The Impact of Mining Production Upon the Ecosystem and the Health of Population1

THE IMPACT OF MINING PRODUCTION UPON THE ECOSYSTEM AND THE HEALTH OF POPULATION1

Armen K. Saghatelyan2, Sergey G. Arevshatyan3, Lilit V. Sahakyan4

Abstract: The research covers the territories of one of Armenia’s largest mining centers – the city of Kajaran and adjacent tailing repositories. Performed were ecological and toxicological assessment of heavy metal pollution of system water-soil-farming produce, and a research on revealing risk groups in the populace under condition of pollution with heavy metals.

The outcome indicates evidence for heavy metal pollution of the soils of the city and the re-cultivated tailing repositories. The analysis of mean heavy metal contents for Kajaran’s soils indicates that molybdenum dominates the series of elements: Mo(29.8)>Cu(5.1)-Pb(2.2)-Co(1.7)-Zn(1.4)-Ni(1)-Cr(0.8) (the index indicates excess vs. the background). Elevated concentrations of highly toxic elements (Hg, As, Cd) are established for the tailing repositories soils and materials.

As established, agricultural crops and fodder grasses accumulate a wide set of heavy metals, molybdenum being dominant. Peak concentrations of all the elements including toxic mercury are established for dill. Presence of heavy metals in fodder grasses implied a probability of their transfer to dairy produce. So analyzed was the milk of cows that graze allover the study site. For the milk, Pb, Hg, As excess vs. MAC is established.

To assess heavy metal effect on separate groups of the population, a so-called “indicator groups” are studied. By a set of objective reasons, children form the most sensitive group in the populace and serve as “indicators” in eco-geochemical studies. The research was performed through sampling children’s hair as one of the most representative bio- substrate in respect to heavy metal accumulation in organisms. The results show evidence that for the hair of 75 and 95% of children living in Kajaran As, and Pb, Ni contents are excessive, respectively, vs. biologically accepted levels. Cd and Cu contents in the hair of 95% children reach the lowest limit of biologically accepted levels. Hg was identified in the hair of 17% of children.

Key words: heavy metals, urban geochemistry, risk groups, children, agricultural crops and fodder grasses.

Introduction

To complexly investigate territories experiencing the impact of mining enterprises, the application of versatile methodic approaches including both the assessment of the state of basic ecosystem components

1Paper was presented at Mining and the Environment IV Conference, Sudbury, Ontario, Canada, October 19-27, 2007. 2 Director, Doctor of geol-mineral. sciences, The Center for Ecological-Noosphere Studies of National Academy of Sciences, Yerevan, Abovyan 68 Str., 0025, Armenia. 3 Senior researcher, PhD in geology, The Center for Ecological-Noosphere Studies of National Academy of Sciences, Yerevan, Abovyan 68 Str., 0025, Armenia. 4 Researcher, PhD student in geoecology, The Center for Ecological-Noosphere Studies of National Academy of Sciences, Yerevan, Abovyan 68 Str., 0025, Armenia. [email protected] ,Tel: (+374-10)56 93 31, Fax: (374-10) 58 02 54 (soil cover, surface waters, farm produce, etc.) and combined analysis of data obtained, are required. All this allows getting a comprehensive picture of ecological state of urban sites from positions of sanitary- hygienic, eco-toxicological, functional, and sustainable development of the territory.

In Armenia, it is the northern and southern portions of the republic, which are attributed to mining centers. Of particular interest is South Armenia where a whole set of mining enterprises is focused. There, the cities of Kapan, Kajaran, Meghri, Agarak etc. are located.

This research covers the areas of both Kajaran and 3 tailing repositories: Darazami, Pkhrut, Voghchi.

A brief description of the territory of the city of Kajaran

The city of Kajaran (Fig. 1) is one of Armenia's largest mining centers. On its territory the Zangezur mining and dressing group of plants is located focused on the obtaining of copper-molybdenum concentrate. The city is situated in River Voghchi gorge. Mean annual amount of precipitation is 600mm. The relief is sharply cut. For geological composition of the region tertiary volcanogenic, intrusive rocks (porphyrites, porphire granites, and monzonites) are common.

