (%r) of the mean concentration of the easily leachable element from its mean total concentration (see also Tables 3 and 6). As seen in Fig. 5. the proportion of leachable Cu and Ni has been increased in the E, 0 and B 1 layers, respectively, and more so at contaminated than background sites. In the Monchegorsk area the increase of Cu was greatest at site Ml and lowest at site M3. The proportion of leachable Ni is, however, elevated slightly more at site M2 than Ml, but it was lowest at site M3. The lower amount of the leachable Ni at site Ml indicates the tendency of Ni to accumulate in the surface layers. This is more distinctly seen in the eroded profile 2P38 in Fig. 6 (the diagram in the centre). In contrast to Cu. Ni was mostly insoluble in the topmost layer (B I), despite its high total concentration (see also Tables 3 and 8). The proportion of leachable Cu was also fairly high in the B2 and BC layers, whereas in the other profiles of site Ml and in the profiles of the other sites, it was in these layers similar to that in the C layer (Figs. 5 and 6). In the Nikel-Zapoljamij area. the order of contaminated sites for Cu differs from that for Ni (Fig. 5). In contrast to Ni, the proportion of leachable Cu was lower at site Nl than N2 and N3, which are actually located closer to the smelters at Nikel than the roasting plant at Zapoljamij. The difference is

Means,

Explnrafion

site MI

Profile

0

SP41, site N2

0 CU

E

E

I’ Ni

/’ /’

82

BC

0

20

40

60

% leach

80

,

\S

/Cu

BC

C 20

40

60

% leach

80

20

40

60

80

100

% leach

Fig. 6. Distribution of the proportions of leachable Cu. Ni and S within the profiles at site MI, within eroded profile 2P38 at site Ml and within profile 5P41 at site N2. In the left-hand diagram. Bleach is calculated from the mean concentrations of two profiles at site Ml in Tables 3 and 6 and in the middle and right-hand diagrams from the concentrations of \ingle profiles in Table 8.

could not be linked as distinctly with the distance from the emission sources as the mobility of Cu and Ni. The low mobility of Co, Mn and Zn in the humus layer at site Ml (Tables 3-S) is noteworthy. In the mineral soil layers, comparison of the leachable proportions is insignificant due to the low concentrations. Alternatively, the differences between the polluted and background sites can be examined in terms of the accumulation. Kabata-Pendias and Pendias (1992) suggested that in polluted soils metals concentrate in the organic-rich surface soil layers and also potentially in the layers rich in Fe-oxides (see also Saur and Juste. 1994). In Figs. 7 and 8 the accumulation (a) is calculated as a percentile proportion of the total concentration of an element in

(a)

OL Ml

, M2

I

M3

T-----T-

NI

N2

N3

FI

F2

locations

(b) 100

0

7

~_--_---i---

MI

,...

M2

M3

NI

N2

_

T. N3

_,_-----_I Fl

F2

locations Fig.

7. Accumulation

of Cu, Co and Ni (a) in the humus (0) layer

and (h) in the upper illuvial

(B I) layer at the study locations.

accumulation

is calculated

concentration

of a metal in the 0 or B

concentrations

as a percentile

I

proportion

The

of the total

layers from the sum of its

in the 0 or B I and C layers.

60 -I MI

~--~ M2

M3

/ NI

N2

N3

-,--p--I FI

F?

locations

Fig. 8. Accumulation (thick lint)

in the upper illuvial a percentile laycn

of the minerogenic

(thin

line) and organic

S in the humus (0) layer and that of the minerogenic (B I) layer. The accumulation

proportion

of the total S concentration

from the sum of its concentrations

is calculated

S a\

in the 0 or B I

in the 0 or BI

and C’

laycrh.

