Abstract

Samples of berries of Vaccinium vitis-idaea, V. myrtillus, Rubus chamaemorus and Empetrum hermaphroditwn and soils (illuvial humus podzol, bog peat soils) from the zone affected by aerial emissions in the Kola Peninsula were analyzed. The Ni and Cu contents in berries were directly proportional to concentrations of these metals in soils. On the area 2:2000 km2 (the ellipse of 20-30 km width and 70-80 km length, with long axis directed from N to S) the concentration of nickel in the berries exceed the sanitary standard.

Introduction

Pilot analysis of nickel content in the edible forest berries (cowberry, cloudberry) and 6 species of mushrooms (Barcan e.a., 1990) showed that on the area polluted by "Severonikel" smelter complex (about 1500 km²) it exceed the sanitary standard.
The aim of present investigation is to define more accurately the area around the city of Monchegorsk where high content of heavy metals in berries makes them dangerous (toxic) for the people.

Materials and Methods

The investigated area is situated at the border of the northern taiga and tundra forests (68-69⁰N) and is affected by emissions of "Severonikel" smelter complex. Southern and northern winds prevail in the region (Yakovlev, 1961). Therefore the sampling plots were mostly chosen along the belts stretched to north and south from the smelter. The plots situated 80-100 km E-SE and 100-300 km S of the smelter were considered as a background, because the epiphyte lichens were alive there at any height of trees. Both soils and berries were collected on 63 plots in 1987-1991.
The prevailing forest soil type in this part of the Kola Peninsula is illuvial humus podzol, with a thick organic horizon (A0), rather a shallow profile, and very clear differentiation of soil horizons. As a rule, the humus (A1) horizon is absent. The bog soils in places of cloudberry growth are sphagnum peat bogs (Belov & Baranovskaya, 1969).