A major portion of the territory (up to 80%) is covered by layers of soil and deluvium (1-5m). Up to 1800m a.s.l., soil cover is mainly represented by brown soil; at 1800-2400m a.s.l - by chestnut soils. Northern slopes are covered by mountain-forest gray skeletal soil. Southern slopes are covered by mountain-xerophile vegetation, northern - by Quercus macranthera, Carpinus betulus L. shrub shoots, and so on.

The territory of Kajaran lies in the area of sulfide copper-molybdenum deposit and is a natural bio- geochemical province described for the first time by D. P. Malyuga [1] and V. V. Kovalskiy[2].

a) b)

Figure 1: Overview map of Armenia (a) and satellite image of the city of Kajaran and adjacent tailing repositories (b).

Tailing repositories of Kajaran

During Soviet era, the tailing repositories (Fig. 1) of the Zangezur group of plants were covered by re- cultivation soil layer. However, re-cultivation actions are not so efficient, when recovering soil and vegetation cover, and often can cause long-term ecological damage. Storing mining production-induced waste contributes to origination of new secondary pollution sources. For recent decades, the surface of the tailing repositories got eroded due to wind and water erosion. This results in active transportation of heavy metals contained in the tailing repository materials and thus intensively polluting the ecosystem's components (soils, waters, plants).

Materials and methods

Soil samples were collected from the city's territory following a topographic plan (1:5000) applying GPS. On “potentially clean” sites the sampling network got rarefied. The total amount of sampling points (soils, crops) and samples (soils, crops) was 66 and 140, respectively.

The soil, water, vegetation samples were collected and processed through methods developed in IMGRE and the V. V. Dokuchaev Soil Institute [3, 4].

The work frame included bioindication studies, too. The materials for eco-toxicological studies were vegetable species and herbs (on tailing repository sites and within the city's territory). Milk samples were taken with regard for the pasture localities. Children's hair was sampled in the presence of parents and a pediatrist. Wholly, hair samples were taken from 12 children. Heavy metal contents were determined by the methods of quantity spectral emission (DFS-13, soils) and atomic-absorption analyses (soil, water, hair, plants, milk) (Perkin Elmer Aanalyst 800).

Accumulation level of chemical elements in separate environments was determined through collation of actual concentrations with data on background plots and Maximum Acceptable Concentrations (MAC) [5-9]. To calculate background concentrations, samples were collected from sites remote from the city.

For cartographic reflection of sampling points and results of further material processing, digital 4-layer maps of the territory were produced (1:5000).

Ecological and geochemical mapping of the territory was performed based on the compiled computer database of chemical element contents in soils and plants applying the licensed program package ArcView 3.2a. While collating mono-element schematic maps, a 3-fold (in some cases 10-fold) grade scale was used.

Results and discussion

Pollution of soils of Kajaran

Soil pollution levels were assessed as a result of collation of established contents with background concentrations. The analysis data indicated domination of Mo, which background concentrations were 51 times excessive vs. lithosphere clarks and more than 10 times excessive vs. MAC (Fig. 2). This is typical of bio-geochemical province rich in molybdenum. Vs. MAC excessive contents were established for Mo (10.2), Ni (8.2), Co (2.6), Cu (1.7 times).

mg/kg 300 MAC Background 250

200

150

100

0 Mo Cu Pb Zn Ni Cr Co V

Figure 2: The background and MAC concentrations of heavy metals in Kajaran's soils (mg/kg).

The analysis of mean contents of heavy metals in Kajaran's soils indicated that in the series of element Mo was dominant: Mo(29.8)>Cu(5.1)-Pb(2.2)-Co(1.7)-Zn(1.4)-Ni(1)-Cr(0.8) (the index indicates excess vs. the background). Ecological risk is seen in elements with high contents vs. MAC. From positions of sanitary-hygienic characteristic of soils, considered were excessive contents of elements vs. MAC, this however being problematic to such bio-geochemical provinces as Kajaran. For spatial analysis of element concentration distribution on the city's territory, specialized mono-element geochemical schematic maps were produced. This presentation includes only the maps of Mo and Cu as dominating pollutants.