the 0 layer from the sum of its concentrations in the 0 and C layers. As shown in Fig. 7, the accumulation of Ni, Cu and Co occurred in the humus layer. but not in the illuvial (B I > layer at strongly polluted sites, whereas the concentration of S is ambiguous (Fig. 8). As seen in Fig. 8. the concentration of S into the organic fraction of the humus layer is lower at strongly polluted sites than at the background. while the contrast in the inorganic fraction is insignificant. In contrast to the metals, S is concentrated slightly more in the illuvial (Bl) layer in the Monchegorsk area than at Zapoljamij and the background sites. It can be concluded that humus can retain airborne metals. but not S. The accumulation of the metals decreases as the distance from the emission source increases. In contrast to humus. the capacity of the Fe-rich illuvial layer or any other podzolic layer to retain the metals is insignificant in most profiles. Since the geological factors did not solely explain the metal variation in the illuvial layer, it must be caused by differences in soil processes at the study sites. This is in contrast to the interpretation of Saur and Juste (19941, who suggested that the increase in metal concentrations in the illuvial layer was caused by the atmospheric deposition of metals. The only exception to the behaviour of metals in the illuvial layer occurred at an eroded site in Monchegorsk; here, Ni but not Cu was very well bound in the upper illuvial layer at the top of the

M.L. Rb‘isiinen et al. / Journal

ofGeochemicu1

profile. The absence of the humus and eluvial layers must have promoted the fixation of Ni in the Feoxides (Coughlin and Stone, 1995). It should be noted that in this case the Ni concentrations in the B2 and BC layers below the Bl layer did not differ greatly from that in the C layer. In contrast to the metals, the concentration of S in the humus layer was not linked to the distance from the emission source. Despite this, the illuvial layer was concentrated by S more in the vicinity of Monchegorsk, but not at Zapoljamij, than at the background sites as seen in Fig. 8. At Monchegorsk the accumulation of S was even more prominent in the eroded profile (Table 8). According to Gustavsson and Jacks (1993), the abundance of organic ligands in the soil solution inhibits the retention of airborne S in mineral soil layers. At Monchegorsk the decreased forest productivity, and particularly the lack of a humus layer at the eroded site must have caused a low organic acid content, which promoted the adsorption of S.

E.rplomtion

5Y (lVY7)

175-195

I93

mobile form. In contrast to the metals, S was not concentrated in the humus layer but was to some extent enriched in the illuvial layers, particularly in the eroded site at Monchegorsk. Here, a large portion of S remained in mobile form and may, therefore, have disturbed the stability of Al-compounds.

Acknowledgements We would like to thank the Geological Surveys of Finland and Norway, the Norwegian Ministry of the Environment and Central Kola Expedition for their support of the project. We would also like to thank the entire project team in all three countries and the guest scientists from Lithuania and Austria who participated in the field work and in many stimulating discussions.

References Aaltonen. V.T.. 1052. Soil formation and soil types. Fennia 72,

4. Conclusions The total concentrations of Ni, Cu. Co. Cr, As and V were much higher in the Monchegorsk, Kurka and Zapoljamij locations than in all other study sites. These elements remained strongly enriched here, particularly in the humus layer, when compared with the composition of the parent till at the various locations, strongly suggesting the presence of an anthropogenic source. The mobilities of heavy metals in the surface layers and that of S in the illuvial layer were much higher at sites near the industry than in the background. The slightly elevated mobilities of Cu at sites N2 and N3 and that of Ni at site N2 compared with those at the background sites (F 1, F2), also showed that the soils of the sites in northernmost Norway and Finland near the Russian border were influenced by contamination. The behaviour of Cu and Ni within the profiles showed that at first both elements tend to accumulate in the organic layer near the emission sources, since the illuvial layer shows a low capacity to retain airborne metals. An exception occurred at the eroded site at Monchegorsk, where Ni was fixed in the upper illuvial layer; here, Cu remained mostly in the