Table. Content of Ni and Cu in berries.
Plot no	Plot position in relation to smelter		Date of sampling	Contents, mg/kg
	distance km	azimuth (°)		nickel		copper
				d.w.	w.w.	d.w.	w.w.
Vaccinium vitis-idaea L.
1	6	315	05.09.87	14.2	1.9	15.8	2.1
2	10	330	04.09.88	15.0	2.2	25.0	3.7
			26.09.89	24.0	3.8	15.0	2.4
3	17	350	26.09.89	24.0	3.8	9.0	1.4
4	16	15	26.09.89	35.0	5.2	23.3	3.6
6	20	0	17.08.88	10.0	1.5	11.0	1.6
			26.09.89	16.7	2.5	14.7	2.2
7	4.5	55	25.08.88	13.3	2.0	8.4	1.3
8	5	55	25.08.88	13.3	0.6	8.0	1.1
10	10	45	04.09.87	25.8	3.4	14.5	1.9
			30.08.88	21.0	3.1	9.8	1.4
11	12	45	04.09.87	20.8	2.8	11.2	1.5
			30.08.88	15.7	2.2	8.5	1.2
13	20	45	30.08.88	5.4	0.8	5.6	0.8
16	30	55	30.08.88	5.0	0.7	6.2	1.0
17	15	60	07.10.89	12.0	1.9	11.3	1.8
24	5	80	25.08.88	9.0	1.4	6.6	1.0
25	6	80	25.08.88	9.5	1.4	6.0	0.9
27	11	85	03.10.90	6.9	1.2	13.0	2.2
28	12	90	15.09.90	4.0	0.6	7.0	1.1
29	13	90	10.09.90	6.0	0.9	7.0	1.0
30	14	90	11.09.87	8.4	1.1	-	-
32	12	125	30.08.88	7.0	1.0	5.6	0.9
33	13	125	29.08.88	5.0	0.7	6.6	1.0
34	13	135	12.09.87	5.3	0.7	4.2	0.6
35	16	125	09.09.87	8.0	1.0	11.0	1.5
			08.09.90	6.1	0.9	11.0	1.7
			10.09.90	4.3	0.7	11.0	1.6
36	18	145	01.10.88	5.3	0.9	16.0	2.6
			09.09.89	9.3	1.3	15.2	2.1
			03.10.90	6.0	1.0	13.0	2.3
37	15	150	02.09.89	6.7	0.9	8.4	1.1
38	25	150	30.08.89	6.0	0.8	9.0	1.0
39	25	160	28.09.88	5.0	1.0	8.0	1.5
			15.09.87	10.0	1.5	15.0	2.1
40	30	170	30.09.88	7.7	1.1	11.0	1.6
41	6	180	06.10.87	96.7	13.2	53.1	7.3
			30.08.90	46.0	6.7	28.0	4.0
42	9	180	06.10.87	52.5	8.0	39.0	5.9
			18.09.90	29.5	4.8	23.0	3.9
43	14	190	31.08.88	6.7	1.0	10.2	1.5
44	16	180	06.10.87	10.0	1.5	21.7	3.3
45	23	180	31.08.88	5.9	0.8	9.0	1.2
46	32	185	31.08.88	6.9	0.9	6.2	0.9
52	32	192	11.09.90	14.0	2.2	11.7	1.8
			11.09.90	7.2	0.9	11.7	1.5
53	32	195	12.09.90	7.5	1.0	8.0	1.2
54	30	200	19.09.90	14.0	2.0	15.5	2.2
55	32	205	05.09.90	3.0	0.4	5.7	0.8
			07.10.90	2.7	0.4	6.3	1.2
56	34	218	16.09.87	4.0	0.5	8.0	1.1
			12.09.90	13.0	2.0	15.2	2.3
			12.09.90	7.5	0.9	11.7	1.5
			07.10.90	4.9	0.8	10.0	1.8
61	53	220	31.08.88	3.0	0.4	6.0	0.8
62	80	245	31.08.88	2.5	0.3	4.7	0.7
63	80	247	31.08.88	3.0	0.4	6.8	0.9
Vaccinium myrtillus L.
9	6	60	11.08.87	9.0	1.3	13.0	1.8
			15.08.88	6.9	0.8	5.9	0.7
64	6	90		25.0		16.3
28	12	90	13.09.90	5.3	0.6	9.7	1.2
35	16	125	02.07.89	10.5	1.3	10.0	1.2
37	15	150	02.09.89	5.0	0.6	8.0	1.0
38	25	150	08.09.87	9.0	1.0	14.0	1.6
			30.08.89	9.0	1.1	9.0	1.1
39	25	160	15.09.87	7.0	0.8	10.0	1.1
40	30	170	20.09.87	8.0	0.8	14.0	1.4
49	12	208	28.08.90	10.1	1.4	-	-
			28.08.90	10.2	1.2	11.3	1.5
52	32	192	11.09.90	4.4	0.7	6.6	1.0
			11.09.90	8.4	1.2	7.0	1.0
54	30	200	19.09.90	7.7	1.1	11.6	1.5
55	32	205	15.08.90	6.5	0.9	12.0	1.6
56	34	218	15.08.90	2.8	0.4	7.0	1.0
59	47	243	15.08.90	8.0	1.1	11.2	1.5
60	47	245	15.08.90	10.0	1.4	15.5	2.2
Rubus chamaemorus L.
2	10	330	27.07.88	57.0	8.8	19.0	2.9
3	17	350	30.07.88	47.5	8.1	17.4	2.9
4	16	15	30.07.88	42.5	6.5	19.4	3.0
12	18	45	28.07.88	16.3	2.9	13.3	2.4
17	15	60	09.08.87	8.1	1.2	9.6	1.4
			24.07.88	7.2	1.1	11.0	1.6
19	30	60	07.08.87	7.0	1.0	7.3	1.0
22	100	75	30.07.88	2.9	0.5	5.0	0.8
37	15	150	16.08.87	12.5	1.7	18.0	2.4
43	14	190	28.07.88	66.0	11.2	24.0	4.1
47	13	200	06.08.87	35.0	4.8	23.5	3.2
48	11	210	06.08.90	38.0	5.2	26.2	3.6
50	12	205	06.08.90	56.0	8.0	28.7	4.1
51	26	197	08.08.90	21.0	3.8	17.5	2.8
			08.08.90	30.0	3.8	23.5	3.0
53	32	195	07.08.90	22.0	3.0	27.5	3.8
			07.08.90	16.0	2.8	17.0	3.0
63	80	245	28.07.88	3.3	0.5	5.8	0.8
Empetrurum hermaphroditum (Lge.)
20	46	60	09.09.87	10.8	1.5	7.9	1.1
26	10	85	18.10.87	16.7	2.0	23.8	2.8
41	6	180	18.09.90	83.0	11.6	115.0	17.4
49	12	208	28.08.90	25.0	2.8	30.8	3.5
50	12	205	28.08.90	18.3	2.2	26.0	3.0
51	26	197	25.09.90	19.0	2.2	25.0	2.8
			25.09.90	14.0	1.6	13.7	1.6
52	32	192	11.09.90	5.8	0.6	12.5	1.3
			21.08.90	17.0	1.7	23.0	2.3
53	32	195	12.09.90	6.8	0.8	12.8	1.4
54	30	200	19.09.90	16.0	1.8	24.3	2.8
55	32	205	05.09.90	6.9	0.7	15.0	1.6
56	34	218	12.09.90	5.9	0.7	11.1	1.2