Molybdenum (Fig 3)

On the city's territory the fields for 3 concentration levels are contoured out. A field with peak values (>0.5%, a 100-time and more excess vs. the background) surrounds the group of plants and spatially stretches out to collieries. The soils of the basic part of the city are attributed to the 2nd level of Mo concentrations 0.051-0.51% (10-100 times). The whole west suburb of the city is attributed to a near- background level of concentrations (0.0051-0.051%-1-10 times). Spatial distribution of elevated concentrations of Mo is clearly associated with the group of plants and the colliery.

The contents of Мо in % <0.0051 0.0051- 0.051 0.051- 0.51 >0.51

Figure 3: A schematic geochemical map of the contents of Molybdenum in Kajaran's soils. Copper (Fig. 4)

On the city's territory, fields for 3 concentration levels are contoured out. Spatially, a field with peak values (>0.153%, over 9-fold excess vs. the background) lies near the works chimney and is more developed westward of the group of plants (beyond the limits of the city). On the city's territory 2 basic fields are identified: near-background (0.017-0.051%, 1-3 times) and those of weak pollution (0.051- 0.153%, 3-9 times).

The contents of Cu in % 0.017- 0.051 0.051- 0.153 > 0.153

Figure 4: A schematic geochemical map of the contents of Copper in Kajaran's soils

Pollution of plants in Kajaran

For eco-toxicological assessment of agricultural crops grown on Kajaran's territory we carried out pilot studies on heavy metal accumulation in basic vegetable species grown on agricultural sites within the bounds of the city. The obtained outcomes indicated that but for Zn the contents of practically all the metals were excessive vs. MAC. By the sum of heavy metal concentration excess vs. MAC the crops made up the following averaged accumulation series:

Dill Cr-Mo-Ni>Cu-Pb>Zn (summary intensity 92.6); Beans Mo>Cr-Ni-Cu-Pb>Zn (summary intensity 47.6); Potatoes Mo>Cr-Ni-Cu-Pb>Zn (summary intensity 42.5) Gooseberries Mo-Cr-Ni-Cu-Pb>Zn (summary intensity 22); Carrot Mo,Cr-Cu,Pb,Ni>Zn (summary intensity 12.3).

As seen, the series are identical for all the crops except dill, and it is Mo - a biophile element, which greatly contributes to the intensity of summary accumulation of heavy metals. The lowest pollution level was established for gooseberries and carrot.

High contents of Mo (Fig. 5) are common to the whole of Kajaran's ecosystem, whereas eco-toxicological state of the studied vegetable crops grown in the city may preliminary be attributed to middle level of pollution.

Mo Cu

30 70 25

60 r r tte tte a

a 50 20 m m y r y

r 40 d

d 15 f o f

o 30 g k g / 10 k g / 20 g m

m MAC;5.0 10 5 MAC;2.0 0 0 K9-B K12-A K30-B K12-B K15-A K30-A K12-C2 K9-A K9-B K12-A K30-B K12-B K15-A K30-A K12-C2 K9-A K12-D

Potatoes Beans Carrot Dill Pot atoes Beans Carrot Dill

10 Ni 1,8 Pb 9 1,6 8 r r 1,4 e e t 7 t t t 1,2 ma 6 ma y r y r

d 1

5 d f o f 0,8 o g 4 k g / k 3 / 0,6 mg MAC,0.5 2 mg 0,4 1 0,2 0 MAC;0.5 0 K9-B K12-A K30-B K12-B K15-A K30-A K12-C2 K9-A K12-D K9-B K12-A K30-B K12-B K15-A K30-A K12-C2 K9-A K12-D Potatoes Beans Carrot Dill Potatoes Beans Carro t Dill

Figure 5: The contents of heavy metals in vegetables grown on Kajaran's territory.

However for credible eco-toxicological assessment, studied should be the contents of toxic elements. Additionally, we studied accumulation of elements of 1st grade of hazard (Hg, As, Cd) in crops grown in home gardens on the right bank of River Voghchi, where high concentrations of those elements were established for waters flowing out from the colliery and Darazami tailing repository.