65-73. Alexeyev, V.A., 1993. Air pollution impact on forest ecosystems of Kola Peninsula: history of investigations, progress and shortcomings. In: Kozlov, M.V., Haukioja. E., Yarmishko, V.T. (Eds.), Aerial Pollution in Kola Peninsula. Proc. Int. Workshop 14- I6 April 1992, St. Petersburg, Kola Sctentific Centre, Apatity, pp. 20-34. Andersson, 1976. On the determination of ecologically significant fractions of some heavy metals in soils. Swed. _I. Agric. Res. 6. 19-25. Ayras. M.. De Caritat, P., Chekushin, V.A., Niskavaam, H., Reimann, C., 1995. Ecogeochemical investigation. Kola Peninsula: Sulphur and heavy metal content in snow. Water, Air Soil Pollut. 85. 749-7.54. AyrIs, M., Pavlov, V., Reimann, C., 1997a. Sulphur and some heavy metal abundance in humus and moss in the vicinity of the Kola industrial area. Water, Air Soil Pollut., in press. AyrKs, M., Niskavaara, H., Bogatyrev, I., Chekushin, V.. Pavlov, V., De Caritat. P., Halleraker, J.H., Finne, T.E., Kashulina, G.. Reimann. C.. 1997b. Regional patterns of heavy metals (Co, Cr. Cu, Fe, Ni, Pb. V and Zn) and sulphur in terrestrial moss samples as indication of airborne pollution in a 188,@.?0 km’ area in northern Finland, Norway and Russia. J. Geochem., Explor. in press. Berrow, M.L.. Mitchell. R.L., 1980. Location of trace elements in soil profiles: total and extractable contents of individual horizons. Trans. R. Sot. Edinburgh, Earth Sci. 71, 103-121. Boyd, R., Niskavaara, H., Kontas, E., Chekushin, V., Pavlov, V., Often, M.. Reimann, C., 1996. Anthropogenic noble-metal enrichment of topsoil in the Monchegorsk area, Kola Peninsula, northwest Russia. In: Reimann, C.. Chekushin. V., Ayras,

M.

(Eds.),

Study

Kola

Project-International

iYY4. Norges Geologiska

Report.

Undersokelse

Catchment

Rep. 06.088.

pp. 2744292. Bogaryrev, I.V., De Caritat, P.. Niskavaara,

Reimann

C..

elements

in eight

1996.

C..

Annual

atmospheric

catchments

Chekushin,

Project-International

of

V..

H..

deposition of

the

Barents

Ayras.

M.

region.

(Eds.).

17 In:

Kola

Report, Catchment Study IYY-1. Norges

Geologiaka Undersakelse Rep. 96.08X. pp. 79%YY. Coughlin.

B.R., Stone, A.T..

lYY5. Nonreveraihlc

divalcnt metal ions (Mn”,

Co”.

croethite: effects of acidification.

Nil’.

adsorption of

Cu”.

and Ph”)

onto

Fe ” addition. and picolintc

Pavlov. V.A.,

1996. Stream water geochemistry

selected catchments on the Kola Peninsula (NW in neighbouring areas of Finland and Norway.

from

Russia) and I. Lcvols and

sources. Aquatic Geochemistry. 2. 14Y- 168.

Flctchcr.

W.K..

IYX I.

Analytical

Finl.. Current Rea. lY93-19Y4.

Revised

legend.

I 19 pp.

methods

Niskavaara,

H.. Reimann. C.. Chekushin. V.,

lYY6. Distribution

and pathways of heavy metals and sulphur in the vicinity 01 the copper--nickel

smelters in Nikel

and Zapoljarnij,

Geochcm.

I I.

Pavlov. V.A.,

Kola

7-S-3-1.

Raisanen. M.L..

Composition

Melezhik.

V.. De Caritat, P.. lYY6.

of bedrock and Quaternary

deposits in ctght

in the Barents region. In: Reimann, C.. Chekushin. V.. Ayrls. M.

(Eds.).

Kola

Project-International

Report.

Study lYY4. Norgex Cieologiska Undersokelse

gcochemical

Catchment

Rep. 96.08X.

pp. 18-37. /olization

A.. Peuraniemi, V., Aario. R., lYY2. On pod-

in glaciofluvial

material in northern Finland. Ann.