The samples of the horizon A0 (forest soils) and of 0-5 cm depth (bog soils) were taken and prepared by standard methods (Arinushkina, 1970; Sokolov, 1975). The samples (200-500 g) of berries (cowberry [Vaccinium vitis-idaea (L.) Avz.]- 57, bilberry {Vaccinium myrtillus L.) - 19, cloudberry [Rubus chamaemorus L.]- 18, Empetrwn hermaphroditwn (Lge.) - 13 samples) were dried (without preliminary washing) at 60-65°C in warm air flow. Samples were weighed before and after drying to estimate the water content. The total content of Ni and Gu was determined after ashing and extraction with acid by colorimetric methods: with dimethylglyoxime for Ni, and with lead diethyl carbaminate after extraction with chloroform for Cu (Anonymous, 1988). The results were treated by the standard statistical methods. Linear regressions were calculated by method of least squares after transformation, if necessary (Leontjev, 1966; Svalov, 1977).

Results and Discussion

Dry weight of samples can be estimated with the 5% accuracy, separating the wet weight to 7 for V. vitis-idaea, 8.2 for V. myrtillus, 8.9 for E.hermaphroditum and 6.8 for Rubus chamaemorus. The decrease of nickel and copper content in upper organic layers of soils follows the hyperbolical law with increasing distance. The Ni and Cu contents of both the affected type soils the forest podzol and bog soils are very high within a circle of 7-10 km radius from the smelter. However, the soil pollution was almost independent on the direction. 10-12 km of the smelter, the Ni and Cu contents in the Ao horizon were 50-80 times higher as compared to background. 30 km S of smelter, the concentration exceed the background 20 times, and 40-50 km NE of it - 2-3 times (Fig. 1 and Fig.4).

Figs. 1-2. Content of metals at different distances south of the smelter:
1 - in organic soil layer A0; 2 - in berries of V. vitis-idaea.
A - nickel, В - copper.



Fig. 3. Regression of the metal content in berries to one in soil south of the smelter:
A - V. vitis-idaea, В - E. hermaphroditum.



Figs. 4-5. Content of metals at different distances south of the smelter:
4 - in sphagnum bog layer 0-5 cm depth; 5 - in berries of Rubus chamaemorus.
A - nickel, В - copper



Fig. 6. Regression of the metal content in berries of R.chamaemorus to one in sphagnum bog S of the smelter.



Fig. 7. The area with high nickel content in berries (shaded). The sampling plots are marked by circles.