The obtained results indicated excessive concentrations of Hg only (Fig. 6). Especially high concentration was common for dill 0.8-1mg/kg of dry matter (a 51.5 time excess vs. MAC).

Cd Hg

0,04 1,2

r 1,03 e t 0,86

er MA C; 0, 03 0,03

mat 0,8

y 0,59 matt

y 0,02

dr 0,4 dr of 0,4 0,01 g k g of k / g 0 mg/ 0 MAC; 0,02 m K30B K12-C2 K9-A K12-D K30B K12-C2 K9-A K12-D

Potato Carrot Dill Potato Carrot Dill

Figure 6: The contents of heavy metals in vegetables grown on Kajaran's territory.

Ecological assessment of tailing repositories

It should be noted that the whole set of heavy metal found in the city's soils, is fixed in the soils of the 3 tailing repositories. For soils and ground of tailing repositories soils high indices for Mo, Cu, Ni, Co, V are common. While performing the research, a new problem emerged related to the study objects: additional analyses of contents of elements of 1st grade of hazard (Hg, As, Cd) on re-cultivation soil and ground layer indicated high concentrations of mercury, arsenic and cadmium. Figure 7 shows the contents of elements of the 1st grade of hazard in the soils and grounds of the tailing repositories.

mg/kg 50,00

40,00

30,00

20,00

10,00

0,00 Pkhrut Darazami Voghchi MAC Hg 4,80 3,46 3,72 2,10 As 48,03 14,77 18,30 2,00 Cd 0,12 0,07 0,05

Figure 7: The contents of elements of the 1st grade of hazard in the soils and grounds of the tailing repositories.

Crops

These outcomes are valuable from ecological viewpoint because both the citizens of Kajaran and peasants from adjacent villages use the study sites mostly for agricultural purposes (grazing cows, cultivation). So, we investigated farm produce adding vegetable and melon-field species grown in the area of the 3 tailing repositories.

The obtained research outcomes indicated that for all the studied species concentrations of heavy metals except Zn were excessive vs. MAC. Peak pollution was established for green vegetative organs of vegetables and particularly dill, bean, and green portion of onion. Such regularity is true to all the studied tailing repositories. Especially harmful turned out to be potato, in which high contents of mercury (a 31.5 time excess vs. MAC) were established (Fig. 8). Such a situation is alarming indeed.

Hg r

e 0,7

tt 0,63 0,6 ma

y 0,5 0,4 0,37 dr f 0,3

g o 0,2 0,16 k 0,1 mg/ 0 MAC; 0,02 K-10 K-11 K-70 K-1

Darazami Darazami Voghchi Pkhrut

Bean Potatoes

Figure 8: The contents of Hg in vegetables grown on tailing repository sites

Fodder grasses

Investigations of fodder grasses are conditioned by the fact that the tailing repository sites and mostly Voghchi are used as pastures, too. In the grasses from Darazami and Voghchi tailing repositories high concentrations of Hg are established (Fig. 9). In grass stuffs and separate grass species from Voghchi and Pkhrut tailing repository high contents of Mo, Cu, Ni, Cr are established, too.

MAC; 0,3

Cd Hypericum; Voghchi Trifolium; Darazami

MAC; 0,5

As Hypericum; Voghchi Trifolium; Darazami

MAC; 0,05 Hypericum; Voghchi; Hg 0,48 Trifolium; Darazami; 1,44 mg/kg 0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 of dry matter

Figure 9: The contents of toxic elements in grasses on the tailing repository sites

Fresh milk

Availability of heavy metals including those highly toxic (Hg) implies that fodder grasses may serve as a source, through which mercury and other heavy metals enter the human organism via food chain. That is why our research covered the contents of heavy metals in fresh milk as well.