Acad. Sci. Fenn.. Ser. A 111, Geol.-Geogr,

in

Spec. Pap. 20.

167-175.

PetajP-Ronkaincn.

1988. Soil Map of the World.

World Soil Resources Report 60. FAO.

Cieol. Sure

catchments subJected to detailed ecogeochemical investigatron

De Caritat, P., Reimann, C.. Ayras, M., Niskavaara. H., Chekushin.

FAO-Unesco.

IYYS. A comprehensive scheme of analysrs for

Peninsula. Russia as revealed by different sample media. Appl.

icid addition. Environ. Sci. Technol. 29, 2445-24.55. V.A.,

H..

soils. sediments. humus and plant sample\ using inductively coupled plasma atomic emission spectrometry (lCP-AESJ

Chekushin. V.A..

Reimann,

Niykavaara,

Raisinen. M.L..

156. I9 pp.

1994. Reflection of bedrock on the \oil geochem

prospecting. In: Govett. G.J.S. (Ed.). Handhook of Exploration

iatry and weathering

in the tundra region of northernmost

GeochemistI-y. Vol. I. Elsevicr. Amsterdam, 255 pp.

Finland.

J.M.

Cerasimovski.

V.I..

Volkov, V.P.. Kogarko, L.N.. Polyakov, A.I.,

1973. Kola Peninsula. In: Sorensen. H. (Ed.). Rocks. Wiley. London, pp. 206-22

The Alkaline

by acidic deposition and rxtractahle

organic carhon. Environ. Pollut. 81. 185-191. Hlmiil‘uinen,

L..

pretreatment

Raislnen.

M.L..

and partial

Lehto.

Ahrens.

0..

decomposition

fcctcd Soil\.

July lYY4. USDA.

Riiisanen. M.I...

IYYh. Geochemistry

implications fat- aluminium

of podzolized tills and the

study in Kuopio. castrrn Finland. Geol. Surv. Finl. Bull.. 3X7. 1997.

Effects

techniques

oi

on the

72 pp. R;iis;inen. M.L..

HBmBlainen, L., IYY I. Selective sequential disso-

Current Res. l99S- 1996. Spec. Pap. 23. in press.

Fin].. Spec. Pap. Y. 157-162.

in the eastern part of the

ice divide in Finnish Lapland. Geol. Surv. Finl. A.. Pendtas, H..

1992. Tract

Elements in Soils

MI..

mineralogy

Tenhola.

M..

Makitten,

J.,

1992.

Surv.

Effects

of

and physical properties on till geochemistry

in

K9ia:;lnen. M.L..

L&to.

0..

HdmZiinen,

L.,

1993. Mohtlity

01

toxic metals and arsenic, and determination of pollution risk in

and Plants. CRC Press, Boca Raton, FL. 365 pp. Kahkonen, A.-M..

Riiisanen.

sediments. Geol.

central Finland. Bull. Grol. Sot. Finl. 64 (1). 35-58.

Bull., 3X3. 72 pp. Kabata-Pendias,

Service.

mobility near Industrial aitcs: A

lution 01 polluted and non-polluted

Weichselian

Proc. Mtg.

Soil Conservation

leachability of elements in podzolized tills. Geol. Sure. Finl.. Johansson, P.. lY95. The deglaciation

R.J. (E&J.

Classificatirnr. Correlation. and Management of Permafrost-atNational So11 Survey Center. pp. 9Y- I I I,

I.

Gustavsson, J.P.. Jacks. G.. 1993. Sulphur status in some Swedish podzols a:, influenced

In: Kimblc.

1996. The geochemistry of podrol soils and its

\oils and acdimcnts. In: Tuomisto. J., Ruuskanen, J. (Eda.).

relation to lake water chemistry. Finnish Lapland. Geol. Sure.

Proc. 1st Finnish Conf. Environmental Sciences Kuopio, Octo-

Finl. Bull., 385. 89 pp.

her X-9,

Koljonen, T. (Ed.).

1992. The Geochemical Atlas of Finland. Part

Raiaanen, M.L..