Content of nickel and copper in berries depend on the distance and direction from the emissions source (Tab.). In general, it decreased hyperbolically along the line of emission plume (Fig. 2 and Fig. 5). Maximum content of Ni and Cu exceed the background as follows: cowberry - 33 and 9, bilberry - 9 and 2, E.hermaphroditum - 14 and 14, cloudberry - 22 and 6 times, respectively. The contamination of berries strictly (correlation r = 0.99-1.00) depend on metal content in soils (Fig 3. and Fig. 6). Basing on these results, I accept the hypothesis that heavy metal accumulation by berries is mainly caused by extraction of dissolved metals from contaminated soils. Sedimentation of dust particles on a leaf plate, the following ionization of metal and absorbtion of ions through the stomata (Elpatjevsky e.a., 1985; Karaban e.a., 1985), as well as an irrigation of leaves by rains or thawing snow, containing heavy metals, are also possible. But direct absorption of metals by berries seems to be impossible, because berries are protected from external impact much better than leaves.
According to standards of Health Protection Ministry, maximum permissible metal concentrations in berries are 0.5 mg/kg w.w. of nickel (Anonymous, 1982) and 5 mg/kg w.w. of copper (Anonymous, 1986). The nickel content in all species at all sampling plots on the territory exceeding 2000 km2 (Fig. 7) was higher than sanitary standard. Only 53-80 km from the smelter, the concentration of nickel in cowberry was less as compared to the permissible level. Although the absolute values of copper accumulation were close to ones of nickel, 10 times lover sanitary standard of copper in most samples was not exceeded.

Conclusions

The berries of V. vitis-idaea, V. myrtillus, R. chamaemorus, E. hermaphroditwn on the area >2000 km2, with the town of Monchegorsk in the centre and along the belt 20-30 km wide and 70-80 km long stretched to north and south from "Severonikel" smelter complex, contain nickel and copper tens of times more than sanitary standards and are unsuitable for food. Content of metals in berries and soils strongly correlate with each other; contamination decreased hyperbolically when moving from the smelter.

Acknowledgements

The authors gratefully acknowledge to A. Koshurnickov for great help in mathematical treatment of results.

References

Anonymous. 1982. Provisional hygienic norms of contents of several chemical elements in basic food products 2450-81. Moscow. 11 p. (in Russian)

Anonymous. 1986. Maximum permissible concentrations of heavy metals and arsenic in the food. Sanitary Rules and Norms 142-123-4089-86. Moscow. 12 p. (in Russian)

Anonymous. 1988. Methods of colorimetric determination of nickel and copper in solutions, used in "Severonikel" smelter complex (unpublished manuscript). Monchegorsk. 15 p. (in Russian)

Arinushkina, E.V. 1970. Handbook on Soil Chemical Analysis. Vyshaya Shkola, Moscow. 487 p. (in Russian)

Barkan, V.S., Pankratova, R.P. & Silina, A.B. 1990. The accumulation of nickel and copper by forest berries and mushrooms in surroundings of "Severonikel" smelters (Monchegorsk, Kola Peninsula). Rastitelnye resursy (Plant resources) 26 (4):498-509. (in Russian)

Belov, N.P. & Baranovskaya, A.B. 1969. The soils of Murmansk region. Nauka, Leningrad. 148 p. (in Russian)

Elpatjevsky, P.V., Arjanova, V.S. & Vlasov, A.V. 1985. Interaction of plants with air flow of metalliferous aerosols. In: Krivolutski, D.A. (Ed.) Migration of pollutants in soils and contiguous mediums. Nauka, Leningrad. P. 97-100. (in Russian)

Karaban, R.T., Nazarov, I.M., Rudneva, LA. & Sisigina, T.N. 1985. On the accumulation of nickel in soil and forest plants grown around smelters of the non-ferrous metallurgy. In: Krivolutski, O. (Ed.) Migration of pollutants in soils and contiguous mediums. Nauka, Leningrad. P. 109-117. (in Russian)

Leontyev, N.L. 1966. Technique of statistical calculations. Nauka, Moscow. 250 p. (in Russian)

Sokolov, A.V. 1975. Agrochemical methods of soil research. Nauka, Moscow. 656 p. (in Russian)

Svalov, N.N. 1977. The variation statistics. Lesnaya promyshlennost, Moscow. 177 p. (in Russian)

Yakovlev, B.A. 1961. Climate of Murmansk region. Murmansk Regional Publ. House, Murmansk. 199 p. (in Russian)