Of all the studied elements, substantial excess of maximum acceptable concentrations was established for lead, mercury, and arsenic. Lead was detected only in the milk of cows from Araler district of the city of Kajaran, mercury and arsenic in the milk of cows grazing on the Voghchi and Pkhrut tailing repository sites (Fig. 10).

mg/l mg/l Pb 0,012 Hg 0,25 0,01 0,2 0,008 0,15 0,006

0,004 0,1

0,002 0,05

0 0 1 2 3 4 5 6 7 9 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 29 30 31 32 33 34 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 29 30 31 32 33 34 Kajaran, Arailer region, Lernadzor vil., pasture on Pkhrut Lernadzor vil., Kajaran, Arailer region, pasture on Lernadzor vil., pasture on Pkhrut and Lernadzor vil., pasture on pasture on Darazami tailing and Vokhchi tailing repository pasture on Pkhrut Darazami tailing repository site Vokhchi tailing repository sites Pkhrut tailing repository and adjacent sites repository site sites tailing repository and mg/l As 0,09 0,08 0,07 0,06 0,05 0,04 0,03 0,02 0,01 0 1 2 3 4 5 6 7 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 29 30 31 32 33 34 Kajaran, Arailer region, pasture Lernadzor vil., pasture on Pkhrut and Lernadzor vil., pasture on Darazami tailing repository Vokhchi tailing repository sites on Pkhrut tailing site repository and

Figure 10: The contents of heavy metals in fresh milk

Children

To assess the adverse environmental impact upon the populace such indicatory bio-substrates as blood, urine, hair, nails, and so on are studied. In ecological and geochemical studies, hair prevails over the noted bio-substrates due to a more representative character and simplicity of the sampling process [3, 10, 11].

Figure 11 shows that in most cases, concentrations of toxic elements (As, Cd, Pb, Cu, Ni) in the hair of children are excessive vs. the lowest and sometimes peak acceptable levels [12]. The obtained outcomes evidence, that for the hair of 75 and 95% of children living in Kajaran As and Pb, Ni contents are excessive, respectively, vs. biologically accepted levels. Cd and Cu contents in the hair of 95% children reach the lowest limit of biologically accepted levels. Hg was identified in the hair of 17% of children.

mg/kg As mg/kg Cu 1,8 35,00

1,6 30,00 1,4 25,00 1,2 1 20,00 0,8 15,00 0,6 10,00 0,4 5,00 0,2 0 0,00 1 4 5 6 12131617 2 3 1415 1 4 5 6 12 13 16 17 2 3 14 15 Girls Boys Girls Boys mg/kg Cd mg/kg Pb 0,5 7 0,45 6 0,4 0,35 5 0,3 4 0,25 0,2 3 0,15 2 0,1 1 0,05 0 0 145612131617231415 1 4 5 6 12 13 16 17 2 3 14 15 Girls Boys Girls Boys mg/kg Ni 7 BAL (Biological Acceptable Level [12]) 6 5 MIN 4 3 MAX 2 1 0 1 4 5 6 2 3 12 13 16 17 14 15 Girls Boys

Figure 11: Heavy metal accumulation in children's hair, Kajaran

Conclusions

1. The obtained outcomes of the performed geochemical survey of the soil cover of Kajaran and its vicinities allows concluding that: - in pollution of the city Mo and partially Cu are dominant; however no intense pollution of the whole - territory of Kajaran is observed; - fields with peak levels of heavy metal concentrations are focused on the territories of the group of - plants, colliery and behind residential part of the city; - elevated concentrations of Mo in Kajaran's soils are common to biogeochemical provinces and - should not be regarded as an alarming ecological situation; - pollution of the city’s soils is attributed to low and partially middle level.

2. For the tailing repository materials established were high concentrations of high toxic elements (Hg, As, Cd).

3. Eco-toxicological studies of agricultural crops and fodder grasses grown on the tailing repository sites indicated high concentrations a series of heavy metals, in particular mercury.

4. The research results for fresh milk indicated that Hg, As, and Pb contents were excessive vs. MAC.

5. Studying bio-substrates (hair of children) proves that both a long-term man-made environmental stress and presence of heavy metals in food bring to heavy metal accumulation in the organism of children.

Acknowledgments

This research was performed between 2005 an 2006 in the Center for Ecological-Noosphere Studies of NAS RA by the order of the Municipality of Kajaran and under support of the OSCE Office in Yerevan.

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