2. Till. Geological Survey of Finland, Espoo, 2 I8 pp. Melezhik, L.-P.,

VA.

Hudson-Edwards.

K.A..

1994a. Pechenga area, Russia, Part

and comparison with Pasvik, Norway. all., Appl. Earth Sci. l03B. Melezhik, L.N..

Skuf’in.

V.A..

I.

P.K.. Nilsson.

Geological setting

Trans. Inst. Min. Met-

K.A., Green, A.H., Crimenko.

lYY4b. Pechenga area, Russia. Part 2. Nickel-copper

deposits and related rocks. Trans. Inst. Min.

Metall..

Appl.

Sciences. 14, pp. 2366238. Pulkkinen,

forest soils in the surroundings of the Pechenga nickel smelter

19-38. M.L..

Tarvainen,

Aatoa,

F&h.

IYYS. NORMA-a

M..

Fiiren. Stockholm

117. 215-224. Niskavaara.

H.. Chekusin.

J.H.. Volden. T., Ayrii\.

V.A..

Pavlov,. V.A.,

lY96a.

Rainwater composition in eight arctic catchments of Northern Europe

Chckushin, V., AyrP,

Research Station. Rovaniemi.

S..

and rocks trom chemical analysis. Geol.

complex. In: Derome, J. (Ed.), Lapland Forest Damage Pro-

pp. 68-85.

T.,

program to calculate a normative mineralogy for glacial tills

.ject. Russian-Finnish

Cooperation Report. The Finnish Forest

IYY4. Alteration ot smelters at Montch-

gorsk, Kola Peninsula, Russia. Bull. Geol. Sot. Finl. 66 (I).

Reimann. C.. De Caritat. P.. Halleraker.

Earth Sci. 103B. 146-161. Nikonov, V., 1993. Pollution-induced changes in the properties of

Research Institute. Rovaniemi

E.. Kontio. M.,

podzolizcd tills by acid load near Ni-Cu

Rlisanen,

129-14.5.

Hudson-Edwards,

IYY3. Kuopio University Publications C. Natural and

Environmental

Report, 60-78.

(Finland. Catchment

Norway

and Russia).

In: Reimann,

C..

M. (Eds.), Kola Project-international

Study

1994.

NGU

Report

Y6.08X.

pp.

ML.

Riiisiinen

et ul. / Journul

qf Geodremicul

Reimann, C., Boyd. R., De Caritat, P.. Halleraker. J.H., Kashulina. G., Niskavaara, H., Bogatyrev, I., 1996b. Topsoil (O-S cm) composition in eight arctic catchments in northern Europe (Finland, Norway and Russia). In: Reimann, C., Chekushin. V., AyrBs. M. (Eds.), Kola Project-International Report. Catchment Study 1994, NGU Report 96.088, pp. 253-273. Reimann. C., Niskavadrd, H., De Caritat, P., Finne. T.E., Ayriis. M., Chekushin. V.. 1996~. Regional variation of snowpack chemistry in the vicinity of Nikel and Zapoljarnij, Russia. northern Finland and Norway. Sci. Total Environ, 182. 147158. Report of the Murmansk region Committee of Ecology and Nature Resources, 1995. Review of pollutant fallout\ in the atmo-

Explorurion

5Y CIYY7) 175-198

195

sphere on the territory of the Murmansk region in 1994. Murmansk 1995. Saur, E., Juste, C.. 1994. Enrichment of trace elements from long-range aerosol transport in sandy podzolic soils of Southwest France. Water. Air, Pollut. 73, 235-246. Tarvainen. T., 1995. The geochemical correlation between coarse and fine fractions of till in southern Finland. J. Geochem. Explor. 54, 187- 198. Tikkanen, E.. Niemeli. 1. (Eda.), 1995. Kola Peninsula pollutants and forest ecosystems in Lapland. Final Report of the Lapland Forest Damage Project. Gummerus Kirjapaino Oy. JyvPskyb. 81 PP.